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B. Li, R. Prasad, S. R. Batten, J. Wu, J. Jin and Y. He, CrystEngComm, 2017, DOI: 10.1039/C7CE01341H.

Volume 18 Number 1 7 January 2016 Pages 1–184 This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
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Towards design strategies for anion–π interactions in crystal engineering
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 Page 1 of 19 CrystEngComm
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A 3D luminescent Zn(II) MOF for the detection of high

explosives and the degradation of organic dyes: an
experimental and computational study
Jun-Cheng Jina, Jian Wub, Yong-Xiang Hec, Bao-Hong Lic*, Jian-Qiang Liu*c, Rajendra
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Prasad,d Abhinav Kumare* and Stuart R. Battenf

CrystEngComm Accepted Manuscript

a
Technology Promotion Center of Nano Composite Material Preparation and Application; Anhui
Provincial Laboratory of Biomimetic Sensor and Detecting Technology, West Anhui University,
Anhui 237012, China
b
Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi University
for Nationalities, College of Chemistry and Chemical Engineering, Nanning, Guangxi 530006,
China
c
School of Pharmacy, Guangdong Medical University, Dongguan, 523808 and Dongguan key
laboratory of drug design and formulation technology, Dongguan, 523808, P. R. China
d
Department of Chemistry, S.G.B. Amravati University, Amrawati, Maharashtra, India
e
Department of Chemistry, Faculty of Science, University of Lucknow, Lucknow 226 007,India
f
School of Chemistry, Monash University, Victoria 3800, Australia
E-mail: gdmcli@126.com; jianqiangliu2010@126.com and abhinavmarshal@gmail.com,
Tel/Fax: 0769-22896560
_______________________________________________________________________________ 
A new metal–organic framework, formulated as {[Zn2(L)(DMF)3]·2DMF·2H2O} (1),
has been synthesized using a symmetrical rigid carboxylate ligand terphenyl-3,3ʹʹ,5,5ʹʹ-
tetracarboxylic acid (H4L). Single-crystal X-ray diffraction analysis shows that 1
possess 3D uninodal 4-c lonsdaleite (lon) topology based on binuclear Zn clusters. 1
behaves as a fluorescent chemosensor for highly selective and sensitive detection of
Fe3+/Fe2+ ions, 2,4-dinitrophenol (2,4-DNP), p-nitrophenol (PNP) and 2,4,6-
trinitrophenol (TNP). Furthermore, the photocatalytic properties of 1 for degradation of
the methyl violet (MV) and Rhodamine B (RhB) have been explored. The possible
emission quenching of 1 in presence of aromatic compounds have been addressed by
theoretical calculations and the photocatalytic activity of 1 against organic dyes have
been addressed using density of states (DOS) calculations.
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Introduction
Rapid and selective detection of hazardous aromatic benzene and its derivatives are
now-a-days the concern of national environmental security.1 Amongst these, explosives
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like nitro-aromatics for example nitrobenzene (NB) and its derivatives, 2,4-
dinitrophenol (2,4-DNP), p-nitrophenol (PNP) and 2,4,6-trinitrophenol (TNP), etc., are
the major molecular systems. Therefore, it is very essential to detect these aromatics
systems expeditiously with high selectivity.1 In the past few years there have been an
increasing interest to focus on the detection of explosives using luminescent MOFs, Li
et al. reported the first highly luminescent metal-organic framework (MOF) that is
capable of detecting traces of nitroaromatic explosives viz. 2,4-dinitrotoluene (DNT)
and 2,3-dimethyl-2,3-dinitrobutane (DMNB).2
Iron is an important metal in industry and mostly exist in ferrous (Fe2+) and ferric
(Fe3+) forms.3 The cationic form Fe3+ exhibit different effects on the human body and
other biological tissues. Fe3+ ions play an indispensable role in a variety of vital cell
functions such as hemoglobin formation, muscle and brain function, and electron
transfer processes in DNA and RNA synthesis.4 However, excess of Fe3+ in a living cell
may cause damage to nucleic acids and proteins through catalyzing the production of
reactive oxygen species (ROS). Hence, selective detection or sensing of Fe3+ over other
metal ions seems to be very important for human health.5
To obtain appropriate sensors to selectively detect abovementioned aromatic systems
and ion, most of the reported MOF-based fluorescent sensors are constructed using
aromatic ligands having non-detrimental metal ions. The most likely reasons6 for this
choice can be attributed to: (i) the aromatic ligands are widely used to build porous
MOFs by taking advantage of their rigidity and chemical stability; (ii) the π-electron
rich aromatic ligand endows the MOFs with luminescent properties, which may
efficiently promote sensing performances.7 Thus, the employment of π-electron rich
aromatic polycarboxylates as building blocks is a promising approach for constructing
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luminescent MOFs for sensing purpose.8

Recently, we had designed and synthesized a rigid symmetrical tetracarboxylate
ligand, terphenyl-3,3ʹʹ,5,5ʹʹ-tetracarboxylic acid (H4L), which has been used for the
synthesis of a lanthanide coordination framework.9 The presented investigation was the
first report in which lanthanide-based MOFs were used for the removal of fluoride ions
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from water. To further extend our work in the area of designing the novel luminescent

CrystEngComm Accepted Manuscript

MOFs for potential sensing of nitroaromatic explosives and cations, in this paper, we
had utilized terphenyl-3,3ʹʹ,5,5ʹʹ-tetracarboxylic acid (H4L) ligand and d10 cation Zn(II)
to generate a novel luminescent Zn-MOF {[Zn2(L)(DMF)3]·2DMF·2H2O} (1). The
MOF 1 comprises of 3D uninodal 4-c lonsdaleite (lon) topology based on binuclear Zn
clusters and had been exploited as a luminescent sensor for the detection of Fe3+/Fe2+
ions, 2,4-dinitrophenol (2,4-DNP), p-nitrophenol (PNP) and 2,4,6-trinitrophenol (TNP)
as well as the photocatalyst for the degradation of the methyl violet (MV) and
Rhodamine B (RhB).
Materials and Method
General Considerations
All the purchased chemicals were used without further purification. Powder X-ray
diffraction (PXRD) data was collected on Bruker D8 ADVANCE X-ray diffractometer
with Cu-Kα radiation (λ=1.5418 Å) at 50 kV, 20 mA with a scanning rate of 6°/min
and a step size of 0.02°. The simulated powder patterns were calculated using Mercury
2.0. The purity and homogeneity of the bulk products were determined by comparing
the simulated and experimental X-ray powder diffraction patterns. Fourier transform
infrared (FT-IR) spectra as KBr pellet were measured using a Nicolet Impact 750 FTIR
in the range of 400-4000 cm-1. Thermogravimetric analysis (TGA) was performed
under nitrogen atmosphere from room temperature to 650 °C at a heating rate of 10 °C
min-1, using a SDT Q600 thermogravimetric analyzer.
X-ray Crystallography
Single crystal X-ray diffraction data collection were carried out on a Bruker SMART
APEX diffractometer that was equipped with a graphite monochromated Mo
radiation (λ = 0.71073 Å) by using an -scan technique. The intensities of the
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absorption effects were corrected by using SADABS. The structures were solved by
direct methods (SHLEXS-2014) and refined by a full-matrix least-squares procedure
based on F2 (Shelxl-2014).10 All the hydrogen atoms were generated geometrically and
refined isotropically using the riding model. The hydrogen atoms of water molecule are
not located, but they were included in the formula. Because guest molecules (H2O
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and DMF) in the channels of 1 were highly disordered and could not be modeled

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properly, the SQUEEZE routine of PLATON was applied to remove their contributions
to the scattering.11 All non-hydrogen atoms were refined with anisotropic displacement
parameters. Crystallographic details and selected bond dimensions for 1 are listed in
Tables S1 and S2. CCDC number: 1556453.
Synthesis of {[Zn2(L)(DMF)3]·2DMF·2H2O} (1)
A mixture of terphenyl-3,3ʹʹ,5,5ʹʹ-tetracarboxylic acid (H4L) (0.1 mmol, 0.025 g),
Zn(NO3)2·6H2O (0.2 mmol, 0.055 g) and DMF (3 mL) was stirred for 30 min in air.
The resulting solution was placed in a 25 mL vial container and heated to 105 °C for
72 h. After that the reaction mixture was cooled to room temperature at a rate of 2 °C/h.
Colorless block crystals of 1 were obtained in 32 % yield based on zinc. Anal. (%) calcd
for C23.89H39.07O10.5N4.3Zn: C, 46.28 %; H, 6.35 %; N, 9.72 %; found: C, 46.01 %; H,
6.50%; N, 9.58 %. IR: 3371(vs); 2361(v); 1644(vs); 1616(v); 1574(v); 1372(vs);
1260(m); 1093(m); 897(m); 779(vs); 716(m); 647(m).
Computational Details
In order to provide possible quenching mechanism and to ascertain the nature of
highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbital
(LUMO) of different analytes, the ligand H4L as well as MOF 1, density functional
theory (DFT) calculations were performed. Optimized molecular geometries were
calculated using the B3LYP exchange-correlation functional.12 The 6-31G** basis set
for all the atoms were used for geometry optimization All the calculations were
performed using Gaussian 09 programme.13a GaussSum 3.1 was used to obtain density
of state (DOS) plots.13b
Results and discussion
{[Zn2(L)(DMF)3]·2DMF·2H2O} (1)
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The structure of 1 contains one unique L ligand, two unique Zn(II) ions, and three
coordinated and two intercalated unique DMF molecules and two free water molecules
(Fig. 1a). The metal ions are bridged by L ligand to form a binuclear cluster, with the
two metals bridged by three carboxylate groups of L ligands (Fig. 1b). The four
carboxylate groups of L4- linker adopt three different coordination modes: the μ3-
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chelating-bridging tridentate node, chelating bidentate and the bridging bidentate, to

CrystEngComm Accepted Manuscript

coordinate with seven Zn atoms (Scheme S1). The coordination sphere of the Zn1 ion
is then completed by coordination of three DMF molecules, one of which is disordered
over two sites, while the coordination sphere of the Zn2 ion is completed by chelation
of another L ligand carboxylate. Each dinuclear cluster is thus coordinated by four L
ligands; each ligand in turn coordinates to four dinuclear clusters (Fig. 1b). Thus each
dinuclear cluster is bound to four ligands. Each ligand in turn is bonded to four Zn2
clusters (Fig. 1b). The combination of the {Zn2(CO2)5} molecular building blocks
(MBBs) and the 4-connected ligands in a 1 :1 ratio leads to the formation of a 3D
framework that exhibits elliptical channels of dimension 11.5×14.8 Å2 along the ab-
plane (atom-to-atom separations) (Fig. 1c). Topologically, each ligand and dinuclear
metal cluster thus act as 4-connecting nodes, and an overall 3D network with the
uninodal 4-c lonsdaleite (lon) topology is formed (Fig. 1d).14 The effective free volume
is ~68.3%, as calculated by PLATON.11 The thermogravimetric analysis indicates that
the framework of 1 is stable up to 400 °C (Fig. S1). The permanent porosity of the
framework of 1 has been found to be of type I N2 adsorption profile (Fig. S2) indicating
that 1 is a microporous material with pore volume of 334.94 cm3 (STP) g−1 and the BET
surface area is 1046.01 m2/g.15
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Fig. 1 (a) view of the coordination environments of Zn(II) in 1; (b) local coordination environments
of both the ligand and the Zn2 metal cluster in the structure of 1. For clarity, the two unique metal
ions are shown in different colours (Zn1 in pink, Zn2 in orange), the coordinated DMF ligands are
shown on only one Zn2 cluster, with only one position of the disordered DMF shown, and hydrogen
atoms are omitted; (c) view of the 3D porous network; (d) underlying lonsdaleite (lon) net in the
structure of 1; black spheres represent the ligand nodes, while pink spheres represent the Zn2 cluster
nodes (although all nodes are topologically equivalent).

Luminescence sensing

The solid state luminescence of 1 and of the free H4L ligand were investigated at room
temperature on excitation at 290 nm (Fig. S3). The free H4L ligand displays one
emission peak at 414 nm, while the emission peak of 1 was observed at 455 nm. The
above emissions can be ascribed to the π* → π or π* → n transition of the ligand.16
Compared with the free H4L ligand, the obvious red-shift of 41 nm for 1 may be
attributed to ligand to metal charge-transfer (LMCT) transitions.17 Owing to its good
luminescence properties, thermal stability and the potentially active site, 1 has drawn
our attention to be used as luminescent probes in sensing metal ions and NACs.
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The MOF 1 was treated with different amount of M(NO3)x in DMF solution to form
the metal ion loaded 1@M powder solids. The luminescence intensities of Mn+@1
solutions were recorded and compared (Fig. 2a and Fig. S4) which showed markedly
different luminescent intensities. As shown in Fig. 2a, a slight luminescence
enhancement was found for K+, Na+, Cd2+, Zn2+ and Li+. Notably, the luminescent
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intensity of compound 1 was selectively quenched by Fe3+ ions. When the amount of

CrystEngComm Accepted Manuscript

Fe3+ increases, the intensity of the emission decreases. To further explore the sensitivity
of 1 towards Fe3+ ion, the concentration gradient experiments were performed by
changing concentrations of Fe3+ solutions from 0 to 600 ppm (Fig. S5a). As shown in
Fig. S5a, it is evident that the luminescence intensities of Fe3+@1 solutions gradually
decreases with the increase in amount of Fe3+. Furthermore, the fluorescence lifetime
of 90.15 ns in the 1 was observed to get reduced to 13.80 ns in the presence of 1.0 mM
Fe3+ (Fig. S6). Hence, it can be inferred that the energy transfer may be responsible for
the quenching phenomenon.18 To elucidate the possible mechanism for such
luminescence quenching by metal cations, O1s X-ray photoelectron spectroscopy (XPS)
studies were carried out on 1 and Fe3+@1 (Fig. S7). The O1s peak from the free oxygen
atoms of coordinated carboxylate at 531.65 eV in 1 gets shifted to 532.19 eV on the
addition of Fe3+ (Fig. S8) which indicates weak binding of oxygen atoms to Fe3+ in
Fe3+@1. The powder X-ray diffraction (PXRD) patterns (Figure S9) indicated possible
structural and/or symmetry changes within the crystal structure of 1 upon dispersion in
the metal ion solutions after 24 h.
The Stern–Volmer plots for Fe3+ are nearly linear at low concentrations with the Ksv
value of 7.83×103 M-1 (Fig. S5b). The Fe3+ detection limit is calculated to be 1.22 ppm.
Further competition experiments in presence of one equivalent of other metal ions
revealed that the luminescence response of 1 induced by Fe3+ ions did not get affected
by other ions. In addition, even Zn2+ and Cd2+ do not cause interference of the
fluorescence quenching induced by Fe3+ which suggest that 1 can sense Fe3+ with
remarkable selectivity (Fig. S11). To explore the potential application of 1 to detect
Fe3+ in aqueous medium, fluorescence quenching titration was performed by gradual
addition of aqueous solution of Fe3+ in 1.
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Fig. 2 (a) Photoluminescence intensity of 1 dispersed in different metal ions, excited at 290 nm (b)

luminescent quenching of 1 dispersed in water on gradual addition of 1 mM solution of Fe3+; (c)

Stern–Volmer plot for the fluorescence quenching of 1 upon the addition of Fe3+.

As expected, the incremental addition of Fe3+ resulted in fast and efficient fluorescence
quenching up to 95% (Fig. 2b). The Stern–Volmer plots for Fe3+ are nearly linear at
low concentrations with the Ksv value of 2.08 ×104 M-1 in water. This Ksv value is
comparable to the previous reports for detection of Fe3+ (typical Ksv of about 104 M−1).19
Furthermore, a linear correlation between I0/I and the concentration of Fe3+ ions was
obtained, and following the 3δ/slope, the detection limit of 1.56 ppm was calculated for
1 (Fig. 2c),20 which is comparable to/or better than previous MOF reports (Table S3).21
To examine the sensing sensitivity of 1 towards ferrous (Fe2+) ions, a series of titration
experiments were carried out in aqueous medium. The emission responses were
monitored by the gradual addition of different concentrations of FeCl2 into the
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suspension of 1@H2O. The luminescence intensity gradually decreases as a function of

increased concentration of Fe2+ (Fig. S12a). The Stern–Volmer quenching coefficient
(Ksv) for Fe2+ is calculated to be 2.88 ×103 M−1. The detection limit of 1.08 ppm was
calculated for 1 (Fig. S12b), which is a little lower than that of a terpyridyl-imidazole
(tpy-HImzPh3) based bifunctional receptor.22 Thus, 1 can be used as a highly sensitive
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luminescent probe for the quantitative detection of Fe2+ ions.

CrystEngComm Accepted Manuscript

It has confirmed that some factors are responsible for quenching in luminescence
emissions by Fe3+.23 (i) the collapse of backbone network; (ii) the resonance energy
transfer, and (iii) the weak interaction between ion and organic ligand. The UV-Vis
spectra for Fe3+@1 powder emulsion has been recorded (Fig. S13) which shows a large
overlap with the excitation spectrum of Fe3+@1. Thus, the competitive absorption
would have been taking place between Fe3+@1 and 1, which may be responsible for the
quenching effect. Actually, the XPS result also confirmed that the typical energy of Fe
2p1 shifts to 723.25 eV, giving an obvious increase of ca. 50 eV compared to the
standard value (Fig. S7).23-27
The fluorescence responses of 1 towards small molecules were also measured in
DMF suspensions by the addition of different organic molecules (Fig. S14).25 It was
observed that NB was able to quench the emissions of 1 effectively (Fig. S14 and Fig.
3a). Thus, the DMF suspension of 1 was chosen to detect different kinds of aromatics
(ACs), including 2,4,6-trinitrophenol (TNP), 2,4-dinitrotoluene (2,4-DNT), 2,6-
dinitrotoluene (2,6-DNT), 2-nitrotoluene(2-NT), 4-nitrotoluene (4-NT), 1,3-
dinitrobenzene (1,3-DNB), 1,2,4-trimethylbenzene (1,2,4-TMB), 1,3,5-
trimethylbenzene (1,3,5-TMB), o-nitrophenol (MNP), p-nitrophenol (PNP), 2,4-
dinitrophenol (2,4-DNP). All the twelve ACs can decrease the luminescent intensity of
1 to a different extent. The order of quenching efficiency is 2,4-DNP ≈ PNP ≈ TNP >
MNP >4-NT>2,6-DNT > 2-NT> 2,4-DNT> 1,3-DNB > NB > 1,2,4-TM >1,3,5-TMB
(Fig. 2b). Furthermore, the fluorescence intensity decreases steadily along with the
increase in the concentrations of 2,4-DNP, PNP and TNP. Upon addition of 130, 200
and 500 ppm of 2,4-DNP, PNP and TNP, respectively, the luminescent intensity of 1
was nearly quenched (Fig. 3c-3e).
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Fig.3 (a) Photoluminescence intensity of 1 dispersed in different solvents, excited at 290 nm; (b)
the order of quenching efficiency of different explosives; (c) -(e) emissive response spectra of 1 for
2,4-DNP, PNP and TNP in DMF solutions.
Upon adding 600 ppm of 1,3,5-TMB and 1,2,4-TMB, the fluorescence intensity of 1
remained almost unaffected (Fig. S15-S18). However, all other nitro-aromatics also
showed effect to different degrees on the fluorescence intensity of 1 (Fig. S19-S32).
These results demonstrated that 1 possess high selectivity for 2,4-DNP, PNP and TNP
in presence of different NACs (Fig. 3c-3e and Fig. S33-S35). The fluorescence
quenching efficiency can be quantitatively explained by the Stern–Volmer (SV)
equation: (I0/I) = 1 + Ksv[Q]. The Stern–Volmer plots for 2,4-DNP, PNP and TNP are
nearly linear at low concentrations (R2 = 0.99/0.989/0.992) with the Ksv value of
2.40×104, 1.52×104,and 2.61×104 M-1, respectively (Fig. S33-S35). The Ksv for TNP is
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as high as 2.61×104 M-1, a value comparable to the best conjugate polymer sensors and
Eu2(bdc)3(H2O)2(H2O)2 (H2bdc =1,4-benzenedicarboxylic acid).23c,27d The 2,4-DNP,
PNP and TNP detection limits are calculated to be 0.77, 1.03 and 0.64 ppm, respectively.
Therefore, 1 can be used to distinguish between nitroaromatics and aromatics with
different electron-withdrawing/donor -NO2 group groups. Considering the sizes of
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aromatic compounds and the absence of large pores in this MOF, the possibility of the

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accommodation of these analytes in the pores of 1 can be ruled out. As a result of the
combined processes of electron-transfer, energy transfer and electrostatic interactions
between nitro-aromatics and oxygen atoms of carboxyl group from the ligands, the
quenching efficiencies of NACs gets significantly enhanced.

Table 1. The HOMO-LUMO energies (in eV) for different analytes, ligand and 1.

Ligand/Analyte HOMO LUMO

H4 L -6.36 -1.84
1 -5.70 -1.83
2-nitrotoluene (2-NT) -7.28 -2.32
4-nitrotoluene (4-NT) -7.36 -2.32
Nitrobenzene (NB) -7.60 -2.43
2, 6-dinitrotoluene (2,6-DNT) -7.91 -2.87
2, 4-dinitrotoluene (2,4-DNT) -8.11 -2.98
1, 3-dinitrobenzene (1,3-DNB) -8.42 -3.14
2,4,6-trinitrophenol (TNP) -8.54 -3.55
1,2,4-TMB -6.03 0.28
1,3,5-TMB -6.18 0.26
2,4-DNP -7.62 -3.33
o-nitrophenol -6.80 -2.72
p-nitrophenol -7.43 -2.39

The possible quenching mechanism associated with the addition of nitroaromatics

(NACs) to 1 and markedly affected emission of 1 in presence of 2,4-DNP, PNP and
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TNP in the presented study DFT calculations were performed and the HOMO–LUMO
energies of all the nitro-aromatic and aromatic compounds along with MOF 1 and H4L
were calculated using density functional theory (DFT) at the B3LYP level (Table 1, Fig.
S37). The possible reason behind quenching in the emission of 1 in presence of NACs
will be the charge transfer from the framework of 1 to the LUMO of the NACs. For
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successful charge transfer the LUMO of the donor MOF 1 must have higher energy in

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comparison to LUMO of the acceptor NACs.24-27 The HOMO-LUMO energy
parameters presented in Table 1 indicates that the LUMO levels for all the acceptor
NACs are lower in energy scales in comparison to 1 the outcome of which is the charge
transfer from 1 to NACs. This in turn results in lowering in emission intensity of 1 in
the presence NACs in the suspension of 1. Notably, the observed order of lowering in
emission intensity of 1 by these NACs is not in full agreement with the corresponding
LUMO energies of NACs, which indicates that in addition to charge transfer
phenomenon there may be the existence of electrostatic interaction between the 1 and
NACs which contribute to the fluorescence quenching.24-27 It is noteworthy here that
the LUMO levels of 1,3,5-TMB and 1,2,4-TMB are at the higher energy scales than
that of 1 which rules out the possibility of charge transfer from 1 to these aromatics and
hence no significant changes in the emission intensities of 1 were observed when these
aromatics were added to 1.
Photocatalysis
The photocatalytic activities of 1 was evaluated by the photo-degradation of MV/RhB in
aqueous solution with UV light irradiation using a 250 W Hg lamp. The degradation ratios
of MV/RhB dyes in water were monitored by observing the intensity of the characteristic
absorption band of MV/RhB. No new absorption band was observed in the UV–vis
absorption spectra, indicating the total decomposition of MV/RhB in water. The
absorption peaks of MV and RhB were found to decrease with increasing reaction time
for 1 (Fig. 4). The calculation results show that the conversion rates of MV and RhB are
72.5% and 92.8 % under UV irradiation, respectively. For the sake of comparison, the
total catalytic degradation efficiency of the control experiment (without any catalysts)
had also been carried out. The degradation rates of MV and RhB were just 13.2% and
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Fig. 4. (a) and (b) UV–vis absorption spectra of the MV and RhB solution during the
decomposition reaction under 250W Hg lamp irradiation in the presence of 13, respectively.
10.3%, respectively within 100 min under the same condition without catalyst. These
results demonstrates that the presence of 1 is necessary for the degradation of MV and
RhB. Also, 1 exhibits better photocatalytic activity against MV than that of RhB under
similar conditions. Although dyes of MV and RhB possess the same cation organic
molecules, different cation backbones between them may lead distinct bandgap sizes,
which give rise to the discrepancy in their photocatalytic processes.28
After photocatalysis, the PXRD patterns and IR spectra of 1 were similar with the
original one, implying that 1 maintains its structural feature (Fig. S9 and S10). The
robustness of the framework of 1 can attributed to the [Zn2(CO2)5] geometries of the SBU
and the high connectivity of the ligands, for which ligand displacement is not favorable
for this arrangement. The UV-vis-NIR spectra confirms that 1 can be activated by
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DOI: 10.1039/C7CE01341H

radiation from ultraviolet and by visible light regions (Fig. S36). Thus, the evidences
indicated that 1 can separate the electron-hole pair generated by UV-vis irradiation. 29-31
To investigate the kinetics of MV/RhB photocatalytic degradation by 1, experimental
data can be described by the Langmuir–Hinshelwood model as expressed by ln (C/C0) =
−kt (k = apparent reaction rate constant). C0 is the initial concentration of MV/RhB, t is
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the reaction time, and C is the concentration of RhB/MV at the reaction time t. The plot

CrystEngComm Accepted Manuscript

of ln (C0/C) and irradiation time (t) is approximately linear and approximated the first-
order kinetic equation (Fig. S37). The calculated apparent rate constant k values of Rh B
and MV are 1.67×10-2 and 2.12×10-2 min-1 for 1, respectively. Thus, MV are much higher
than that of Rh B. So, 1 could be chosen as photocatalysts to degrade MV.32

Fig. 5 DOS and pDOS for 1.

To gain insight into the possible photocatalytic mechanism band structure of 1 based on
DFT method was performed. As presented in Fig. 5, the valence band lying just below
the Fermi level of 1 is mainly contributed by the Zn(II) center with almost negligible
contribution by the oxygen and aromatic carbons. The conduction band lying just above
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DOI: 10.1039/C7CE01341H

the Fermi level in the range of -2.15-0.07 eV have been derived from aromatic fragments
with admixture of oxygen centers and having meager contribution from the Zn(II) center.
Therefore, the electronic transition in 1 mainly takes place from the Zn(II) center and
oxygen and aromatic region. In the typical photocatalytic process, the sample 1 can be
excited to produce electron-hole pairs under visible light irradiation and as band structure
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calculations reveal that the hole moves to Zn(II) centers and the electron migrates to

CrystEngComm Accepted Manuscript

conjugated tetra-carboxylate entity. The generation of holes on the d10 Zn(II) centers will
correspond to its oxidation which is now capable to oxidize the dye to re-reduce back to
Zn(II) again and in turn degrading the dyes. On the basis of DOS calculations the
schematic representation for the possible photocatalytic mechanism is presented in Fig.
6.

Fig. 6 The schematic representation for the possible photocatalytic mechanism

exhibited by 1.

Conclusion
The luminescent MOF 1 comprising of d10 based Zn(II) centres exhibits dual sensing
capability for Fe3+/Fe2+ ions and nitro-aromatics and also displays photocatalytic
degradation of methyl violet and Rhodamine B dyes. The possible mechanism for the
quenching in luminescence have been addressed using theoretical calculations which
indicated that there may be the occurrence of both electron and energy transfer
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DOI: 10.1039/C7CE01341H

processes in addition to electrostatic interaction between the MOF 1 and nitro-aromatics

which may be responsible for the unprecedented selective luminescence quenching.
The DOS calculations reveals that under irradiation of 1 the hole moves to Zn(II)
centers and the electron migrates to terphenyl-3,3ʹʹ,5,5ʹʹ-tetracarboxylate entity. The
generation of holes on the Zn(II) centers will correspond to its oxidation which is now
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capable to oxidize the dye to re-reduce back to Zn(II) again to eventually decompose

CrystEngComm Accepted Manuscript

the organic dye. In conclusion, the synthesized d10 based luminescent MOF having
symmetrical terphenyl-3,3ʹʹ,5,5ʹʹ-tetracarboxylate entity is not only an effective sensors
for nitroaromatics and iron ions rather they prove to be a good catalyst for organic dyes
and such systems will be worthy to develop new and versatile materials as sensors and
photocatalyts. Additionally, the use of symmetrical terphenyl-3,3ʹʹ,5,5ʹʹ-tetracarboxylic
acid ligand will provide necessary impetus to deploy similar symmetrical ligand
systems to develop new MOFs which can be utilized for sensors as well as photocatalyts. 
 
 
Acknowledgments
This work was partially supported by the grants from the Science and Technology Plan Projects of
Dongguan (2016108101005), NSF of China (No 21401143), Science Foundation funded project of
Guangdong Medical University (Z2016001 and M2016023),
the Excellent Young Support Program of Anhui Province (gxyqZD2017073), innovative
Entrepreneurial Training Plan of undergraduates in Guangdong Province (201610571060;
201610571089; 201610571086; 201610571083; 201610571089 and 201610571066), the Public
Research and Capacity Building Projects of Department of Guangdong Province
(2017A010103022), Natural Science Foundation of Guangdong Province (2017A030313079).
AK is grateful to CSIR, New Delhi for the financial support in the form of project no.
01(2899)/17/EMR-II.

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