Synthesis and Characterization of Mofs - : Patricia Vanessa Palma Da Silva

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Patricia Vanessa Palma da Silva
Bachelor of Science in Chemical and Biochemical Engineering
Synthesis and Characterization of MOFs –

Metal Organic Frameworks
Dissertation for obtaining the Master's Degree in

Chemical and Biochemical Engineering
Advisor: Ana Margarida Sousa Dias Martins,

Structural Chemistry Center, IST–UTL
Co-supervisor: Inês Alexandra Morgado do Nascimento

Matos, Catalysis, FCT – UNL
Jury:
President: Prof. Doctor Rui Manuel Freitas Oliveira
Argue: Prof. Doctor Isabel Maria de Figueiredo Ligeiro da Fonseca
November 2012
Synthesis and Characterization of MOFs – Metal Organic Frameworks

New University of Lisbon – Faculty of Science and Technology
Synthesis and Characterization of MOFs –

Metal Organic Frameworks
Copyright © Patrícia Vanessa Palma da Silva, from FCT/UNL and UNL.
The Faculty of Science and Technology and the Universidade Nova de Lisboa have the perpetual right
and without geographical limits, to file and publish this dissertation through copies
printed material reproduced on paper or digitally, or by any other means known or
that may be invented, and to disseminate it through scientific repositories and to admit its
copying and distribution for educational or research, non-commercial purposes, provided
that credit is given to the author and publisher.
ii

This dissertation had the
duration of 9 months
at the Instituto Superior Técnico,

Technical University of Lisbon,
no Chemistry Group
Organometallic and Catalysis
Homogeneous from the Chemistry Center
Structural, supervised by
Professor Ana Margarida Martins.
iii

I dedicate this work to my beloved
family, especially my parents
Francisco and Helena, to my beloved
João, and to my sister Andreia.
“The most beautiful experience
we can feel is the Mystery. he is the

source of all Art and Science”
Albert Einstein
iv

Thanks
I begin by thanking Professor Isabel Maria de Figueiredo da Fonseca, for having

forwarded to carry out this internship at IST, which had been my wish for a long time.
much. Without his eternal sympathy and attention to the students he tutors, it would not have been
forwarded to this great opportunity. My big thanks to Professor Ana Margarida Martins (my dear
Professor “Guigas”), for helping me and clarifying
promptly all doubts, for having guided me in this fantastic and complex world of
chemical synthesis, for having guided me throughout this process, which was to be in a new
“home”, and to work independently in a laboratory that has become, for me, very
Special. I thank Inês Matos for being present as my Co-Advisor, and for having
helped whenever I needed it. My dear Maria Augusta Antunes, who received me from
open arms in the laboratory, who guided me, who guided me, who helped me, who was
my confidant throughout this process. Without your patience, experimental work
would undoubtedly have been very different. To my labmates Clara, Claudia,
Patrícia, Sónia, Suresh and Li Dong for their company and smiles. Thank you
special to Luís Alves for his sympathy and precious help in the characterizations by X-Rays
crystal of the compounds, and to Vânia André and Auguste Fernandes for their help in the X-Ray
characterization of powders. To Doctor Teresa Nunes for her help in the
NMR characterization of Solids, and to Tiago for the kindness with which he always received me at the
IR Spectroscopy laboratory.
I thank all my dear family that I love and that gives me the strength I need to
face all obstacles. Especially to my dear sister Andreia, and to my dear
and beloved parents, Francisco and Helena, who made me the person I am today, for whom I
I feel enormous pride and affection, and to whom I owe everything I am and have.
To you João, for being my pillar, the person who has walked by my side for so many years,
bear with me all the good and bad moments, I thank you for your companionship,
friendship, patience, good mood and of course, your love.
To all my colleagues and college friends, who enriched my knowledge,
they filled my days with a good mood, they offered me their friendship. In particular,
a big thank you to my friends Raquel, Ana Lúcia Rodigues, Sónia, Ricardo, Mário,
Alexandra, Andrea, and Joana.
Finally, I want to thank all those who contributed in some way.

to make me grow as a person and professional that I am today.
in

we

Summary
The present Dissertation aimed at the synthesis and characterization of some types of
MOFs – Metal Organic Frameworks.
MOFs are porous hybrid solid compounds, derived from zeolites, which result from the reaction between
organic and inorganic species, which gives rise to a network (framework)
three-dimensional porous that contains both species, coordinated by strong bonds.
The main difference between zeolites and MOFs lies in their structure. both play
important catalytic activity, however, the three-dimensional porous structures of MOFs
enable important applications in the area of adsorption and storage of gases.
The inorganic species used in the present work were the metals of Cadmium, Zinc,
Cobalt, Chromium and Iron; while the organic species coordinated with them were
benzenic acid ligands with amines, e.g. pyrazolyl benzene.
Cadmium (II) and Zinc (II) compounds were synthesized with bipyridine ligands.
coordinates with 1,4 –Benzenedicarboxylic acids and 1,2,4,5 –Benzenetetracarboxylic acids; and
compounds of Cobalt (II), Chromium (II) and Iron (II), with the ligand 1,4 – Bis(4´-
Pyrazolyl)Benzeno e [NH2(CH3)2](COO)3.
The characterization of the compounds was carried out using several techniques, namely,
elemental analysis, nuclear magnetic resonance of liquids and solids, X-ray diffraction of
powders and single crystal, and Infrared spectroscopy.
vii

viii

Abstract
The aim of these experimental work was the synthesis and characterization of some types of
MOFs - Metal Organic Frameworks.
The MOFs are hybrids porous solid compounds, which result from the reaction between organic
and inorganic species, giving rise to a network (framework) where both species are linked by
strong covalent bonds.
The main difference between Zeolites and MOFs lies in its structure. Both play an important
catalytic activity, however, the three-dimensional porous structures of MOFs enables important
applications in the field of gas adsorption and storage.
The inorganic species used in this work were the metals cadmium, zinc, cobalt, chromium and
iron, coordinated with ligands such acids with amines benzene, and the benzene pyrazolyl.
The compounds synthesized were Cadmium (II) and Zinc (II) with bipyridine ligands coordinated
with 1,4-benzenedicarboxylic acids and 1,2,4,5 - benzenetetracarboxylic, and compounds of
Cobalt (II), Chromium (II) and Iron (II), with the ligand 1,4 - bis (4'-pyrazolyl) Benzene and
[NH2(CH3)2](COO)3.
The characterization of the compounds was carried out using various techniques, including,
elemental analysis, nuclear magnetic resonance in solution and in the solid state, X-Ray
diffraction of powders and single crystals, and infrared spectroscopy.
ix

x

Index
Thanks................................................. ................................................................ .......................... v

Summary ................................................ ................................................ ..................................... vii
Abstract .........................................................................................................................................ix
Index ................................................. ................................................................ .......................................... xi
Figure Index ..................................................... ................................................................ ......................xv

Table Index ..................................................... ................................................................ ...................... xvii
Index of Equations ..................................................... ................................................................ ....................xix
Symbology and Notations ..................................................... ................................................................ .............xxxi
CHAPTER 1 - Introduction……………………………………………………………………………….1
1. Introduction ............................................... ................................................................ ............................. two
1.1. A historical approach: Zeolites – Characteristics and Synthesis ................................... 2
1.2. Definition of MOFs – Metal Organic Frameworks................................................. ............... 3

1.3. Zeolites versus MOFs – Overview ........................................................... ............................ 4
1.4. MOFs – Synthesis, Approaches and Properties ................... 5

1.4.1. Synthesis ..................................................... ................................................................ ............... 5
1.4.1.1. The first problem – Predicting the structure of the network ................................... 6
1.4.1.2. Approaching the First Problem ..................................................... ...................... 8
i) Use of rigid ligands ................................................................... ................................... 8
ii) Exploration of the most used coordination models ................................................ 8
iii) Anion effect ..................................................... ................................................................ ...... 9
iv) ROP- “Ring opening polymerisation” relationships ................................................ ............. 9
1.4.1.3. The Second Problem – Interpenetration ............... 9
Use of bulky ligands ................................................... ................................... 10
i) ii) Concentration effect ..................................................... ................................................... 10

1.4.2. Properties ................................................. ................................................................ .... 11
1.4.2.1. Molecular Structure ..................................................... ................................................... 11
1.4.2.2. Structural Stability, Adsorption and Ion Exchange of Liquids and Vapors ........ 13
1.4.2.3. Chirality ..................................................... ................................................................ ... 14
1.4.2.4. Solubility and Ion Exchange ................................................... ................................. 14
1.4.2.5. Catalysis................................................. ................................................................ ......... 14
1.5. Ligands used ........................................................... ........................................................... ..... fifteen

1.5.1. Ligands of Bipyridines with Carboxylic Acids (Polycarboxylates) ................... 15
1.5.2. Ligands de Pyrazolyl(Benzeno) (H2BPB)............................................. ................. 16
1.6. Description................................................. ................................................................ ........... 17
1.6.1. IV spectroscopy.................................................... ............................................ 17
1.6.2. MRI................................................... ................................................ .................. 18
1.6.3. X ray............................................... ................................................................ ............... 19
xi

CHAPTER 2 – Cobalt (II), Iron (II) and Chromium (II) MOFs with the ligands 1,4 – Bis(4'- Pyrazolil)Benzene and
(CHOO)3[NH2(CH3)2]………… ………………………………………………….23
1. Introduction ............................................... ................................................................ .......................... 24 2.
Synthesis of Cadmium (II) and Zinc (II) MOFs ....... ................................................................ ............... 25
2.1. Materials................................................... ................................................................ ..................... 25
2.2. Experimental Method ..................................................... ................................................................ .. 28

2.2.1. Preparation of starting compounds M(bpy)(NO3)2.H2O (M = ZnII/ CdII)......... 28 Synthesis of Zinc
2.2.2. (II) and Cadmium (II) compounds.. ................................................ 28
2.2.3. Results and discussion............................................... ................................................. 30
2.2.3.1. Characterization of the starting compounds M(2,2´-bipy)(NO3)2.H2O (M = ZnII/

CdII)………………………………………………………… ……………………………………30
2.2.3.2. Elementary Analysis ..................................................... ................................................. 30
2.2.3.3. Infrared Spectroscopy ..................................................... ................. 30 Characterization of

2.2.4. MOFs (1), (2), (3) and (4).............. ................................................ 32
2.2.4.1. Solubility Tests ..................................................................... ..................................... 32
2.2.4.2. Elementary Analysis ..................................................... ................................................. 33
2.2.4.3. Infrared Spectroscopy ..................................................... ..................... 34 i) Compound (1) -

[ZnII(2,2'-bipy)(bdc)(H2O)]n... ................................................................ ... 34
ii) Compound (2) - ZnII(2,2´- bipy)(btec)1/2(H2O)]n...................... ............................ 35 iii) Composto (3)
- [CdII(2,2´- bipy)(bdc)( H2O)]n .............................................. ........ 36 iv) Composto (4) - [CdII(2,2´- bipy)
(btec) 1/2 (H2O)]n ............. ................................... 37 2.2.4.4. Solid-state NMR
spectroscopy .............................................. ....................... 38
2.2.4.5. X-Ray Diffraction of Powders of Compounds (1), (2), (3) and (4).............. 40 2.2.4.6. Single-Crystal
X-Ray Diffraction of Compound (1) ................................. 40 2.2.4.7 . X-ray Powder
Diffraction ............................................ ................................. 43
3. Conclusion of Results ................................................... ................................................................ ... 46
CHAPTER 3 – Cobalt (II), Iron (II) and Chromium (II) MOFs with the ligands 1,4 – Bis(4'- Pyrazolil)Benzene and
[NH2(CH3)2](COO)3………… ………………………………………………………………………………………49
1. Introduction ............................................... ................................................................ .......................... 50
2. Synthesis of Cobalt (II), Iron (II) and Chromium (II) MOFs with the ligand of 1,4 – Bis(4'-
pyrazolyl)benzene .............. ................................................................ ................................................................ ..... 51
2.1. Materials and Techniques ..................................................... ................................................................ ....... 51
2.2. Experimental Method.............................................. ........................................................... ..... 52

2.2.1. Preparation of Ligand 1,4 – Bis(4'- pyrazolyl)benzene (H2BPB) [13] ............. 52 i) Approach 1:
Solubility Tests ...... ................................................................ ............... 53
ii) Approach 2: Purification of the H2BPB Ligand.............................................. ............... 53 Synthesis of
2.2.2. compounds (5) [13], (6) and (7)................. .......................................... 54 Synthesis of Cobalt
2.2.3. MOFs ( II) and Iron (II) with the ligand [NH2(CH3)2](COO)3]
……………………………………………………………………… ………………..55
2.2.3.1. Preparation of the starting compound NaCHOO.2H2O................................. 55 2.2.3.2. Synthesis

of Compounds (8) [6] and (9) ..................................... .......................... 55
2.3. Results and discussion ............................................... ................................................ 55
xii

2.3.1. Characterization of the H2BPB ligand............................................................ ......................... 55

2.3.1.1. Elementary Analysis ..................................................... ................................................ 55
2.3.1.2. Liquid NMR Spectroscopy ..................... 56 Characterization of Cobalt Compound with

2.3.2. H2BPB ..................................... ................... 57 2.3.2.1. Single crystal X-ray diffraction for
compound (5) [CoII(BPB).3DMF]. 57
3. Conclusion of Results ................................................... ................................................................ ... 62
CHAPTER 4 - General Conclusions and Prospects for Future Work……………………………65
CHAPTER 5 - Bibliography……………………………………………………………………………..69
xiii

xiv

Index of Figures
Figure 1 - Principle of formation of polymeric structures [10] ..................................... ............... 7

Figure 2 - Examples of rigid ligands most used in the synthesis: Polycarboxylic aromatics,
bipyridines and polyazaheterocycles (imidazoles, triazoles, pyrimidines, pyrazines) [10]...................... 8
Figure 3 - Interpenetration of two layers of cavities in networks such as M(CN)2 (M = Cd,
Zn) ............................................................................................................................................... 10
Figure 4 - Topology of some coordination polymers [7]................................................ ............. 12
Figure 5 - Coordination modes of some dicarboxylate groups [7] ..................................... 16
Figura 6 - Ligand 1,4 - Bis(4' - pyrazolyl)Benzeno .................................. .................................... 17
Figure 7 - Electromagnetic Spectrum................................................... ........................................... 18
Figure 8 - Representation of the crystallographic plane (111).. ..................................... ................... 19
Figure 9 - Lei de Bragg ............................................ .................................................. .................. 20
Figure 10 - PerkinElmer PE 2400 Series II Elemental Analysis Apparatus ............................. 25
Figure 11 - Bruker Vertex 700 FTIR Spectrophotometer .......................................... ................... 25
Figure 12 - Rucker AMSL 300 P Spectrophotometer............................................... ......................... 26
Figure 13 - Bruker AXS-KAPPA APEX II Single-Crystal X-ray Diffraction ................................. 27
Figure 14 - Detail of the Bruker AXS-KAPPA APEX II single crystal X-ray diffractor,
used in the characterization of compounds. ................................................................ ............................. 27
Figure 15 - Bruker D8 ADVANCE powder X-ray diffractor ..................................... ............. 27
Figure 16 - Infrared spectrum for the starting compound ZnII(2,2'-bipy)(NO3)2.H2O. 31
Figure 17 - Infrared spectrum for the starting compound CdII(2,2'-bipy)(NO3)2.H2O 31
Figure 18 - IR spectrum referring to the first synthesis of compound (1). ................................ 34
Figure 19 - IR spectrum referring to the second synthesis of compound (1) ................................. 35
Figure 20 - IR spectrum referring to the first synthesis of compound (2).................................. 35
Figure 25 - NMR spectrum for compound (2) ....................................... ................................... 38
Figure 26 - NMR spectrum for compound (3) ...................................... ................................... 38
Figure 27 - NMR spectrum for compound (4) ....................................... ................................... 39
Figure 28 - Comparative solids NMR spectrum for compounds (2), (3) and (4)......... 39
Figure 29 - Electron microscopy photograph of the crystal obtained for compound (1) ........ 40
Figure 30 - Representative structure of the crystal obtained for compound (1)................................. 41
Figure 31 - Representative packed structure of the crystal obtained for compound (1).......... 41
Figure 32 - Diffractograms obtained for compound (1). ................................................ ........ 44
Figure 33 - Compound structure (1) ................................................... ..................................................... 47
Figure 34 - Rucker Avance II+ 300 Spectrophotometer............................................... ........................... 51
xv

Figure 35 - Formation of ligand H2BPB: a) Vilsmeier Complex, DMF, 70°C, 18h; B)
Hydrazine Hydrate, EtOH, reflux, 3h................................................. ................................................... 52
Figure 36 - Detail of the sealed ampoule, containing the solution of Co(NO3) 2.6H2O + H2BPB..... 54 Figure 37- 1H
NMR spectrum for the Ligand H2BPB ............. ................................................ 56 Figure 38 - 1H NMR spectrum for
the Ligand H2BPB ................................................... .................. 57 Figure 39 - Electron microscopy photograph of
the crystal obtained from [CoII(BPB).3DMF]....... 58 Figure 40 - Representative structure of the crystal obtained from
[CoII(BPB).3DMF]............................. 58 Figure 41 - Structure representative packaging of the crystal obtained from
[CoII(BPB).3DMF].......... 59
Figure 42 - Packaging structure of the compound (5). ................................................................ .... 63
xvi

Table Index
Table 1 - Amounts obtained and reaction yield for the compounds of Zn(2,2'-
bipy)(NO3)2.H2O e Cd(2,2´- bipy)(NO3)2.H2O .......................... .................................................. .. 28
Table 2- Amounts obtained from (1), (2), (3) and (4) ............................. ................................................ 29
Table 3 – Time for crystals to appear for each of the compounds. ................................. 29
Table 4 - Elemental Analysis Results obtained for ZnII(2,2'-bipy)(NO3)2.H2O and
CdII(2,2´-bipy)(NO3)2.H2O ................................... .................................................. ..................... 30
Table 5 - Solubility Tests carried out on compounds (1), (2), (3) and (4)........................ 32
Table 6 - Elementary Analysis carried out in the syntheses of compounds (1), (2), (3) and (4) .......... 33
Table 7 - Results obtained in the characterization by Single Crystal X-Ray for the compound
(1). The left column refers to the characterization of the compound in the first synthesis, and the
right column, to the compound of the second synthesis. .......................... 42
Table 8 - Results obtained in the X-ray powder diffraction, for the compound (3)................... 44
Table 9- Elemental Analysis performed on Ligand H2BPB, in the synthesis before and after the
purification ..................................................... ................................................................ ................................ 55
Table 10 - Data obtained in the resolution of the structure of [CoII(BPB).3DMF]............................. 59
xvii

xviii

Index of Equations
Equation 1 - a, b, c are the moduli of the mesh base vectors; ÿ, ÿ, ÿ are the angles
formed between and ,

and , ee respectively................................................ .................. twenty
Equation 2 – Determination of crystalline lattice parameters, with a = b= c = 1/ a, and ÿ = ÿ = ÿ

= p/ 2 .............................................. ................................................ ........................................... 20
xix

xx

Symbology and Notations
Sail Full name

MOF Metal Organic Framework
AlPOs Aluminophosphates
SAPOs Silico-Aluminofosfatos
GaLOs Galofosfatos
SBU Second Building Units

ROP Ring opening polymerisation
TG Thermogravimetric Analysis
MRI Nuclear Magnetic Resonance
bpi- 2,2’ – bipiridina (C10H8N2)
H2bdc 1,4-Benzenedicarboxylic Acid 1,2,4,5-
H4btec Bezenotetracarboxylic Acid

BUT Elementary Analysis
IV Infrared (Spectroscopy)
ASTM American Society of testing materials
BUT Brunauer-Emmet-Teller
CDII Nd2+ (Coordination 2)
ZnII Zn2+ (Coordination 2)
KBr Potassium Bromide
13C carbon 13
EtOH Ethanol
Zn(NO3)2.6H2O Zinc Nitrate Hexahydrate
Cd(NO3)2.4H2O Cadmium Nitrate Tetrahydrate
DMF Dimethylformamide
N(CH2CH3)3 Triethylamine
HNO3 Nitric acid
C4H10O Diethyl Ether
DMSO dimethyl sulfoxide
H2BPB 1,4-bis(4'-pyrazolyl)benzene
H2Ca Calcium Hydride
NaCOOH Sodium Format
Me2NH2Cl Dimethylamine Chloride
xxi

Chapter 1 - Introduction
CHAPTER 1
Introduction
1

1. Introduction
1.1. A historical approach: Zeolites – Characteristics and Synthesis
For a better understanding of the variants of the structural and synthetic characteristics of the
MOFs, a brief historical approach to the use of zeolites, their
characteristics, as well as the exemplification of the most common synthesis techniques.
Natural zeolites are usually found in volcanic or metamorphic rocks and the
its growth occurs over thousands of years, under specific geological conditions
(Low temperature, medium pH). The first studies were based on these minerals and
aimed at reproducing in the laboratory the appropriate conditions for training and
growth of crystals with identical structural characteristics.
The first works of synthesis used only as reagents, components
however, in the early 1960s, the range of reagents also began to include
organic compounds. Since then, a large number of new structures have been synthesized
zeolites, as well as new families of materials analogous to zeolites, including
found aluminophosphates (AlPOs), silica-aluminophosphates (SAPOs), gallophosphates
(GaPOs) and titanosilicates. These microporous materials have different composition
chemical and may also present different structures from those found in
aluminosilicates (Zeolites). More recently, in the early 1990s, materials
mesoporous, synthesized with the help of surfactants that present periodic structures with pores that can have diameters
up to about 200 ÿ.
The wide variety of structures and compositions found in the sieve class
molecular structures, which encompasses the family of zeolites and other similar materials, implies
necessarily a wide variety of synthesis procedures, most
optimized for a given structure and using certain experimental parameters.
Zeolites are usually prepared by hydrothermal synthesis, which involves heating
of an aqueous reaction mixture and under pressure. This synthesis consists of transforming
a mixture of silicon and aluminum compounds, alkaline cations or organic molecules and
water, in a microporous crystalline aluminosilicate, via a supersaturated alkaline solution.
A typical synthesis of a zeolite comprises the following steps:
1) The reagents, generally non-crystalline, containing the structural elements (Si and Al in the
case of zeolites) are mixed with a cation-supplying reagent, usually
in a basic medium (high pH). This mixture causes the formation of a gel by
dissolution of the starting reagents in monomeric and oligomeric species of
silicate and aluminum;
2

2) The reaction mixture, or gel, is generally heated to temperatures between 50°C and
300 º C, in a sealed autoclave. Thus, working pressure is self-generated pressure;
3) Reagents remain “amorphous” for some time (induction period),

even after increasing the temperature. During this period, the first
crystalline nuclei that, due to their small size, are not detected by diffraction
of X-rays. These nuclei are formed from oligomeric species
aluminosilicate (designated by Barrer et al. as SBU) specific precursors gives
zeolitic structure to be prepared;
4) After the induction period, the first zeolite crystals begin to be detected;
5) Gradually, all amorphous material gives rise to zeolite crystals, which are
subsequently recovered by filtration, washing and drying. [1]
1.2. Definition of MOFs – Metal Organic Frameworks
In a simple approach, MOFs are a recent class of porous hybrid solids, which
result from the reaction between organic and inorganic species linked together in order to give rise to
a three-dimensional network whose skeleton contains both species – organic and inorganic –
linked together by strong bonds. [two]
This definition, however, covers a wide variety of metals and organic molecules with
different characteristics, as these can be, from porous solids, to non-porous and even
crystalline.
In 2001, Theo Masen and Bonnie Marcus announced the emergence of this new class of solids.
porous hybrids. Since then, there have been numerous investigations in this area, especially in the
concerning the crystalline structures formed, as well as the porosity of the compounds.
In this way, a series of different structures were made known that led to some
authors and scientists to consider this new family of compounds as a (r)evolution, because
these new porous solids have great structural versatility.
Conceptually, there is no difference between classic porous solids and hybrids. In

In fact, the three-dimensional skeleton can be described in both cases as the association of SBU.
However, while inorganic SBUs contain only inorganic elements (tetrahedral species such as SiO4, PO4,
AsO4, SO4) associated with metallic cations that are
tetra, penta or hexa coordinates; in hybrid SBUs, the tetrahedral elements are
replaced by organic ligands. This factor introduces a contrast between the bonds of the
network: mostly organic for the organic parts, inocovalent for the inorganic parts.
In fact, with regard to porosity, organic ligands with multiple bonds are
preferable, in order to ensure more rigid topologies than those existing in solids
organics with open networks.
3

With the great development of this family, it was necessary to define a new
vocabulary. In the first open hybrid networks, the inorganic part contained either compounds
isolated polyhedral or small groups. For this reason, these solids were initially
instance, called coordination polymers. However, it was later
demonstrated that these hybrid solids could contain inorganic parts with great
dimensionality, allowing the formation of chains (1D), layers (2D), and even networks
inorganic (3D). Thus, to qualify this new family, the term MOFs – Metal Organic
Frameworks – was introduced by Yaghi and O'Keeffe. [3]
As will be shown later, the inorganic part and its dimensionality have
a decisive role in MOF topology and ownership.
1.3. Zeolites versus MOFs – Overview
The study of MOFs was developed through the study of Zeolites.
While the inorganic solids used in zeolites require the use of organic (amines, among others) and
inorganic compounds, in addition to the components of
compound skeleton and solvent, this situation becomes simpler for MOFs. Us
MOFs, the solvent itself acts as the main responsible in the formation of the skeleton
molecular. This feature represents a great advantage because the skeleton of the large
Most MOFs become a neutral element in the composite structure.
This factor becomes important as, in most zeolites, often the

structure of inorganic solids with a cationic skeleton, collapsed in the extraction of
model due to the strong electrostatic molecule–host interactions, which energetically
make an important contribution to latent energy.
In MOFs, solvents have weaker interactions with the network and thus make
more accessible the development of the structure at lower temperatures, as well as a
porosity more easily accessible by neighboring molecules. Furthermore, the existence of
organic and inorganic halves in the structure allow the coexistence of the hydrophilic and
hydrophobic properties between the pores, which can play a crucial role in the properties of
compound adsorption.
Another interesting property of MOFs is related to the number of cations that can
be part of the network. When comparing with inorganic networks, based on just a few
cations (Silica and Aluminum for Zeolites - possibly “enriched” with some metals
transition), MOFs can accept almost all cations in the periodic table, at least
those that are di, tri, or tetravalent.
There is a wide variety of functional organic ligands that can be associated with
the inorganic parts. The functional groups of the ligand contain oxygen or oxygen donors.
4

Nitrogen. With regard to Oxygen donors, these can be, for the most part, mono or
polycarboxylates, mono or polyphosphonates and, rarely, sulfonates. all of them even
combined, can provide different possibilities of binding with inorganic ions.
Nitrogen derivatives (cyanides, pyridines, imidazoles, among others) are fixed directly in the
cation. Furthermore, the carbon sub-lattice (rigid or not) of the ligand itself can be
functionalized, depending on the expected applications (halogen groups, amine groups,
between others). This means that the possibilities of combinations between this new family of
porous hybrid solids are almost infinite, and from this factor comes a disadvantage: The almost
infinite number of potential products, as it becomes very difficult to select which ones are
potentially valid for eventual applications.
These properties will, however, be further explored later.
1.4. MOFs - Synthesis, Approaches and Properties
1.4.1. Synthesis
The parameters that play a decisive role in the synthesis of MOFs are the pH
(mostly acidic), the Concentration (which varies over a wide range), and the Temperature.
Temperature is one of the main synthesis parameters and, considering water as

solvent, it is divided into two distinct ranges: Above and below 100 ºC. This is related
with changing solvent properties above this limit: As soon as conditions
hydrothermal temperatures are reached, the dielectric properties of the solvent change, leading to a
weakening of interactions between molecules, and an increase in dissociations of
same. [4]
MOFs are generally synthesized at low temperatures (< 250°C).
The synthesis method generally requires mixing two solutions that contain the metal and the
organic component, either at room temperature or under hydro or solvothermal conditions
and with or without the addition of auxiliary molecules. [5]
MOFs have the ability to incorporate virtually all types of cations, be they
di, tri, or tetravalent, and a wide variety of metals in their steady state of
oxidation – alkali, alkaline – earth, transition metals, and rare elements.
As organic components, rigid molecules such as conjugated aromatic systems are preferable , rather
than flexible molecules, as these favor the
preparation of crystalline, porous and stable MOFs.
The choice of ligands is mainly based on their core and includes elements such as
polycarboxylic aromatic molecules, bipyridines, and polyazaheterocycles (imidazoles, triazoles,
tetrazols, pyrimidines, pyrazines) and their derivatives. [4] However, water is also a
5

widely used solvent. Synthesis often requires the addition of amines,

as they favor the reaction, without, however, participating in the formula of the final compound. [5]
In addition to this function, amines play an important role in the packaging of the structure,
thus promoting its stability.
Either neutral or charged molecules can be used in the synthesis, however, the
Cationic ligands are less common due to their poor coordination affinity with
metal ions.
The nature of the solvent, the ligand, and the presence of cations or other molecules in the synthesis,
can have a dramatic effect on the crystal structure of the obtained compound. So, a
specific metal-alloying combination can lead to a large number of different
structures (polymorphism), which depend on small changes in the aforementioned
synthesis parameters.
Regarding the chemical parameters of the synthesis, this is carried out in a diverse range of
concentrations and temperature.
1.4.1.1. The first problem – Predicting the structure of the network
For the formation of a coordination polymer, a reaction between a

binding potential with a metal ion that has more than one vacant or labile site,
as can be seen in Figure 1.
6

Figure 1 - Principle of formation of polymeric structures [6]
Currently, the most detailed way to obtain information about a structure is by

single crystal X-ray crystallography. In fact, without being aware of the structure
crystal, it becomes quite difficult to interpret the properties of compounds. So it makes
it is imperative to obtain unique crystals with the highest “quality” possible.
Amorphous solid phases and gels have not yet been studied in depth, despite being
equally promising at the chemical synthesis level. The use of amorphous products is to be avoided
when, for example, the metal-ion combination is highly labile, that is, when the formation
of bonds is quickly reversible so that the initial products (which can also be
mixtures) have the possibility of rearrangement and can provide thermodynamic stability to the ,
Ag2+ , final product. Among the most commonly used labile ions are Cu+ Cu2+ , Ag+ ,
Zn2+, Co2+ and Ni2+ and these have wide applications in the field of coordination polymers.
A potential problem concerning the use of these labile ions is that they do not impose
often a preferred geometry in compounds, as opposed to other metal ions.
This can lead to a poor prediction of the obtained network structure.
Another potential problem concerns the flexibility of the binding ligand. if one calling
has a large number of possible conformations, it is again difficult to predict the
network geometry. [6]
7

1.4.1.2. Approach to the First Problem
i) Use of rigid ligands
The freedom of orientation of ligands in the bonds with metal ions can be reduced
through the use of “skeletons” or rigid elements, as is the case of 4,4'-bipyridine.
In this case, although the rotation is carried out on the central connection C – C, this rotation does not affect
the mutual orientation of peers that are not linked. Examples of rigid structures of this
type, as well as ligands consisting of nitrogen, are exemplified in Figure 2.
Figure 2 - Examples of rigid ligands most used in the synthesis: Polycarboxylic

aromatics, bipyridines and polyazaheterocycles (imidazoles, triazoles, pyrimidines,
pyrazines). In the first row, from left to right, are, for example, 4,4'-bipyridine compounds;
Hexamethylenetetramine (3rd compound); and Tetra(4-
Cyanophenyl)methane (4th compost).[6]
ii) Exploration of the most used coordination models
Although the coordination of the metal ion is often flexible, it is possible to identify
recurrent structural models, either from existing polymeric structures or from models
discrete complexes much more numerous. An example of this type, found in several
coordination polymers is the dimetallic tetracarboxylate – M2(O2CR)4. There are a number of
8

di and tricarboxylate ligands that, in the reaction with Cu2+, generate networks based on this
structure.
When a structural unit has similarities between metal ions and ligands, it is
called SBU, as seen before. That is, ligands and ions work
as the primary binding units. [6]
iii) Anion effect
Anions can play a major role in determining the structure

polymeric. Apart from the obvious differences in volume and shape that will be accommodated in the structure
crystal, the different coordination skills and its ability to connect
metallic centers (often act as ligands themselves) may play a role
very important role. [6]
iv) ROP- “Ring opening polymerisation” relationships
ROP is a new development for coordination rings in which the big difference
relates to the dative covalent bonds of the compound, rather than the bonds
common covalents. The existence of an ROP relationship indicates that it occurs at the surface
of a growing polymeric crystal. Thus, open ring elements are retained in a
relatively insoluble polymeric material.
It would be interesting to see if the ROP concept leads to an increase in structure prediction and
control in coordination polymers, and whether it has an advantage over current techniques of
crystallization of the coordination polymer. If ROP does occur, there must be
an additional intermediate compound than what is observed in NMR spectroscopy. [6]
1.4.1.3. The second problem – Interpenetration
Once the possibility of forming coordination networks has been established,

three-dimensional, with some prediction in their connectivity, it appears that the use of
long ligands leads to the formation of structures with large open cavities,
much wider than in zeolites. However, as demonstrated by Robson and others
groups, what typically happens is that the second coordination polymer interpenetrates a
first (Figure 3). [6]
9

Figure 3 - Interpenetration of two layers of network cavities such as M(CN)2 (M

= Cd, Zn) [6]
Thus, there is the possibility of two types of approaches to the second problem exemplified.
i) Use of bulky ligands
The use of bulky ligands promotes a decrease in the tendency of interpenetration.

In this approach, the size of the cavities must be reduced, and the polymer chain that
will pass through these cavities, it becomes more voluminous. Taking into account that the
problem of interpenetration is controlled, and that resulted in a material with a cavity
of appreciable dimensions, the question of stability arises. The solvent molecules make
departs from any cavity that is large enough to receive them, and can still
contribute to the definition of the molecular structure. Thus, the molecular structure becomes
unstable in the loss of these molecules and may even collapse. This stability can only be
maximized if the formation of strong bonds between the ligand and the metal is ensured. [6]
ii) Effect of concentration
In the most significant examples of MOFs to date, Yaghi et al. were successful
in producing a series of compounds with square pore cavities with a diameter of 19.1 ÿ, and a
porous diameter of 28.6 ÿ. [6]
The calculated densities of these materials are so low as to be on the order of 0.21 g/cm3 , the
lowest value found in a crystalline material. These compounds consist of
rigid dicarboxylate ligands and octahedral SBU, linked in cubic networks. The control of
Interpenetration can be controlled by diluting it. [6]
10

1.4.2. properties
1.4.2.1. Molecular Structure
One of the most challenging fields of investigation of MOFs relates to the

development and synthesis of multifunctional compounds and materials, with structures and
properties that are as predictable as possible. The growing interest in this field has
originated, not only increasingly complex and diversified crystalline structures, as well as,
potential applications in the field of catalytic, optical, electronic, magnetic,
electronics, and adsorption.
Molecular coordination architectures consist of metal ions that function as

“nodes”, and organic ligands as “bridges” between them. These architectures can vary
from zero-dimensional arrays (0D) to three-dimensional networks (3D) with different
structural characteristics, which result from different types of connections:
coordination, hydrogen bonds, ÿ–ÿ rigid aromatic interactions, or Van bonds
der Walls. Although the type of connection plays an important role in the structure of the
compound, other elements such as the presence of counter-ions or solvent molecules
are also a strong influence on it. Thus, the ions or molecules do not
coordinates, are often used to control the crystallization processes and the
consequent architecture of the compounds.
Molecular architectures, which result in multidimensional networks, are generally

constructed using metallic ions that have various coordination geometries
(tetrahedral, trigonal bipyramidal, octahedral, among others), and that coordinate with ligands
multifunctional (linear or angular bidentate, planar or pyramidal tridentate, planar or
quadridentate tetrahedral).
The new approaches are based on supramolecular structures that contain in their
essentially static ÿ–ÿ bonds or hydrogen bonds, insofar as, in these cases,
there is greater control and foresight regarding structural and geometric diversity
(size, shape and symmetry), flexibility, and even the synthesis process. So, the architectures
supramolecular, based on coordination bonds and/or supramolecular interactions,
allow for greater prediction and control of solid-state multidirectional arrays.
In the mid-1970s, AF Wells focused on the generality of compound structures.

inorganic and crystalline structures in terms of their topology, reducing them to a series of
points of a certain geometry connected to a fixed number of other points. The final structures,
can be described as polyhedra or as infinite networks. Around 1990, R. Robson
developed and extrapolated the work done by Wells and turned it into what is
currently, the chemistry of organometallic and supramolecular coordination compounds. [7]
11

In 1998, Kitawaga suggested classifying porous hybrid networks into three categories, the
which he called "generations". The first concerns networks that are supported only by
neighboring molecules, and which irreversibly collapse upon removal. The second
generation concerns stable and robust porous networks, which exhibit permanent porosity and
that do not contain any neighboring molecules in their pores. Finally, the last category
refers to flexible networks whose structure undergoes irreversible changes, with stimuli
external. These stimuli can be temperature, pressure, light, electric field or
magnetic, or the presence of neighboring molecules. [7]
Figure 4 - Topology of some coordination polymers [8]
In class 1 D, the spaces between the chains are occupied by small molecules, and can
ion exchange occurs between them. As an example of this type of polymer chain, we have the
bipyridine ligands, studied in this dissertation. The presence of this ligand attenuates the
tendency of metal complexes to form carboxylate-metallic chains of
large dimensions, which have mononuclear metal ions that function as nodes.
This is because most metal ions have coordination numbers equal to or
less than 6. In this case, the polycarboxylates, also studied and subsequently
detailed in the present dissertation, are widely used in the union of architectures
supramolecular structures, due to their great diversity of coordination modes and their great
binding capacity (Figure 4).
In class 2 D there are two different types of situations: One, in which the way in which the
layers are arranged, depends largely on the nature of the neighboring molecules and the weak
12

interactions they have with the layers; and a second, in which the layers are
overlapping forming 1D structures, which close if no molecules are present.
neighbors, and open in the presence of some of them (Figure 4).
Class 3D has three types of situations. In the first one, stacked layers are considered,
in which the reversible phenomenon of shrinkage and expansion between the interlayers is
controlled by non-rigid connections that act as pillars between them. In the second case, the
phenomenon of shrinkage/expansion of the network makes it act like a sponge, or
that is, there may be a decrease in volume that is induced by the inclusion of neighboring molecules
in the same. Depending on the structure, this volume increases or decreases according to the
evacuation or inclusion of neighboring molecules in the polymeric network. In the third case, one is in the
presence of impenetrable networks, which are quite dense with the absence of neighboring molecules. The
introduction of these molecules makes the networks "slip" one in
in relation to the others (Figure 4).
1.4.2.2. Structural stability, adsorption and ion exchange of liquids and

vapors
Assuming that the interpenetration is controlled, and that the material has a cavity
appreciable, the question of stability arises. Solvent molecules are usually
included in any cavity large enough to accept them, and thus become part of the
structure. A frequent problem is that networks are not stable enough to lose
neighboring solvent molecules. There are already networks that provide evidence of stability in the event of
loss of neighboring solvent molecules, as well as the exchange of neighboring molecules for others,
without collapse of the structure.
The great kinetic stability of zeolites is due to the great energy required to break
the strong Si – O and Al – O bonds. In MOFs, the bond strengths are smaller, so it is
MOFs are expected to be more thermally unstable. This is usually the case, since
that typical decompositions occur at lower temperatures than in zeolites. THE
network stability can be maximized by promoting stronger links by linking –
metal.
Studies show that thermogravimetry is the technique indicated to determine the

decomposition temperature.
The adsorption of liquids and vapors has been widely used in research, both in
effective porosity of the networks, or in the application of compounds in the storage of gases.
The latter has become an expanding field in the application of MOFs and these have become
showed great promise in the storage of gases such as Hydrogen, Methane,
Carbon Dioxide, as well as in other applications in the field of “clean” energies. Due
the ability to almost be able to monitor the pore size of the nets, allows
13

researchers focus on the most promising factors, increasing either the volume
available adsorption capacity or network affinity for gas storage.
[9]
1.4.2.3. chirality
Chiral MOFs can be applied to enantioselective separations especially due to the
difficulties in preparing zeolites from pure enantiomeric networks. The fact that MOFs are
prepared in a “module” or “building blocks” form, means that chirality can
be introduced simply by choosing a chiral module, more convenient in ligands
organic. [6]
1.4.2.4. Solubility and Ion Exchange
Studies carried out in this area concluded that when the crystals formed were immersed in
2-
aqueous solutions of PF6 - , MoO4 - , BF4 - or SO4 , anion exchange took place. This is because, the
aqueous anion, which was in excess in the solution, was incorporated by the crystals and
consequently, the anionic crystals of the compounds were later released to
the solution.
This proves that the supernatant solution becomes decisive since the polymers of
coordination are usually obtained as crystals from the solution. So that X-ray analysis
of the crystalline structure is viable, it becomes essential that it has long chains and that
be highly insoluble. The stability of coordination polymers becomes a point
essential for the potential applications of MOFs in ion exchange and purification
water/solvent. [6]
1.4.2.5. Catalysis
Catalysis is one of the main and desirable characteristics desired in the applications of
MOFs, and becomes the great justification in what involves research related to these
materials. Currently, there are few references to catalytic activities of these compounds.
and those that exist, report unsatisfactory results, especially with regard to
selectivity of compounds. [6]
14

1.5. ligands used
1.5.1. Ligands of Bipyridines with Carboxylic Acids (Polycarboxylates)
Polycarboxylates have been widely used in the development of networks

supramolecular structures organized through coordination bonds,
hydrogen, and rigid ÿ–ÿ interactions. [10]
These are used in the formation of supramolecular structures due to their diverse
coordination modes, as well as its numerous applications as a structural ligand.
Benzenedicarboxylic acids are ideal ligands for the formation of polymers of

coordination and open network structures. An important aspect of these compounds is their
ability to form MOFs in the presence or absence of chelating aromatic amines, for
through weak supramolecular interactions with solvent molecules, which can
be coordinated or be present in the crystallization process. [11]
The compound chain [Zn(2,2'- bpy)(bdc)(H2O)] , for example, is a single helix,

in which each zinc ion is hexa–coordinated with the two nitrogen atoms of bipyridine, one
oxygen atom from water, two oxygen atoms from bdc, and another oxygen atom from
another bdc. Each bdc acts as a bridge between the two zinc ions. [12] The molecular structure
represented in Figure 5, mirrors the constitution of 1,2 – Benzenedicarboxylic acid,
previously designated bdc.
Figure 5 – Phthalic Acid (Trade Name) or 1,2 – Benzenedicarboxylic Acid (bdc).
The 2,2'-bipyridine dicarboxylates are a special class of multidentate ligands as they

simultaneously possess the bipyridine and carboxylate groups in their constitution.
The bdc ligand can also act as a bi-bisdentate (a), bis-monodentate (b),
mono-bidentado (c), ligando bis-bidentado (d), monodentado-bidentado (e), ou quelante/
bis-bidentate ligand (f), as shown in Figure 6.
15

Figure 6 - Coordination modes of some dicarboxylate groups [8]
Thus, there is great interest in the use of polycarboxylates as ligands in

construction of coordinating polymeric architectures, due to the fact that these polymers
have a great diversity of structural arrangements and various applications such as
porous.
1.5.2. Pyrazolyl(Benzeno) Ligands (H2BPB)
This class of ligands has been widely used in coordination chemistry and
organometallic, as it is a highly versatile ligand that can present
different properties, transposing them to the metallic center, by the simple
modification of the groups present in the different positions of the pyrazole ring.
In this particular case, the pyrazole group is linked in the fourth position to the aromatic group
(Figure 7), which confers a high degree of stability and rigidity to the compound,
crucial in the synthesis of compounds since, as already explained, the use of ligands
rigid is always preferred.
16

Figura 7 - Ligand 1,4 - Bis(4' - pyrazolyl)Benzeno [13]
The bound Cobalt, Iron and Copper compounds, linked by these polyazaheterocycles,
therefore present themselves as versatile and promising compounds, which is why they are being
currently studied by the industry for possible practical applications. In these systems, the
collinear geometry of the active centers, the rigidity of the one-dimensional network, its magnetic
response, the transition and spin properties and even its photomechanical effects, gives
wide range of possible applications.
However, one of the major related problems has to do with the characterization of the
compounds with this ligand, as they often produce few or no crystals and tend to behave very
differently with only minor variations.
in its synthesis. [14]
1.6. Description
1.6.1. IV Spectroscopy
IR spectroscopy was a technique widely used in the course of the work.

experimental, as it is a very useful tool for a first analysis of the constitution
of the compounds. This technique is based on the principle that chemical bonds have
specific frequencies, which vibrate at well-defined and quantified energy levels.
These vibration (or resonance) frequencies are determined by the shape of the molecule,
by its energy levels, and by the mass of the atoms that constitute it.
The resonance frequencies of a chemical bond are related, in a first

approximation, with the bond strength and mass of the atoms at each end. So,
each frequency of vibration can be associated with a type of chemical bond.
There are several ways to describe the possible movements of atoms in a molecule,
however, the formula that determines the changes in coordinates so that all
possible movements can be classified is 3N-5 for linear molecules, and 3N-6
for nonlinear molecules, and for each movement, the frequency of each vibration
of the atom is always the same. These changes in coordinates are called modes .
vibration normals. In vibrational spectroscopy, vibration frequencies are analyzed
17

of atoms in molecules. The variations in the energies of the vibrations are such that the radiation
commonly used is in the infrared region of the light spectrum. In this way, the
IR spectroscopy is also called vibrational spectroscopy.
From the observation of Figure 8, it can be seen that the vibration frequency of the IV is between
10-8 and 10-3 m -1
.
Figure 8 - Electromagnetic Spectrum [15]
Whereas, simple diatomic molecules have only one bond that can be
deform (stretch), molecules with a greater number of atoms have a greater number of
connections, and the vibrations can be coordinated. Thus, IV absorptions can be observed
to characteristic frequencies, related to the chemical groups that are in the constitution
of the molecule.
To obtain the IR spectrum of a sample, a beam of light is passed through it.

infrared, and the amount of energy absorbed by the sample is measured at each length
wave. From this information, the transmission or absorption spectrum is obtained, which
shows the IR wavelengths at which the sample absorbs radiation. This way,
one can then interpret the type of chemical bonds present.
This technique, however, only works for covalent bonds and the spectra become more
difficult to interpret the greater the number of active bonds in the IV of the molecule. To the
guarantee of good results in the reading, it is necessary that the molecule is also, free
of contaminations.
1.6.2. MRI
NMR spectroscopy is a characterization technique that explores the properties

magnetic properties of atomic nuclei, in order to determine the physical or chemical properties
of the atoms and molecules in which they are contained. The technique is based on the principle
that, in the presence of a magnetic field, NMR-active nuclei (such as 1H and 13C) absorb
electromagnetic radiation at a frequency characteristic of the isotope.
18

Magnetically active nuclei have spin and behave like small bars.
magnetic fields by orienting, in the absence of a magnetic field, their North/South poles
randomly in space.
When these are subjected to an NMR spectrometer magnetic field, the nuclei
align their magnetic poles in the same direction, and in the opposite direction to the field, in
equal probability. The irradiation of the nuclei with a radiofrequency of variable energy ÿE
= hÿ, leads to the absorption of this energy by nuclei with magnetic poles at the same
direction, reversing its magnetic spin to the opposite direction.
This phenomenon is called resonance, and it is the energy absorbed by the nuclei,
or emitted after its relaxation to the ground state, which gives rise to the NMR signal.
Chemical shift provides information about the electronic environment of a certain type
nucleus, while the integration reveals the number of protons responsible for a peak
of NMR. The multiplicity reveals information about the neighborhood of the protons under study.
1.6.3. X ray
X-ray analysis is one of the main tools for characterizing MOFs, because only
it allows to understand with exactitude, the structure of the complexes.
It is a technique that uses monochromatic radiation of wavelength ÿ. the sample is
consisting of a large number of crystals whose orientation is statistically random. At the
However, there are a number of crystallites that are in the Bragg position for a given
plane family hlk, that is, for an incidence ÿ such that nÿ = 2d (hkl) sin(ÿ) (Figure 9).
a
b
Figure 9 - Representation of the crystallographic plane (111). n – Integer number of

wavelengths; ÿ – Bragg angle; d – distance between the inter planes –
reticular; hkl – Miller indices, of the hkl plane family, are integers that correspond to the ratio
between the crystal lattice dimensions a, b, and c, and the intersection distances of the
respective crystallographic axes. [16]
Bragg's law defines the possible positions of diffracted rays. (Figure 10)
19

Figure 10 - Lei de Bragg [17]
For the set of families of crystallographic planes compatible with the resolution condition (sin(ÿ) < 1, that is, d (hkl) >
ÿ/2), the diffracted rays will form a set of
families of coaxial cones of revolution, whose beam is the incident beam.
The determination of the distances between the inter-reticular planes d (hkl), allows to obtain the
crystalline parameters of the network.
Thus, it is shown that (Equation 1):
Equation 1 - a, b, c are the moduli of the mesh base vectors; ÿ, ÿ, ÿ are the angles formed between and and
and
respectively.
,
and ,
For a cubic lattice with parameter a, where a = b= c = 1/ a, and ÿ = ÿ = ÿ = ÿ/ 2, we have that
(Equation 2):
Equation 2 – Determination of crystalline lattice parameters, with a = b= c = 1/ a, and ÿ = ÿ = ÿ

= ÿ/ 2
Another important piece of information relates to the I (Intensity) of the diffracted rays, which
depends on the atomic content (nature, number, and relative position of atoms) of the lattice
element, and also the dimensions of the crystals.
There is an ASTM file, with thousands of files corresponding to numerous substances. THE
from the X diffractogram of a given substance, its identification can be carried out
referring to this file. The procedure generally followed is as follows:
20

- Whether there is any prior knowledge about the chemical nature of the compounds to be
identify, a list of substances is used, placed in alphabetical order. The identification
is done when a card is found in which the list of d (hkl) and I (hkl) is identical to the
obtained in the compound to be identified;
- In the absence of information on the chemical composition, the three-line method is used.
From the experimental diffractogram obtained, the three most intense lines are selected. takes place
a list of substances classified according to the d of the three strongest lines. the scratch
more intense (d, I = 100), allows the selection of a first large group of substances,
passing successively to the less intense stripes, until reaching a small number
of possible substances. The final identification will be carried out by consulting the respective sheets
ASTM, with all values of d. [16]
21

22

Chapter 2 - Zinc (II) and Cadmium (II) MOFs, with bipyridine ligands coordinated with 1,4 -
Benzenedicarboxylic acids and 1,2,4,5 - Benzenetetracarboxylic acids
CHAPTER 2
Zinc (II) and Cadmium (II) MOFs, with bipyridine ligands coordinated
with the acids 1,4 –
Benzenedicarboxylic acid and 1,2,4,5 –
benzenetetracarboxylic acid
23

1. Introduction
This chapter describes the synthesis of MOFs with the compositions [Zn(2,2'- bpy)(bdc)(H2O)]n
(1), [Zn(2,2´- bpy)(btec)1/2(H2O)]n (2), [Cd(2,2´-bpy)(bdc)(H2O)]n (3) e [Cd(2,2´-
bpy)(btec)1/2(H2O)]n (4). [10]
The synthesis of the compounds was carried out twice, due to the fact that the first synthesis had
generated a small amount of product, insufficient for all the characterizations that were
intended to do. Thus, in the subsequent synthesis, it was decided to triple the amount of
reagents used, and produce a greater amount of compound. It becomes relevant to discriminate this fact,
since single crystals of compound (1) were generated in both
the syntheses, and both produced different results in terms of diffraction characterization
Single Crystal X-Ray.
The compounds were characterized by the methods of AE, Solubility Tests,

IR Spectroscopy, Solid NMR Spectroscopy and Crystal X-ray Diffraction
single and post.
The starting compounds [Zn(2,2'- bpy)(NO3)2.H2O] and [Cd(2,2'- bpy)(NO3)2.H2O], were
characterized by AE and IR Spectroscopy.
24

2.Synthesis of Cadmium (II) and Zinc (II) MOFs
2.1. materials
Reagents of AR purity, obtained from commercial sources (Sigma –

Aldrich, Merk), without further purification required.
In addition to the use of current material used in the laboratory, the characterizations of
compounds were performed using various analysis devices, which served as
support for obtaining the results obtained.
Elemental analyzes were obtained using a PerkinElmer PE 2400 Series II device (Figure 11),
with simultaneous determination of C, H, N, S and O, from samples weighing 0.03 to 10 mg.
It has a capacity of 120 samples. The average time required for analysis of compounds
is 10 minutes, and the detection percentages are from 0 to 100 % for each of the
referred elements.
Figure 11 - PerkinElmer PE 2400 Series II Elemental Analysis Apparatus
Infrared spectra were performed on a Bruker Vertex 700 FTIR spectrophotometer (Figure 12), with
an operating range between 4000 and 200 cm -1 . The samples were
mixed with KBr, and subjected to high pressure, in order to obtain
translucent enough to read.
Figure 12 - Bruker Vertex 700 FTIR Spectrophotometer
25

NMR analysis of solids was performed on a Bruker AMSL 300 P spectrophotometer (Figure 13) at 75.74
MHz. The CP/MAS 13C spectrum was obtained at a cross-polarized radio frequency, with a magic angle
of rotation (with proton decoupling during signal acquisition), at a contact time of 1 ms, 3 s relaxation delay
and 6 ÿs of
pulse duration (corresponding to the 90° magnetization angle).
Figure 13 - Rucker AMSL 300 P Spectrophotometer
Single crystal X-ray diffraction was performed on a Bruker AXS-KAPPA diffractometer
APEX II (Figure 14), using Mo-Kÿ radiation (ÿ = 0.71073 Å) of monochrome graphite. A data sphere was
collected at 150(2)K, with omega scans of 0.5° per frame. The parameters
of the cell were obtained using the Bruker SMART or Bruker APEX2 software, and were
refined using Bruker SAINT on all observed reflections. The corrections of
absorption were applied using SADABS [18]. The structural solution and the respective refinement were
carried out by direct methods, using the SIR2004 programs [19]
and SHELXS-97 [20], both including the WINGX-Version 1.80.05 software package. [21] The
non-hydrogenated atoms were anisotropically refined. All hydrogens were
inserted in idealized positions that allowed a refined reading of the neighboring carbon atom. In compound
(1), the N-H atoms of the dimethylammonium cation were not included due to
to the high disorder observed. The compound (1) obtained in the second synthesis crystallized in the group
monocyclic spacer Cc, with a possible disordered solvent molecule. All
Attempts to model this disordered molecule have not led to acceptable solutions. For this, the sequence
Squeeze/PLATON was applied. [22] Torsion angles and parameters
geometry were calculated using SHELX. [23] Illustrations of structures
Molecular tests were performed in the ORTEP3v2 software. [24]
26

Figure 14 - Bruker AXS-KAPPA APEX II Single Crystal X-ray Diffraction
Figure 15 - Detail of the Bruker AXS-KAPPA APEX II single crystal X-ray diffractor, used in the
characterization of the compounds.
X-ray powder diffraction was performed on a Brucker D8 ADVANCE powder diffractometer

(Figure 15), with copper radiation.
Figure 16 - Bruker D8 ADVANCE powder X-ray diffractor
The compounds M(bpy)(NO3)2.H2O (M = ZnII/ CdII) were prepared using the procedure
carried out by Sen et al. [25].
27

2.2. Experimental Method
2.2.1. Preparation of the starting compounds M(bpy)(NO3)2.H2O (M = ZnII/ CdII)
In a beaker, 1.10 g of 2,2'-bipyridine (7.08 mmol) was added to 30 mL of EtOH.

This operation was repeated.
Then, in a 250 mL round bottom flask, 2.08 g (7.02 mmol) of
Zn(NO3)2.6H2O to 120 mL of distilled water. The process was repeated for 2.16 g (7.02
mmol) de Cd(NO3)2.4H2O.
The bipyridine and ethanol solutions were added to the zinc and cadmium solutions.
separately, and they were stirred for half an hour at room temperature.
environment. They were evaporated on a rotary evaporator for 40 to
55 minutes, in a bath at approximately 60 °C, in order to remove the solvent from the mixture.
A white precipitate was obtained in both mixtures (Table 1), which was analyzed by
Elementary Analysis and IR Spectroscopy.
Table 1 - Amounts obtained and reaction yield for the compounds of Zn(2,2'-
bipy)(NO3)2.H2O e Cd(2,2´- bipy)(NO3)2.H2O
compounds Quantity obtained (g) Reaction yield (%)

[Zn(2,2´- bipy)(NO3)2.H2O] 2,87 69,9
[Cd(2,2´- bipy)(NO3)2.H2O] 2,87 70
2.2.2. Synthesis of Zinc (II) and Cadmium (II) Compounds
In a 100 mL round bottom flask, 0.166 g of H2bdc acid (1 mmol) was dissolved in 6
mL of DMF, 2 mL of EtOH, 0.14 mL of N(CH2CH3)3 and 15 drops of a solution of HNO3 at
65% previously prepared (pH 4 – 5) until the solution becomes clear. The process was repeated
to 0.127 g of H4btec acid (0.5 mmol).
The complexes were synthesized by adding 0.363 g of ZnII(2,2'-bipy)(NO3)2.H2O (1 mmol) and 0.410 g
of CdII(2,2'-bipy)(NO3)2. H2O (1 mmol) separately to H2bdc solutions
and H4btec prepared above.
The mixtures were heated to 120 °C, with stirring and at reflux for 8 hours, obtaining a
white precipitate in the four flasks. The mixtures were allowed to cool and then, in a
Buchner funnel, each mixture was vacuum filtered, yielding a white solid and
a yellowish filtrate.
The precipitates were washed with cold ethanol and with ethyl ether three times. The filtrate was
stored at 4°C.
The compounds were transferred to schlenks, the precipitates were dried in a vacuum line and
weighed himself. The compounds obtained acquired a white crystalline powder appearance. Finally,
28

a second synthesis was carried out as described, but the amount of reagents was tripled
used. The yields of the syntheses described in the literature under the same conditions as
exemplified synthesis, and those obtained in the present experimental work respectively,
are described in Table 2.
Table 2- Amounts obtained from (1), (2), (3) and (4)
Theoretical Yield Compound income obtained income obtained
(%) (%) (%)
Synthesis 1 synthesis 2
(1) 77 27 49
(2) 93 54,8 75,4
(3) 66 59 61,2
(4) 69 14,5 79,8
From the filtrate stored at 4 °C, the presence of crystals of compound (1) was observed after two
weeks, compound (2) after 10 days, compound (3) after one week, and compound
(4) after three weeks (Table 3). However, not all crystals formed will be viable.
for reading and interpreting the compounds, as will be discussed later in this
dissertation.
Table 3 – Time for crystals to appear for each of the compounds.
Composed Metal Turning on Time for
appearance of
crystals
(1) Zinc bpy(bdc) 2 weeks
(2) Zinc bpy(btec) 10 days
(3) Cadmium bpy(bdc) 1 week
(4) Cadmium bpy(btec) 3 weeks
The compounds were then characterized by elemental analysis, spectroscopy of
Infrared and X-ray diffraction.
29

2.2.3. Results and discussion
2.2.3.1. Characterization of the starting compounds M(2,2'-bipy)(NO3)2.H2O (M =
ZnII/CdII)
In a first approach, an elemental analysis and a spectroscopy of
Infrared to the synthesized starting compounds, in order to exclude the presence of
impurities that could affect subsequent syntheses.
Next, we proceeded to characterize the MOFs (1), (2), (3) and (4), starting with the
Solubility and AE Tests, including IR Spectroscopy, NMR and X-Ray Diffraction (powder and Single Crystal).
2.2.3.2. Elementary Analysis
In the elemental analysis of the starting compounds of ZnII(2,2'-bipy)(NO3)2.H2O and of CdII(2,2'-
bipy)(NO3)2.H2O, the following results were obtained (Table 4):
Table 4 - Elemental Analysis Results obtained for ZnII(2,2'- bipy)(NO3)2.H2O and CdII(2,2'-
bipy)(NO3)2.H2O
ZnII(2,2´-bipy)(NO3) 2.H2O CdII(2,2´-bipy)(NO3)2.H2O

N (%) C (%) H (%) N (%) C (%) H (%)
Value
15,41 33,03 2,77 13,64 29,25 2,45
Theoretical
BUT 14,63 31,36 2,36 13,6 30,3 2,29
By observing the results, it is verified that they are in accordance with the values
theoretical, that is, there are no major deviations from what is expected.
2.2.3.3. Infrared Spectroscopy
The IR spectra obtained for the starting compounds ZnII(2,2'-bipy)(NO3)2.H2O and of CdII(2,2'-bipy)(NO3)2.H2O
were as follows (Figures 17 – 18 ):
30

Figure 17 - Infrared spectrum for the starting compound ZnII(2,2'-

bipy)(NO3)2.H2O
Figure 18 - Infrared spectrum for the starting compound CdII(2,2'-

bipy)(NO3)2.H2O
The analysis by IR spectroscopy of the compounds becomes crucial as, once

that the ions of the ligands present in the compounds can coordinate in different ways
with metallic ions, it becomes an important tool in the diagnosis of nature
of the coordination of these compounds.
High intensity bands are observed in the spectra of both compounds at 3550 – 3200 cm-1 . These are
compatible with the presence of water molecules (OH), as well as
such as NH bonds.
The absorption band at 3040 – 3500 cm-1 , indicates the presence of hydrogen bonds. At the
In the case of the zinc complex, the bands that appear at 3105 – 3035 cm-1 and at 1567, 1600 and 765 cm-1
, are characteristics of 2.2' – bpy absorptions. In the case of the Cadmium complex, this presence
is verified in the low intensity peak at 3067 cm-1 , as well as in the peaks
medium and high intensity at 1593, 1602 and 770 cm-1 .
31

Thus, it appears that the composition of the starting compounds is in accordance with what was
intended to obtain.
2.2.4. Characterization of MOFs (1), (2), (3) and (4)
2.2.4.1. Solubility Tests
Solubility tests were carried out, not only to try to predict some
of the compounds, as well as to know how to proceed in future characterization methods. It is a qualitative
characterization method, but quite useful for a
first understanding of the behavior and nature of the compounds under study. These tests
were carried out by dissolving the compounds in various types of solvents
most commonly used commercials in the laboratory, from smallest to largest
boiling.
The compounds were found not to be soluble in any of the solvents (Table 5).
Table 5 - Solubility Tests carried out on compounds (1), (2), (3) and (4)
Dissolution of compounds (1),

Solvent Boiling Temperature (ºC)
(2), (3) and (4)
Ethanol 35 No
Acetone 56 No
Chloroform 61 No
Methanol 65 No
Ethanol 78 No
H2O 100 No
toluene 111 No
DMF 153 No
DMF (hot) 153 No
DMSO 189 No
32

The tests were carried out, in a first approach, not only to help predict the
constituent elements of the compounds, as well as to enable the subsequent analysis of the
composed by NMR. This is because, to carry out this type of analysis, it is necessary that the
compounds are soluble in deuterated or chlorinated solvents.
Given the visible difficulty in dissolving the compounds in the most common solvents, the process
was repeated for a wide range of them, and none of them were found to be soluble.
in any of the most commonly used commercial solvents in the laboratory.
Thus, it became necessary to resort to NMR analysis of solid compounds. This review
does not require the compounds to be soluble in any deuterated or chlorinated solvents. THE
analysis was carried out on only three of the compounds, given the fact that the apparatus had failed
during the period in which the dissertation took place.
Although this type of Test has only a qualitative character, some of the
obstacles that would come later in the analysis of the compounds. Once the compounds
did not dissolve in any of the common solvents, the crystallization process would be
something time consuming and difficult to accomplish.
In the elemental analysis of the compounds, the following results were obtained (Table 6):
Table 6 - Elemental Analysis performed in the syntheses of compounds (1), (2), (3) and (4)
1st Synthesis 2nd Synthesis
N (%) C (%) H (%) N (%) C (%) H (%)

Value
6,94 53,55 3,50 6,94 53,55 3,50
Theoretical
(1)
BUT 4,85 36,58 2,78 6,96 54,13 2,93
Value
7,68 49,41 3,04 7,68 49,41 3,04
Theoretical
(2)
BUT 7,62 47,87 3,09 8,74 47,09 3,30
Value
6,22 47,97 3,13 6,22 47,97 3,13
Theoretical
(3)
BUT 6,31 47,98 2,97 6,26 47,57 2,80
Value
6,80 43,76 2,69 6,80 43,76 2,69
Theoretical
(4)
BUT 6,44 41,35 2,47 6,99 41,43 2,09
It is verified, in both syntheses, that the compounds had small deviations in relation to the
literature values.
This situation was more evident in the case of the presence of N and C, in the first synthesis carried out
to compound (1), in which the deviation of the values from the theoretical values is much more
significant. The values shown in Table 6 are, however, the result of the purification
to which the compound was subjected. The compound was dissolved in water and then in
33

MeOH, with a small increase in temperature, in order to extract the maximum amount of impurities
that could exist. It is verified in this way, that the purification process turned out to be
insufficient. In view of the noticeable deviation, it can be concluded that the compound (1) obtained
in the first synthesis it is not the intended compound.
In the second synthesis, the deviation of the values obtained from the theoretical values is much smaller,
which is an indicator that the composition of the compounds will be more reliable compared to the values
in the literature. This deviation reduction could be related to the fact that the compounds
have been purified after synthesis, which minimized the presence of impurities, producing
thus better results.
2.2.4.3. Infrared Spectroscopy
The Infrared spectra obtained from the compounds were as follows (Figures 19 – 25):
i) Compound (1) - [ZnII (2,2´-bipy) (bdc) (H2O)] n
Figure 19 - IR spectrum referring to the first synthesis of the compound (1)
34

Figure 20 - IR spectrum referring to the second synthesis of compound (1)
ii) Compound (2) - ZnII (2,2´-bipy) (btec) 1/2 (H2O)] n
35

iii) Compound (3) - [CdII (2,2´-bipy) (bdc) (H2O)] n
36

iv) Compound (4) - [CdII(2,2 ÿ-bipy)(btec) 1/2 (H2O)]n
High intensity peaks are observed at 1700 – 1200 cm-1 , which are compatible with the
bpy and phenyl groups of the carboxylate ligands. The bands observed at 1570 – 1380 cm
1
, correspond to the COO bonds of the ligands. The peaks in the regions between 3400 – 3200 cm-1, ~700 and ~600
cm-1 , correspond to water molecules coordinated at different positions
of the molecule.
37

2.2.4.4. NMR spectroscopy of solids
The solid NMR spectra of compounds (2), (3) are shown below.
and (4) (Figures 26 - 28). An illustrative graph of the spectra is also represented.
obtained for the three compounds (Figure 29).
968
2 1781
. .6068 1370 2
32
.4345
2 53.
4672 6.
2 4802
1753801 3 9697.53.
. . 193711 4612
562
12 .92.14111
75 367 786..
64
463 12 .7082. 8791594.402.
698074 4135536. 017..
2
270 240 210 180 150 120 90 60 30 0

(ppm)
Figure 26 - NMR spectrum for compound (2)
1086 1891 174

2 7 1080
182
.4679 . .3610 . 509
2
.7487
7877
18111 2
05 .84106.
1390.709419 173170. . 0
852
2
5415.13111
12 5838213
3 .63. 150630.
.949 12 103101. 91 74806077.865. 7.
2
240 220 200 180 160 140 120 100 80 60 40 20 0

(ppm)
38

1318 7783 94
72 406
2 8
142 7087
.3450 .8762 .
.860
41
2 7368.13130639
12 .9496.3. 151147390. 1683759174.. 18317838
13 17 .. . 2
905 01197830. 3.
12 84756. 959843. 730732. 6. 4592
38032 64. 1
2
240 220200 180 160140 120 100 80 60 40 20

(ppm)
Figure 29 - Comparative solids NMR spectrum for compounds (2), (3) and (4).
The upper spectrum, represented in black, corresponds to compound (2). The spectrum of the
medium, represented in red, corresponds to compound (4). The lower spectrum, represented
in green, corresponds to compound (3). The arrow indicates the presence of Zinc which,
compared to the others, allows a clear distinction of the compounds. The rectangle
corresponds to the highest intensity peaks of the diffractograms.
By observing the 13C NMR Spectrum , the presence of COO- bonds is verified
in the ligands at peaks between 198.4106 and 170.1086 ppm. the presence of
39

bpy group is evident in peaks between 150.66 and 123 ppm. The presence of protons in the
water molecule is evident in peaks between 102 and 73 ppm.
2.2.4.5. X-Ray Diffraction of powders of compounds (1), (2), (3) and (4)
As already mentioned, the compounds obtained acquired a white crystalline powder appearance.
Thus, in a first approach, it was decided to carry out their characterization by
powder X-ray diffraction. Since these are compounds with a high
complexity in terms of structure, equipment and the database available for
analysis of them, there was no reference that could be compared to each of the
compounds. Therefore, this analysis was not possible.
It was then decided to try to obtain single crystals of the compounds, submitting them to
known crystallization. After filtration and drying of the compounds, the previously washed filter solvent
was stored at -4°C. From this storage, compound (1) generated crystals
of the two syntheses carried out, after about two weeks.
Storage of compound (3) at 4°C after four weeks also generated the formation
of a small number of crystals, of very reduced dimensions.
These, however, proved to be insufficient for the resolution of the compound structure,
as will be discussed in the next paragraph.
Thus, the analysis of the single crystals obtained by single-crystal X-ray diffraction was carried out,
as will be exemplified in the next point.
2.2.4.6. Compound Single Crystal X-Ray Diffraction (1)
After storing compound (1) at 4°C for about two weeks, the
formation of single crystals resulting from both syntheses performed.
Next, a photograph obtained by electron microscopy of one of the crystals of
(1) obtained (Figure 30).
Figure 30 - Electron microscopy photograph of the crystal obtained for compound (1)
40

It follows the representation of the representative structures (Figure 31) and in packaging of the
compound (Figure 32).
Figure 31 - Representative structure of the crystal obtained for compound (1)
Figure 32 - Representative packed structure of the crystal obtained for compound (1)
The results obtained in the single crystal X-ray diffraction analysis of the compound,
are schematized in Table 7.
41

Table 7 - Results obtained in the characterization by X-Ray of single crystal for the compound
(1). The left column refers to the characterization of the compound in the first synthesis, and
the right column refers to the compound of the second synthesis.
C5H9NO6Zn C68H53N15O13Zn2
Empirical formula
244.38 1419.03
Formula weight
150(2) 150(2)
Temperature [K]
Crystal system, Rhombohedral Monoclinic

space group
R-3c Cc
Space group
a = 8.767(1) Å ÿ ÿ ÿÿÿÿÿÿÿÿº a = 13.5959(5) Å ÿ ÿ ÿÿº
Unit cell
dimensions b = 8.767(1) Å ÿ ÿ ÿÿÿÿÿÿÿÿº b = 23.6806(9) Å ÿ ÿ ÿÿÿÿÿÿÿÿÿÿº
c = 8.767(1) Å ÿ ÿ ÿÿÿÿÿÿÿÿº c = 22.6608(8) Å ÿ ÿ ÿÿº
427.0(2) 7123.1(5)
Volume [Å3 ]
2 4
FROM
Calculated 1.902 1.323

density [g.cm-3 ]
Absorption 2.875 0.744

coefficient [mm-1 ]
248 2920
F(000)
0.04 x 0.04 x 0.04 0.30 x 0.30 x 0.10

Crystal size [mm]
ÿ range of data 3.42 to 28.25 2.52 to 25.40

collection [º]ÿÿÿ
-10 ÿ h ÿ 10, -11 ÿ k ÿ 11, -9 ÿ l ÿ 11 -15 ÿ h ÿ 16, -28 ÿ k ÿ 28, -27 ÿ l ÿ 26

Index ranges
Reflections 2845 / 355 [R(int) = 0.0331] 36376 / 11664 [R(int) = 0.0415]

collected / unique
Completeness to q = 100.0% 99.6%

28.25
42

Max. and min. 0.8937 and 0.8937 0.9293 and 0.8076

transmission
Data / restraints /
355 / 0 / 31 11664 / 2 / 885
parameters
Goodness-of-fit
1.253 1.038
on F2
Final R indices [I >

R1 = 0.0293, wR2 = 0.0676 R1 = 0.0432, wR2 = 0.1053
2s(I)]
R indices (all
R1 = 0.0319, wR2 = 0.0681 R1 = 0.0525, wR2 = 0.1094
data)
Largest diff. peak 0.370 and -0.524 0.596 and -0.290

and hole [eA-3 ]
The study by single crystal X-ray diffraction was performed only for compound (1),
since it is the only one of the four compounds that generated unique crystals that can be obtained
a calculation of the structure by this method. The crystals were generated in the two syntheses
performed on the compounds, and Table 7 presents the values obtained in the resolution of the
structure.
Determination of the structure shows that compound (1) exists as a one-dimensional infinite chain coordinated
in a zig–zag fashion. Each ZnII center is surrounded by
Oxygen atoms from the nitrogen donors of the 2,2'-bipyridine rings, and by
Oxygen atoms from the carboxylate groups of the ligands. In this structure, the
bpy molecule acts as a peripheral ligand, and prevents the chain from developing into a
linear direction. For this reason, the chain grows in a zig–zag fashion.
The results obtained, however, fall short of what has already been obtained in the literature for this
compound. The studies carried out indicate that it exists as a chain of
neutral one-dimensional infinite coordination, and in a zig–zag fashion. However, each ZnII center is
surrounded by two nitrogen donors from the 2,2'-bipyridine ring, and by two
oxygen atoms of the carboxylate groups of two different terephthalic acid molecules,
coordinates with a water molecule in a pentacoordinate geometry.
2.2.4.7. X-ray Diffraction of Powders
This characterization was possible due to the fact that viable single crystals were obtained for
reading compound (1) because, as already mentioned, it did not exist in the system database
any compound that can be compared with the compounds synthesized in this dissertation.
43

Thus, the following diffractograms were obtained for compound (1) (Figure 33):
Figure 33 - Diffractograms obtained for compound (1). In blue and above, the
compound resulting from the first synthesis is represented. The pink diffractogram shown
below represents the compound synthesized in the second synthesis.
For compound (3), the unit cell was determined by single crystal, but the
diffraction proved to be insufficient to resolve the structure, in order to start the calculations
indexing of the experimental diffractogram.
Thus, the mesh indexing was determined by powder X-rays, using the mesh
determined from the single crystal as a starting point for refinement.
The results obtained for compound (3) are shown in Table 8.
Table 8 - Results obtained in the X-ray powder diffraction, for the compound (3)
what
l a b c a b c Vol.
O
refined mesh 0 1.541 80.297 134.975 194.004 96.89 94.05 91.6 2080.8
Errors associated
0 0 0.0149 0.024 0.0416 0.114 0.17 0.163
with refinement
Regarding compound (4), it was not possible to determine the unit cell through
single crystal, due to the absence of single crystals to start the indexing calculations of the
experimental diffractogram.
44

The X-ray powder diffraction was a somewhat difficult characterization to perform due to the
obligation to obtain single crystals of the compound, so that they could be
compared with the diffractograms obtained for the powders of the same compound.
In the case of the compound synthesized in the first synthesis, the presence of three peaks of
high intensity at 10, 15 and ~21 ÿ/º; while in the second synthesis these peaks
are evident at 8, 13 and ~21 ÿ/º.
45

3. Conclusion of Results
In this chapter, the compounds [Zn(2,2'- bpy)(bdc)(H2O)]n (1), [Zn(2,2'-

bpy)(btec)1/2(H2O)]n (2), [Cd(2,2´-bpy)(bdc)(H2O)]n (3) e [Zn(2,2´- bpy)(btec)1/2(H2O)]n (4).
According to the results presented, it is concluded that these were quite satisfactory,
given the problem related to the synthesis and, above all, to the characterization of this type
of compounds.
After the synthesis was carried out, the compounds acquired the form of a white powder, and the
presence of single purple crystals in compounds (1), (3) and (4). However, only the
compound (1) generated crystals that could be observed and characterized by diffraction of
Single-crystal X-rays.
This technique is one of the most used and explored techniques in the study of MOFs, since
which is the only tool that predicts the three-dimensional structure that is characteristic of MOFs.
One of the major issues of this experimental work was precisely the formation of
single crystals. The four compounds generated obtained an amorphous powder appearance and, for
enable the formation of single crystals, the solutions had to be subjected to temperatures of 4
°C and below.
Since the single crystals generated come from the filtration solvent and are not
product of the synthesis itself, it is not possible to affirm that the products obtained are the
intended and that the single crystals generated are faithful to the structure of the compound.
The crystallization process is also quite slow and time-consuming and results are only observed when
after a few weeks, often subjecting the compounds to temperatures each time
smaller, in order to be able to observe the formation of crystals that, many times, are not
feasible for predicting the structure.
This is evident in the fact that, despite having obtained crystals of all compounds, the only
viable for the study of the structure were those obtained for the compound (1).
As can be seen, the explicit structure in Figures 31 and 32 obtained for the compound is quite
different from that obtained in Figure 34, which is presented below.
46

Figure 34 - Compound structure (1) [10]
This is because zinc is coordinated with the nitrogen atoms of bipyridine, something that
it is not verified in the case of the obtained structure.
In the case study, it is verified that the nitrogen atoms of bipyridine coordinate with the
Oxygen present at the end of the complex which, in turn, is coordinated with the
Metal.
Despite having formed a different compound from the one obtained in the literature, it can be concluded that,
there is no doubt that there is the formation of a one-dimensional network coordinated between the
bipyridine alone, and the Metal ion coordinated with the carboxylate group, that is, there is a
formation of a MOF with different structural characteristics compared to what already exists in the
literature for the same compound.
Thus, it is concluded that, despite being in the presence of the synthesis of four compounds
distinct, whose ligands are coordinated with metallic centers of Zinc and Cadmium,
it can only be concluded with some certainty the formation of a Zinc MOF, coordinated
with a dicarboxylic acid and bipyridine.
The problem with this conclusion is related to the fact that the work of synthesis is not something
linear, and whose small variations can generate a countless number of secondary species, which
may interfere in the later stages of synthesis, thus generating new products
different than expected.
Although the synthesis of these MOFs does not require extensive manipulation of temperature or
pressure, despite having purified the starting compounds to the maximum before the synthesis of the
compounds themselves, it was verified by the characterizations carried out, that it may have
there was the presence of impurities in the final product, according to what was obtained in the structure of the
compound (1).
47

Thus, although MOFs are undoubtedly a species of expanding compounds with

applications, have several associated problems, namely, in the synthesis and
prediction of the structure, which can be overcome by carrying out several synthesis of a
same compound, something that was not possible in the present practical work, due to the time
available for completion.
By ensuring that several syntheses are carried out, with due care associated, you can
ensure the formation of several crystals that may be viable for the prediction of
structure.
48

Chapter 3 – Cobalt (II), Iron (II) and Chromium (II) MOFs with the ligands 1,4 – Bis(4'-
Pyrazolyl)Benzeno e [NH2(CH3)2](COO)3
CHAPTER 3
Cobalt (II), Iron (II) and Chromium (II) MOFs with the
ligandos 1,4 - Bis(4´- Pyrazolyl)Benzeno e
[NH2(CH3)2](COO)3
49

1. Introduction
In this chapter, the compounds with the following composition were synthesized: (5)
[CoII(BPB).3DMF] [13], (6) [FeII(BPB).3DMF], (7) [CrII(BPB).3DMF] and (8) [Co[NH2(CH3)2](COO )3]
[26] (9) [Fe[NH2(CH3)2](COO)3].
These compounds were prepared through the solvothermal reaction of Cobalt Nitrate
hexahydrate and Iron Chloride tetrahydrate with the ligand H2BPB and with the
[NH2(CH3)2](COO)3; and Chromium Chloride hexahydrate with H2BPB.
The synthesis of Cobalt and Iron compounds with the ligand [NH2(CH3)2](COO)3 was carried out,
not only to try to obtain a better yield in the reaction, but also, in order to
simplify the synthesis, and minimize the variables that can interfere with the final product of the reaction.
50

2.Synthesis of Cobalt (II), Iron (II) and Chromium (II) MOFs with the
ligando de 1,4 – Bis(4´-pyrazolyl)benzeno
2.1. Materials and Techniques
Reagents of AR purity, obtained from commercial sources (Sigma –

Aldrich, Merk), without further purification required.
In addition to the use of current material used in the laboratory, the characterizations of
compounds were performed using various analysis devices, which served as
support for obtaining the results obtained.
The elemental analyzes were obtained on the PerkinElmer PE 2400 Series II device, according to the
which has already been exemplified in Chapter 2 (Figure 11).
Liquid NMR analysis was performed on a Rucker Avance II+ 300

MHz, which operates in a temperature range from -100 to 150 ºC, with an operating system
Topspin 2.1, ideal for the characterization of small and medium-sized organic and organometallic
compounds (Figure 35). 13C and 1H spectra were performed for the
starting compounds, using DMSO as a solvent.
Figure 35 - Rucker Avance II+ 300 Spectrophotometer
Single crystal X-ray diffraction was performed on a Bruker AXS-KAPPA APEX II diffractometer, using Mo-
Kÿ radiation (ÿ = 0.71073 Å) from monochromatic graphite (Chapter 2, Figures 14 – 15). A data sphere
was collected at 150(2)K, with omega scans of 0.5° per frame. Cell parameters were obtained using Bruker
SMART or Bruker software.
APEX2, and were refined using Bruker SAINT on all observed reflections. At
absorption corrections were applied, using SADABS [20]. The structural solution and the
respective refinements were carried out by direct methods, using the
SIR2004 [21] and SHELXS-97 [22], including both the WINGX-Version software package
1.80.05. [23] The non-hydrogenated atoms were anisotropically refined. All the
51

Hydrogens were inserted in idealized positions that allowed a refined reading of the
neighboring carbon atom. In compound (5), the N-H atoms of the dimethylammonium cation do not
were included due to the high disorder observed. Torsion angles and parameters
geometry were calculated using SHELX. [24] The illustrations of the molecular structures were made in
the software ORTEP3v2. [27]
2.2. Experimental Method
2.2.1. Preparation of Ligand 1,4 – Bis(4'- pyrazolyl)benzene (H2BPB) [13]
In a beaker, the Vilsmeier complex was prepared by adding 11 mL of

Phosphorus (0.12 mol) to 11.4 ml of DMF (0.15 mol) with stirring at 0°C. A compound was obtained
yellow with a gelatinous consistency.
In a 250 mL volumetric flask, 3.80 g of Phenylenediacetic Acid (20 mmol) was added to
10 ml of DMF. The Vilsmeier complex prepared above was added to this mixture.
The resulting mixture was stirred and refluxed at 70°C overnight. One was obtained
compound with a reddish color and an equally gelatinous consistency.
In a beaker, a solution of NaOH was prepared in 100 g of crushed ice, at pH = 14.

The above mixture was added to this preparation and the resulting mixture was vacuum filtered.
The resulting solution was transferred to a 250 mL round bottom flask and concentrated
the same using rotavapor evaporation, in a bath at 70 ºC, for 1h40 minutes.
To the resulting mixture was added 100 ml of Ethanol and refluxed at 80°C. Occurred
the formation of a white precipitate and the solution homogenized.
Then, hot filtration was carried out, which resulted in an off-white solid and
a reddish-colored filtrate. 5 ml of Hydrazine Hydrate was added to the filtrate and
the mixture was refluxed at 120°C for 3h15 minutes.

The synthesis process is shown in Figure 36.
Figure 36 - Formation of ligand H2BPB: a) Vilsmeier Complex, DMF, 70°C, 18h; B)

Hydrazine Hydrate, EtOH, reflux, 3h
52

The resulting compound was filtered on a porosity 3 plate, and washed with Ethanol and Diethyl
Ether. It was found that the compound acquired a very caramelized consistency,
orange in color and difficult to handle.
Thus, several types of methods were used in order to make the compound with a
loose powder consistency, in order to facilitate future operations with it.
The first approach involved dissolving the ligand in some common solvents. In this
In this approach, the formation of a large amount of ligand was observed, higher than that obtained
in the literature, which made it necessary, in a second approach, to proceed with its purification.
The ligand was characterized by AE (Table 9) and by Liquid NMR (Figures 38 - 39).
i) Approach 1: Solubility Tests
Solubility tests were carried out to try to dissolve the compound in a solvent in order to
remove any impurities that might be present.
After the tests were carried out, the compound was dissolved in DMSO, and left to stir.
overnight. The compost was dried on the vacuum line and there were no changes in its
caramelized consistency.
Thus, the dissolution of the same in Hexane was proceeded. After 5 days, the formation of small
yellow – light aggregates was observed. Then it was filtered, the compound was washed with
Ethanol and Diethyl Ether and dried in the vacuum line.
4.26 g of compound were obtained, corresponding to a yield of approximately 40%.
ii) Approach 2: Purification of the H2BPB Ligand
Purification was carried out using a variety of techniques.
In a schlenk, the compound was dissolved in hot DMSO, and allowed to stir at 85°C.
An orange colored solvent and a white precipitate were obtained, which suggests that the
impurities were partly removed by the formation of this salt. The compost was hot filtered
and the filtrate was evaporated on a rotary evaporator at 80°C for 2h15 minutes.
The compound was dried in the vacuum line, and an orange oil was observed to form.
In this way, the Freezing/Thaw technique was used in the vacuum and
nitrogen to solidify the compound. There were no changes.
Thus, in order to dry the compost as much as possible in order to make it solid again,
it was stirred overnight in Dichloromethane. After decanting and drying
in a vacuum line, there were no changes in the oily consistency of the compound.
53

In this way, methanol was dried in sieves of H2Ca overnight, and the
binding with the dry methanol under stirring for 5 hours. The methanol was decanted and dried
the compound in the vacuum line. After applying the Freeze/Thaw technique in
vacuum line and nitrogen line, the formation of a yellow solid compound was observed
Pale.
About 0.0281 g of Ligand was obtained corresponding to a yield of

approximately 3%.
2.2.2. Synthesis of compounds (5) [13], (6) and (7)
In a glass ampoule, 0.0407 g of Cobalt nitrate hexahydrate (Co(NO3)2.6H2O) (137 ÿmol) and 0.0129
g of ligand H2BPB (38 ÿmol) were placed.
In the same, 4 mL of DMF was added (a reddish-colored solution was obtained), followed by
0.06 mL of a previously prepared 37% HCl solution (the solution turned blue).
The ampoule was sealed at room temperature, and immersed in an oil bath at 40
ºC The temperature was monitored for 4 days, from 40 ºC to 120 ºC, with variations of
approximately 5°C/hour.
At the end of this time, the formation of a blue precipitate was observed, without the formation of
crystals (Figure 37).
Figure 37 - Detail of the sealed ampoule, containing the Co(NO3) 2.6H2O + H2BPB
solution
The procedure was repeated again, and a small amount of

of blue precipitate, with purple crystals.
The procedure was also repeated for 0.0440 g of iron chloride tetrahydrate
(Fe(Cl)2.4H2O) and to 0.0430 g of Chromium Chloride hexahydrate (Cr(Cl)2.6H2O), however,
the Iron compound generated a yellow precipitate (consistent with the oxidation of the compound)
and the Chromium compound did not generate any precipitates or crystals.
54

2.2.3. Synthesis of Cobalt (II) and Iron (II) MOFs with the ligand [NH2(CH3)2](COO)3]
2.2.3.1. Preparation of the starting compound NaCHOO.2H2O
In a beaker, 40 g of NaOH was dissolved in 37 ml of COOH, with stirring. added to
resulting mixture to 18 mL of H2O.
2.2.3.2. Synthesis of Compounds (8) [6] and (9)
In a glass ampoule, 0.0207 g (1 mmol) of Cobalt Nitrate hexahydrate was added.
(Co(NO3)2.6H2O) a 0.0203 g (3 mmol) de NaCHOO.2H2O, 0.00814 g (1 mmol) de Me2NHC2Cl, 8
mL of DMF and 8 mL of H2O.
The ampoule was sealed at room temperature and immersed in an oil bath in
reflux at 140°C for 2 days.
There was the formation of a black precipitate along the walls of the ampoule, however, this
was small, not making it possible to carry out any characterization. There was also formed a
small number of crystals.
The procedure was repeated for 0.0202 g (1 mmol) of iron chloride tetrahydrate
(Fe(Cl)2.4H2O) and an orange precipitate was observed, which indicates that iron
oxidized. It was filtered and the precipitate was washed with EtOH and H2O.
2.3. Results and discussion
2.3.1. Characterization of the H2BPB ligand
Table 9- Elemental Analysis performed on Ligand H2BPB, in the synthesis before and after
purification
N (%) C (%) H (%)
Theoric value 26,65 68,56 4,79
1st Analysis 16,95 7,19 6,05
2nd Analysis (After

6,15 16,49 4,24
purification)
55

It is verified that the EA produced results below the existing results in the literature.
Only the percentage of protons was close to the values intended to be obtained,
while the percentage of Carbons and Nitrogen was far from what was expected.
2.3.1.2. NMR Spectroscopy of Liquids
Figure 38- 1H NMR Spectrum for Ligand H2BPB
56

Figure 39 - 1H NMR Spectrum for Ligand H2BPB
Regarding the analysis by NMR of liquids, the presence of four protons of the
pyrazolyl group, as well as four protons from the benzene group. Thus, it can be seen that
the ligand may have the expected structural characteristics.
2.3.2. Characterization of Cobalt Compound with H2BPB
2.3.2.1. Single crystal X-ray diffraction for compound (5) [CoII(BPB).3DMF]
Single purple crystals formed for compound (5). despite if

have formed a small number of single crystals of compound (8), these do not
proved viable for reading and interpreting the structure of the compound.
Therefore, a photograph obtained by electron microscopy of a

crystal obtained for (5) (Figure 40), as well as the structures obtained by X-ray diffraction of
single crystal, single (Figure 41) and packed (Figure 42), representative of the same.
57

Figure 40 - Electron microscopy photograph of the crystal obtained from [CoII(BPB).3DMF]
Figure 41 - Representative structure of the crystal obtained from [CoII(BPB).3DMF]
58

Figure 42 - Representative packed structure of the crystal obtained from [CoII(BPB).3DMF]
The results obtained in the single crystal X-ray diffraction analysis of the compound (5),
are schematized in Table 10.
Table 10 - Data obtained in solving the structure of [CoII(BPB).3DMF]
Empirical
formula C5H9CoNO6
Formula
237.92
weight
Temperature
150(2)
[K]
Crystal
system, space Rhombohedral
group
Space group R-3c
a = 8.7496(11) Å ÿ ÿ ÿÿÿÿÿÿÿÿº
Unit cell
dimensions b = 8.7496(11) Å ÿ ÿ ÿÿÿÿÿÿÿÿº
c = 8.7496(11) Å ÿ ÿ ÿÿÿÿÿÿÿÿº
59

Volume [Å3 ] 424.5(3)
FROM 2
Calculated
density [g.cm 1.862
3
]
Absorption
coefficient 2.020
[mm-1 ]
F(000) 242
Crystal size 0.10 x 0.10 x 0.10

[mm]
ÿ range for
data 3.42 to 25.36
collection [º]ÿÿÿÿ
Index ranges -9 ÿ h ÿ 8, -10 ÿ k ÿ 8, -10 ÿ l ÿ 10
Reflections
collected / 2408 / 262 [R(int) = 0.0320]
unique
Completeness to
97.8%
q = 25.36
Max. and min.

transmission ion 0.8235 and 0.8235
Data /
restraints / 262 / 0 / 31
parameters
Goodness-of fit
1.315
on F2
Final R
indices [I > R1 = 0.0359, R2 = 0.0831
2s(I)]
R indices (all
R1 = 0.0384, R2 = 0.0837
data)
Largest diff.
peak and hole 0.358 and -0.351
[eA-3 ]
In the analysis of the X-ray diffraction of the compound (5), it is verified that the lattice is constructed by
Cobalt ions that are distributed in parallel in one-dimensional infinite chains and that,
60
Synthesis and Characterization of MOFs – Metal Organic

Frameworks Chapter 3 – Cobalt (II), Iron (II) and Chromium (II) MOFs with
the ligands 1,4 – Bis(4'- Pyrazolil)Benzene and
[NH2(CH3)2 ](COO)3 each Cobalt ion has a tetrahedral coordination with the Nitrogen atoms
from the ligand BPB2- .
61

3. Conclusion of Results
The objective of this part of the practical work was the synthesis and characterization of the compounds (5)
[CoII(BPB).3DMF], (6) [FeII(BPB).3DMF], (7) [CrII(BPB).3DMF], (8) Co[NH2(CH3)2](COO)3] e (9)

Fe[NH2(CH3)2](COO)3].
The first major challenge of the experimental procedure concerned the synthesis of the ligand
H2BPB. In a first instance, a compound of caramelized consistency was generated, which
made handling it a challenge. Thus, as explained above,
several dissolutions of the compound were carried out in common solvents, with manipulation of the
temperature, in order to allow its handling.
Once the desired powder consistency was achieved, purification of the compound was followed,
in order to remove all the impurities present because the yield obtained was much higher
to the expected. However, the purification led to the compound regaining the
initial consistency, making the purification process challenging. It was necessary to resort to
some techniques for the compost to acquire the consistency of powder again,
namely, the “freeze/thaw” technique in the vacuum and nitrogen line.
In this way, a small amount of compound was obtained, sufficient for the synthesis of
aforementioned compounds.
Only compound (5) generated single crystals, capable of being characterized by Diffraction
Single Crystal X-Ray. The remaining compounds also generated crystals, according to the
which has already been described in the experimental procedure, however, these were not likely to be
characterized by their poor “quality”.
The synthesis of compounds with the ligand of [NH2(CH3)2](COO)3 was carried out in order to
simplify the ligand synthesis process and, in this way, minimize the synthesis time of the ligands.
compounds.
Unfortunately, the synthesis of compounds with this ligand did not generate any crystals at all.
little, sufficient quantity of product capable of being characterized. The fact that iron
example, oxidizing very quickly in the synthesis process, caused it not to become
into a synthetically viable metal, unless this was carried out in a
inert environment. Synthesis was not tried under these conditions, since the time in
which the experimental process took place, was not enough.
Thus, the formation of a MOF is verified, with characteristics a little different from what already
was obtained in the literature (Figure 43).
62

Figure 43 - Packaging structure of the compound (5), in accordance with what exists in the
literature. Protons from the DMF molecules have been omitted for clarity in interpreting the
structure. [13]
Thus, despite the formation of the MOF for the compound (5), above all, the
difficulties, once again, in the synthesis of the compounds.
The fact that the H2BPB ligand was subjected to so many dissolutions in so many solvents
different, may have interfered on a large scale in the final product, as it may contain
impurities that affect the final structure of the compound.
The fact that no single crystals were formed, viable for characterization, also had
consequence of characterization. None of the compounds, other than (5), generated single crystals o
which, once again, demonstrates the difficulty that can exist in obtaining results in this type of
organometallic synthesis.
In general, and although the synthesis of these compounds has been problematic for a number of
factors already mentioned, the fact that a MOF of compound (5) was formed,
exemplify once again the complexity associated with this type of structures.
63

64

Chapter 4 – General Conclusions and Prospects for Future Work
CHAPTER 4
General Conclusions and Future Work Prospects
65

The present Dissertation had as objective, the synthesis of MOFs, resorting to the use of
slings with different properties, in order to observe compounds with different
structural features.
Carrying out a general analysis, it appears that, despite the synthesis process not appearing
be complex, i.e. all reactions proceed with only a small increase in
temperature, and without pressure variation, generally, this is divided into many stages
making the process quite lengthy.
Initially, one of the stimulators for the study of these compounds was, in fact, the syntheses
apparently simple, which “promised” the formation of fabulous compounds, distributed in
three-dimensional networks.
The compounds synthesized in Chapter 2 were compounds submitted to a process of

simple synthesis, although quite time consuming.
One of the great challenges in terms of synthesis was undoubtedly linked to the formation of the
ligand H2BPB, exemplified in Chapter 3. This ligand, being a compound
polyazaheterocyclic widely used in the synthesis of MOF's due to its properties
structures, would become one of the most challenging in all experimental work.
This is due to the fact that, after the various syntheses carried out, the resulting compound
systematically acquire a “caramelized” consistency, which almost made its
handling. Only by resorting to a variety of techniques, such as dissolving the
compound into a series of organic compounds, the freeze/thaw technique in
vacuum/nitrogen, it was possible to obtain the desired consistency. However, this process gives rise to
high compost losses, as well as increasing the probability of impurities in the
final compound.
Since obtaining single crystals is one of the main objectives of this type of
compounds, as only single-crystal X-ray analysis enables an
depth of the structural characteristics, this factor could also become a challenge in the
analysis of the products obtained.
The compounds synthesized in Chapter 2 gave a white final product, with the
consistency of an amorphous powder. Powder X-ray analysis was applied, however, because it was not
existing in the system's database, compounds that can be compared with the
compounds obtained, in order to obtain the diffractograms, it was necessary to “force” the formation of
single crystals in order to have a basis for comparison that could be compared.
comparable in the system.
Since single crystals were obtained from the filtration products, it is not possible to
confirm that it is, in fact, the final compound obtained in view of the results obtained in the
66

single-crystal X-ray characterization although, structurally, the compound (1) obtained

in the second synthesis, to produce values similar to those in the literature.
Thus, some points were left open that should be taken into account in future experimental work in the
area of MOFs.
The synthesis of the compounds described in Chapter 2 can be carried out using the 4, 4' –
bipyridine, instead of 2,2'-bipyridine. The coordination of this compound allows the formation of
more stable compounds, with a more rigid structure, and increases the probability of
formation of networks in 3D, precisely due to the coordination positions of the pyridines along the
benzene ring.
In future syntheses, the amounts of reagents used should be increased.

As it turned out, the stoichiometry used in the described syntheses produced small
amounts of compost and, given the subsequent characterization techniques, may make
if insufficient, leading to the need to carry out a new synthesis. despite the
performing a new synthesis is generally necessary, in order to optimize parameters
reaction and characterization, the fact that a greater amount of product is produced,
enables characterization techniques to be further explored.
The use of ligands with simple syntheses, carried out in a few steps.
The synthesis of Iron and Cobalt compounds, (8) and (9) respectively, described in point 3 of the
Chapter 3 did not produce the expected results. Nevertheless, this ligand should be a
bets on the synthesis of compounds using other metals.
Copper and Cadmium, used in Chapter 2, could be used for synthesis with this
turning on.
This ligand is synthesized in a few steps, and has already produced reliable results in the literature.
which prove that this can be a hypothesis in the synthesis of MOFs. [13]
Bearing in mind what has been discussed, there is no doubt that the considerations to be taken in the
optimization of the described synthesis and characterization processes are: The use of ligands
more rigid, as well as ligands whose synthesis process is carried out in a few steps; it's the
increase in the amount of reagents used, since larger quantities are produced
quantities of final product, which allow the exploration of various techniques of
Description.
Going beyond the work carried out in this Dissertation, one of the areas where MOFs
have acquired some relevance, is in the area of gaseous absorption.
Since MOFs are compounds whose pore manipulation is relatively easy to obtain,
simply controlling the architecture of the ligand; as well as, in the case of compounds that
67

produce a very high specific surface area, as already described

in the literature [9]; these become challenging compounds for the storage of gases such as
hydrogen and methane, as well as for capturing carbon dioxide.
Taking into account the emerging need to use alternative energy sources
clean, minimizing the ecological footprint produced, the absorption properties evidenced
in MOFs due to their exploited structural features, makes them a
viable alternative in contributing to the energy industry.
In future work, I think that the applications of MOFs for the energy industry could
come to be explored, given the relevance that the topic has nowadays, and given the
awareness that society has been having, in the use of cleaner energies, which minimize the
negative effects of pollution on our Planet Earth.
68

Chapter 5 - Bibliography
CHAPTER 5
Bibliography
69

[1] Ribeiro, FR and JL Figueiredo, Catalysis Heterogénea. 2nd edition ed. 2007, Lisbon
Calouste Gulbenkian Foundation. Chapter 3: p. 151 - 154.
[2] Cejka J., Bekkum H.v., Corma A., Schuth F., Introduction to zeolite science and practice, 3rd
revised edition, Studies in Surface science and catalysis; Elsevier, vol. 168 Chapter 10, p. 327 –
328.
revised edition, Studies in Surface science and catalysis; Elsevier, vol. 168 Chapter 10, p. 329.
revised edition, Studies in Surface science and catalysis. Elsevier, vol. 168 Chapter 10, p. 331 -
333.
[5] A. Corma, H. Garcia, FX Liabrés and Xamena, Engineering Metal Organic Frameworks for
heterogeneous catalysis. Institute of Chemical Technology, Polytechnic University of
Valencia, Spain, 2009.
[6] James S. L., Metal Organic Frameworks. School of Chemistry, David Keir Building, Queen’s University Belfast,
Belfast, UK, 27th June 2003.
revised edition, Studies in Surface science and catalysis. Elsevier, vol. 168 Chapter 10, p. 337 -
345.
[8] Bao-Hui Ye, Ming-Liang Tong, Xiao-Ming Chen, Metal-organic molecular architectures with
2,2’-bipyridil-like and carboxilate ligands, School of Chemistry and Chemical Engineering, Sun
Yat-University, Guangzhou, China, 22 September 2004.
[9] Shengqian Ma, Hong – Cai Zhou, Gas storage in porous metal – organic frameworks for
clean energy applications. Cambrige , UK, 2 November 2009.
[10] Rishikesh Prajapati, Lallan Mishra, Keisaku Kimura, Pallepogu Raghvaiah, Metal – organic
frameworks (MOFs) constructed from ZnII/ CdII – 2,2´- bipyridines and polycarboxylic acids:
Synthesis, characterization and microstructural studies. Department of Chemistry, Banaras
Hindu University, India; School of Material Science, Japan; National Single Crystal X – ray diffractometer
facility, University of Hyderabad, India; 2009.
[11] A. Thirumurugan, C. N. R. Rao, 1,2 - , 1,3 – and 1,4 – Benzenedicarboxylates of Cd and Zn
of different dimensionalities: Process of formation of the three-dimensional structure. Chemistry
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and Physics Materials Unit, Jawahardal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore,
India, 15th June 2005.
[12] J. C. Yao, W. Huang, B. Li, S. –H. Gou, Y. Xu. Inorgamic Chemistry Commum. 5 (2002)
711.
[13] Lu Y., Tonigold M., Bredenkotter B., Volkmer D., Hitzberg J., Langstein G., A Cobalt(II) –
containing Metal – Organic Framework Showing Catalytic Activity in Oxidation Reactions. Ulm
University, Institute of Inorganic Chemistry II, Materials and Catalysis; Bayer MaterialScience;
July 2008.
[14] Masciocchi, M .; Ardizzoia, G .; Brenna, S .; LaMonica, G .; Maspero, A .; Galli, S .; Sironi, A.,
One – Dimensional Polymers Containing Strictly Collinear Metal Ions: Synthesis and XRPD
Characterization of the Homoleptic Binary Metal Pyrazolates. Milan, Italy, 25 June 2002.
[15] http://sellerink.com.br/blog/tag/isaac-newton/, consulted in June 2012.
[16] Ribeiro, FR and JL Figueiredo, Catalysis Heterogénea. 2nd edition ed. 2007, Lisbon
Calouste Gulbenkian Foundation. Chapter 4: p. 175 - 176.
[17] http://www.profpc.com.br/Os_segredos_da_mumifica%C3%A7%C3%A3o.htm, consulted

in July 2012.
[18] G. M. Sheldrick, SADABS, Program for Empirical Absorption Correction. University of
Göttingen, Göttingen, Germany, 1996.
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Giacovazzo, G. Polidori, R. Spain, J. Appl. Crystallogr. 2005, 38, 381
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Göttingen, Germany, 1997
[21] L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837
[22] a) P. van der Sluis, AL Spek, Acta Cryst. A46, 1990, 194 b) AL Spek, J. Appl. crystal.,
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[25] Sutapa S., Samiran M., Parimal K., Manas KS, Kruger C., Bruckmann J. , synthesis,
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– phenanthroline, 2,2´- bipyridine and 4,4´- bipyridine. Max Plack Institute for Coal Research,
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72
73

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Patricia Vanessa Palma da Silva

Bachelor of Science in Chemical and Biochemical Engineering

Synthesis and Characterization of MOFs –

Dissertation for obtaining the Master's Degree in

Advisor: Ana Margarida Sousa Dias Martins,

Co-supervisor: Inês Alexandra Morgado do Nascimento

President: Prof. Doctor Rui Manuel Freitas Oliveira

Argue: Prof. Doctor Isabel Maria de Figueiredo Ligeiro da Fonseca

Synthesis and Characterization of MOFs – Metal Organic Frameworks

Synthesis and Characterization of MOFs –

Copyright © Patrícia Vanessa Palma da Silva, from FCT/UNL and UNL.

printed material reproduced on paper or digitally, or by any other means known or

copying and distribution for educational or research, non-commercial purposes, provided

that credit is given to the author and publisher.

Synthesis and Characterization of MOFs – Metal Organic Frameworks

This dissertation had the

at the Instituto Superior Técnico,

Organometallic and Catalysis

Homogeneous from the Chemistry Center

Professor Ana Margarida Martins.

Synthesis and Characterization of MOFs – Metal Organic Frameworks

I dedicate this work to my beloved

family, especially my parents

Francisco and Helena, to my beloved

João, and to my sister Andreia.

“The most beautiful experience

we can feel is the Mystery. he is the

Synthesis and Characterization of MOFs – Metal Organic Frameworks

I begin by thanking Professor Isabel Maria de Figueiredo da Fonseca, for having

Finally, I want to thank all those who contributed in some way.

Synthesis and Characterization of MOFs – Metal Organic Frameworks

Synthesis and Characterization of MOFs – Metal Organic Frameworks

Synthesis and Characterization of MOFs – Metal Organic Frameworks

Synthesis and Characterization of MOFs – Metal Organic Frameworks

MOFs - Metal Organic Frameworks.

strong covalent bonds.

applications in the field of gas adsorption and storage.

with 1,4-benzenedicarboxylic acids and 1,2,4,5 - benzenetetracarboxylic, and compounds of

diffraction of powders and single crystals, and infrared spectroscopy.

Synthesis and Characterization of MOFs – Metal Organic Frameworks

Synthesis and Characterization of MOFs – Metal Organic Frameworks

Thanks................................................. ................................................................ .......................... v

Index ................................................. ................................................................ .......................................... xi

Figure Index ..................................................... ................................................................ ......................xv

Index of Equations ..................................................... ................................................................ ....................xix

Symbology and Notations ..................................................... ................................................................ .............xxxi

1. Introduction ............................................... ................................................................ ............................. two

1.1. A historical approach: Zeolites – Characteristics and Synthesis ................................... 2

1.2. Definition of MOFs – Metal Organic Frameworks................................................. ............... 3

1.4. MOFs – Synthesis, Approaches and Properties ................... 5

1.4.1.2. Approaching the First Problem ..................................................... ...................... 8

i) Use of rigid ligands ................................................................... ................................... 8

ii) Exploration of the most used coordination models ................................................ 8

iii) Anion effect ..................................................... ................................................................ ...... 9

iv) ROP- “Ring opening polymerisation” relationships ................................................ ............. 9

1.4.1.3. The Second Problem – Interpenetration ............... 9

Use of bulky ligands ................................................... ................................... 10

i) ii) Concentration effect ..................................................... ................................................... 10

1.4.2.4. Solubility and Ion Exchange ................................................... ................................. 14

1.4.2.5. Catalysis................................................. ................................................................ ......... 14

1.5. Ligands used ........................................................... ........................................................... ..... fifteen

1.6.3. X ray............................................... ................................................................ ............... 19