Chemia związków molekularnych i nanomateriałów

chemia nieorganiczna, koordynacyjna i metaloorganiczna

chemia bionieorganiczna i supramolekularna

podstawy chemii materiałów

UMIEĆ =//= ROZUMIEĆ

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• Niektóre z zamieszczonych rysunków i schematów zaczerpnięto z
oryginalnych publikacji naukowych ( odpowiednie odnośniki
umieszczono w tekście ) oraz z następujących podręczników:
-I. Flaming, Molecular Orbitals and Organic Chemical Reactions,
-C.E. Housecroft, A.G. Sharpe, Inorganic Chemistry
The demarcations between the traditional branches of chemistry have become increasingly
blurred and we are now witnessing a further stage of development in which chemistry is
making substantial inroads into biology and medicine, not to mention materials science and
engineering, with the supramolecular chemist in the vanguard. Gone are the days when
research in chemistry found its raison d’eˆtre in being analytical, inorganic, organic, physical
and theoretical in content.
Nonetheless, much of the formal teaching, particularly in high schools and at the
undergraduate level in colleges and universities, remains locked in these historical artefacts.
One is left wondering when change will visit the classroom as well.

„A Platform for Change”, J. Fraser Stoddart, 2015

 Chemistry in the 20th century
1955 Ziegler-Natta catalyst
1951-52 G. Wilkinson, E. O. Fischer
(Nobel Prize 1963)
(Nobel Prize 1963)

1951 – Turkevich???

Ferrocene

1965 Wilkinson’s catalyst 1991 Grubbs catalyst

(Nobel Prize 2005)
 At the turn of the 20th century
From Molecular System to
Functional Materials

3D – Systems
Nanscience

1D – Systems
2D - Systems

? D – Systems
2D Coordination Polymer of Unique Fabric Topology

J. Lewiński, W. Bury, M. Dranka, W. Śliwiński, I. Justyniak, J. Lipkowski, J. Am. Chem. Soc., 2007, 129, 3096
Area of

Interest
The demarcations between the traditional branches of chemistry have become increasingly
blurred and we are now witnessing a further stage of development in which chemistry is
making substantial inroads into biology and medicine, not to mention materials science and
engineering, with the supramolecular chemist in the vanguard. Gone are the days when
research in chemistry found its raison d’eˆtre in being analytical, inorganic, organic, physical
and theoretical in content.
Nonetheless, much of the formal teaching, particularly in high schools and at the
undergraduate level in colleges and universities, remains locked in these historical artefacts.
One is left wondering when change will visit the classroom as well.

„A Platform for Change”, J. Fraser Stoddart, 2015

Diagram obrazujący porównanie wielkości nanomateriałów z biomolekułami

Maria Jędrzejewska
Optymalizacja syntezy nanocząstek ZnO oraz badanie ich właściwości antybakteryjnych
Człowiek vs Natura
Od atomu do komórki
 Chemistry in the 20th century
1955 Ziegler-Natta catalyst
1951-52 G. Wilkinson, E. O. Fischer
(Nobel Prize 1963)
(Nobel Prize 1963)

1951 – Turkevich???

Ferrocene

1965 Wilkinson’s catalyst 1991 Grubbs catalyst

(Nobel Prize 2005)
“Today’s science fiction is often tomorrow’s science fact”
Stephen Hawking
 Chemistry in the 20th century
1955 Ziegler-Natta catalyst
1951-52 G. Wilkinson, E. O. Fischer
(Nobel Prize 1963)
(Nobel Prize 1963)

1951 – Turkevich???

Ferrocene

1965 Wilkinson’s catalyst 1991 Grubbs catalyst

(Nobel Prize 2005)
Citations Report/Web of Science
Turkevich, J., Discuss. Faraday Soc. 1951, 11, 55.

A STUDY OF THE NUCLEATION AND GROWTH

PROCESSES IN THE SYNTHESIS OF COLLOIDAL GOLD
> 3100
www.scopus.com
Wartości Impact Factor czasopism chemicznych

Journal ROK

1999 2000 2001 2007

NATURE 29.49 25.81 27.96 28.751

SCIENCE 24.60 23.87 23.33 26.372

Angew Chem 8.00 8.26 10.031

J Am Chem Soc 5.54 6.03 6.79 7.885

Chem Eur J 4.81 4.70 4.61 5.33

Chem Commun 3.48 3.70 3.92 5.141

CHEM REV 21.24 20.04 21.44 22.757

INORG CHEM 2.84 2.71 2.95 4.123

J CHEM SOC DALTON 2.31 2.82 4.10

EUR J INORG CHEM 2.22 2.48 2.597

INORG CHIM ACTA 1.30 1.20 1.39 1.713

INORG CHEM COMMUN 0.93 1.09 1.36

J ORG CHEM 3.44 3.69 3.28 3.959

ORG LETT 3.37 3.67 4.802

TETRAHEDRON-ASYMMETR 2.65 2.80 2.27 2.634

TETRAHEDRON LETT 2.40 2.56 2.28 2.615

TETRAHEDRON 2.12 2.36 2.28 2.869

EUR J ORG CHEM 2.15 2.19 2.914

CHEMPHYSCHEM 4.22 3.502

J PHYS CHEM A 2.70 2.75 2.63 2.918

J PHYS CHEM B 3.27 3.39 3.38 4.089

ORGANOMETALLICS 3.22 3.17 3.18 3.833

J ORGANOMET CHEM 1.45 1.63 1.83 2.168

MACROMOLECULES 3.53 3.70 3.73 4.411

POLIMERY-W 0.31 0.33 0.42 1.376

ANAL CHEM 4.56 4.59 4.53

TALANTA 1.19 1.55 1.59

POL J CHEM 0.60 0.58 0.53 0.483

Wartości Impact Factor czasopism chemicznych

Journal ROK

1999 2000 2001 2007

NATURE 29.49 25.81 27.96 28.751

SCIENCE 24.60 23.87 23.33 26.372

Wartości Impact Factor czasopism „materiałowych”
Angew Chem 8.00 8.26 10.031
Journal Rok 2014
J Am Chem Soc 5.54 6.03 6.79 7.885
NATURE MATERIALS 36.50
Chem Eur J 4.81 4.70 4.61 5.33
NATURE NANOTECHNOLOGY 34.05
Chem Commun 3.48 3.70 3.92 5.141

CHEM REV 21.24 20.04 21.44 22.757

NATURE PHOTONICS 32.39

INORG CHEM 2.84 2.71 2.95 4.123 Progres in Polymer Sciences 26.93
J CHEM SOC DALTON 2.31 2.82 4.10 Progress in Materials Science 25.87

EUR J INORG CHEM 2.22 2.48 2.597 Advanced Materials 17.49

INORG CHIM ACTA 1.30 1.20 1.39 1.713 Surface Science Reports 14.76

INORG CHEM COMMUN 0.93 1.09 1.36 Nano Letters 13.52

J ORG CHEM 3.44 3.69 3.28 3.959 ACS Nano 12.88
ORG LETT 3.37 3.67 4.802 Annual Review of Condensed Matter
11.90
TETRAHEDRON-ASYMMETR 2.65 2.80 2.27 2.634
Physics

TETRAHEDRON LETT 2.40 2.56 2.28 2.615 Advanced Functional Materials 11.81
TETRAHEDRON 2.12 2.36 2.28 2.869 Small 8.37
EUR J ORG CHEM 2.15 2.19 2.914 Chemistry of Materials 8,35
CHEMPHYSCHEM 4.22 3.502

J PHYS CHEM A 2.70 2.75 2.63 2.918

J PHYS CHEM B 3.27 3.39 3.38 4.089

ORGANOMETALLICS 3.22 3.17 3.18 3.833

J ORGANOMET CHEM 1.45 1.63 1.83 2.168

MACROMOLECULES 3.53 3.70 3.73 4.411

POLIMERY-W 0.31 0.33 0.42 1.376

ANAL CHEM 4.56 4.59 4.53

TALANTA 1.19 1.55 1.59

POL J CHEM 0.60 0.58 0.53 0.483

 Chemik vs Natura

C C L M

Chemia klasyczna Chemia Natura

katalityczna
 Fiksacja azotu

Przemysłowy proces syntezy amoniaku z azotu – proces Habera- Boscha:

Fe lub Ru
N N + 3H2(g) 2NH3(g)
100-300 atm
400-500 0C

∆H0 = -46.2 kJmol-1, ∆S0 = -99 Jmol-1K-1

Enzymatyczna redukcja cząsteczki azotu:

N N + 8H+ + 8e- + 16MgATP 2NH3 + H2 + 16MgADP + 16Pi
 The slow-chemistry movement

Lichens make acids that react with solid rock in processes

that chemists are trying to mimic.
Nature 2015, 524, 20-21
MECHANOCHEMIA
 Yesterday in an ancient pharmacy

Today in a modern mechanochemical lab

 Mechanochemia

✓ Brak rozpuszczalnika (neat grinding) ✓ kompleksy metali

✓ Niewielka katalityczna ilość ✓ kokryształy
Korzyści Zastosowanie
rozpuszczalnika (LAG or kneading) ✓ nowe formy leków
✓ Wzrost wydajności i czystości produktu ✓ polimery koordynacyjne
✓ Zredukowany czas reakcji ✓ materiały typu MOF

Młynki kulowe Proces reakcji mechanochemicznej

 Solid State and Mechanochemical Cluster-to-Cluster Transformations

tBu tBu tBu tBu

tBu T = 45oC tBu tBu O Zn

O THF Zn tBu
p = 10-3 Torr
Zn Zn O tBu Zn O
tBu Zn tBu
THF O O tBu
grinding O
tBu Zn
Zn O O Zn
tBu THF tBu
tBu tBu
(1) (2) tBu (3)

R
O
R Zn Zn R
O
R (a)
R
O R R R R
R
Zn Zn Zn Zn
O
O O O O
R Zn R R Zn R

R (b) R (c)

J. Lewiński, M. Dutkiewicz, M. Lesiuk, W. Śliwiński, K. Zelga, I. Justyniak, J. Lipkowski, Angew. Chem. Int. Ed. 2010, 49, 8266.
 Alternatywne ścieżki syntezy MOF-ów
Solwotermalna

t = 20 h
T = 100⁰C
Mechanochemiczna

t = 5 min
T =25⁰C
J. Lewiński et. al. Patent and article in preparation
 MECHANOCHEMISTRY
Zinc oxo complexes – predesigned Secondary Buiding Units (SBUs) of MOFs
O
R' Zn R Synthesis time reduced from several hours to several minutes
O
R'
H2O O O
O O

O Zn Zn O 3
R' O O R' HO OH

R' O R'
OO OO
Zn Zn
O
O O 6 R'
OH
R'
Zinc oxo carboxylates MOF-5

J. Lewiński, D. Prochowicz, K. Sokołowski, patent application, P-401074, 5.10.2012 r

 MOFy i materiały porowate

Seperacja
gazów

Sorpcja wodoru
Nośniki
leków

Kataliza

Sensory i luminescencja
 Nanochemia
Sensory
i biosensory

Biologia komórki

Kropki
Białe LED-y
kwantowe
Dostarczanie leków

Diagnostyka
Ogniwa słoneczne Wyświetlacze: następcy AMOLED-ów
Inorganic Chemistry, C.E. Housecroft, A.G. Sharpe Molecular Orbitals and Organic
Chemical Reactions, I. Flaming

Biochemia, L. Stryer Thomas A. Albright

Molecular Orbitals and Organic Chemical Reactions, I. Flaming
Molecular Orbitals and Organic Chemical Reactions, I. Flaming
 Reakcja SN2

Uogólniona krzywa energii potencjalnej

W. L. Hase et. al. Science 2002, 296, 875

J. I. Brauman et. al. Science, 2002, 295, 2245
I. Fernndez et. al Chem. Eur. J. 2009, 15, 2166
R. Otto et al Nature Chem. 2012, 4, 534
K. M. Ervin et. al., J. Am. Chem. Soc. 2002,124, 336
 Zróżnicowanie kierunku reakcji olefin
z kompleksami M-O2

N EWG N
Pd O
N
+ Pd + O2
O N

EWG

L1
M O L1
L2
+ + M
O O L2
 Aspekt biochemiczny - transport O2

Znane są trzy klasy białek biorących udział w transporcie tlenu: hemoglobiny-mioglobiny,

hemocyjaniny i hemerytryny. Funkcje centrów metalicznych tych białek przedstawione są na
poniższym schemacie. O
O
O O
M
Fe M
Fe

N N

HN HN

deoksyhemoglobina oksyhemoglobina

NH HN

N N
I
Cu I
Cu
II
N N N O O Cu O
N
NH HN II
N
O Cu
H N
H

deoksyhemocyjanina oksyhemocyjanina

H H O
O O O
II II III
Fe Fe Fe III
O O Fe
O O O O
C C
O O O O
C C

deoksyhemerytryna oksyhemerytryna
 Powinowactwo O2 i CO do „hem” kompleksów

Modelowy hem kompleks

O O
C O

Fe Fe

N N

N N

Mioglobina, hemoglobina
N N
N N
H H

O O
C O
Fe Fe

Wymuszona geometria N N

N N
The significance of hydroxyzinc moiety in biochemistry
Carbonic anhydrase Enzyme mimics
But
N N
But
N N Zn OH
His H B

Zn OH N N
His But
[Tpt-Bu,Me]ZnOH

His CO2

But
N N
Metabolic pathway of carbonic anhydrase But
H H H N N
O + O H B Zn O
H
2+ 2+
C OH
Zn Zn
N N
His His His His O
His His But
HCO 3-
CO 2
[Tpt-Bu,Me]ZnOCO2H
H 2O
O
O
H C H
O C
O O
O
2+
Zn
2+
Zn G. Parkin, Chem. Rev. 2004, 104, 699
His His His
His
His
His J. Weston, Chem. Rev. 2005, 105, 2151
 OTRZYMYWANIE NANOMATERIAŁÓW Z WYKORZYSTANIEM
ŚCIEŻKI ENZYMATYCZNEJ ANHYDRAZY WĘGLANOWEJ

- optymalizacja syntezy wybranego układu LxZnyRm(OH)n

- wyizolowanie produktów reakcji LxZnyRm(OH)n z CO2
- badania strukturalne i fizykochemiczne otrzymanych
kompleksów
Metalloligand precursors – Cinchona alkaloids

natural Cinchona tree bark alkaloids

H H
* *

HO * N N OH
*
H H
* H H * 9

N N

cinchonine (CN-H) cinchonidine (CND-H)

pseudoenantiomers

Cinchona calisaya
 A Strategy for the Construction of Nanotubular Architectures
and Helical Coordination Polymers

Metalloligand from Cinchona alkaloids

T. Kaczorowski, I. Justyniak, T. Lipińska, J. Lipkowski, J. Lewiński J. Am. Chem. Soc. 2009, 131, 5393.
 Microporous materials based on cinchona metalloligands

double-helix with the “in” and “out” modes:

Al-X bonds facing the inside of the chanel
or are oriented outward
Self-organization process of the metalloligand into the honeycomb network with homochiral channels

Graphical representation of helical architectures based on the cinchona metalloligand and ZnCl2

T. Kaczorowski, I. Justyniak, T. Lipińska, J. Lipkowski, J. Lewiński, J. Am. Chem. Soc., 2009, 131, 5393
Hydraty metanu