A new zinc(II) coordination polymer based on 5-methylisophthalic acid and 4,4′-dipyridylsulfide: Synthesis, structure, and photoluminescent properties

Article abstract of DOI:10.1080/15533174.2012.740752

The use of both 5-methylisophthalic acid (H₂mip) and 4,4′-dipyridyldisulfide (dpds) with Zn(II) ion under hydrothermal conditions has provided a new zinc(II) coordination polymer, [Zn(mip)(dps)] _n (1), and it has been characterized by elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction. The starting reagent dpds ligand was converted to dps (4,4′-dipyridylsulfide) in the resulting complex. It crystallizes in monoclinic space group P2₁/n with a = 12.0091(12), b = 10.9122(11), c = 13.4699(14) A, β =95.1890(10)°, C₁₉H₁₄N₂O₄SZn, M_r =431.75, V = 1757.9(3) A³, Z = 4, μ = 1.545 mm^-1, D_c = 1.631 g·cm^-1, F(000) = 880, R = 0.0380, wR = 0.1050 (I > 2σ(I)). The title complex has a 3-D 4-fold interpenetrating diamondoid network with (6⁶) topology. Photoluminescence measurements show that 1 has medium fluorescent emissions at 458 nm and 543 nm upon excitation at 322 nm. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2012.740752

This article was downloaded by: [The University of Manchester Library]
On: 13 October 2014, At: 05:51
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsrt20
A New Zinc(II) Coordination Polymer Based on 5-
Methylisophthalic Acid and 4,4′-Dipyridylsulfide:
Synthesis, Structure, and Photoluminescent Properties
Min-Le Han a , Xin-Hong Chang a & Xiao-Jie Wu a
a College of Chemistry and Chemical Engineering , Luoyang Normal University , Luoyang , P.
R , China
Accepted author version posted online: 10 Dec 2012.Published online: 26 Feb 2013.
To cite this article: Min-Le Han , Xin-Hong Chang & Xiao-Jie Wu (2013) A New Zinc(II) Coordination Polymer Based on 5-
Methylisophthalic Acid and 4,4′-Dipyridylsulfide: Synthesis, Structure, and Photoluminescent Properties, Synthesis and
Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:4, 479-482, DOI: 10.1080/15533174.2012.740752
To link to this article: http://dx.doi.org/10.1080/15533174.2012.740752
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:479–482, 2013
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.740752
A New Zinc(II) Coordination Polymer Based on
5-Methylisophthalic Acid and 4,4ꢁ-Dipyridylsulfide:
Synthesis, Structure, and Photoluminescent Properties
Min-Le Han, Xin-Hong Chang, and Xiao-Jie Wu
College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, P. R, China
twisted conformation, with a C-S-S-C torsion angle of ca. 90◦
The use of both 5-methylisophthalic acid (H2mip) and 4,4ꢁ-
dipyridyldisulfide (dpds) with Zn(II) ion under hydrothermal
conditions has provided a new zinc(II) coordination polymer,
[Zn(mip)(dps)]n (1), and it has been characterized by elemen-
tal analysis, FT-IR spectroscopy, and X-ray single-crystal diffrac-
tion. The starting reagent dpds ligand was converted to dps (4,4ꢁ-
dipyridylsulfide) in the resulting complex. It crystallizes in mon-
oclinic space group P21/n with a = 12.0091(12), b = 10.9122(11),
c = 13.4699(14) Å, β = 95.1890(10)◦, C19H14N2O4SZn, Mr = 431.75,
V = 1757.9(3) Å3, Z = 4, μ = 1.545 mm-1, Dc = 1.631 g·cm-1,
F(000) = 880, R = 0.0380, wR = 0.1050 (I > 2σ(I)). The title com-
plex has a 3-D 4-fold interpenetrating diamondoid network with
(66) topology. Photoluminescence measurements show that 1 has
medium fluorescent emissions at 458 nm and 543 nm upon excita-
tion at 322 nm.
but also the easy cleavage of the S-S bond to result in diversiform
in situ ligand reactions.[11–15]
Meanwhile, aromatic polycarboxylate are wildly used to con-
struct MOFs.[16–19] As bridging ligands, they can display various
coordination modes and bind to several metal centers to form
fascinating structures. Isophthalic acid (1,3-benzendicarboxylic
acid) and its derivatives are versatile ligands that can coor-
dinate to transition metals in a variety of modes with donor
atoms.[20–24] In this work, we reacted 5-methylisophthalate
(mip), 4,4ꢀ-dipyridyldisulfide (dpds) with Zn(II) ion, yielding
a new polymer, namely [Zn(mip)(dps)]n (1). In this case, the
starting reagent dpds ligand was converted to dps in the re-
sulting complex. Herein, we report its hydrothermal synthesis,
structural characterization, and photoluminescent properties.
Keywords 4, 4ꢀ-dipyridylsulfide, 5-methylisophthalic acid, photolu-
minescent properties, zinc(II) complex
EXPERIMENTAL
Materials and Physical Measurements
INTRODUCTION
All reagents were commercially purchased and used without
further purification. Elemental analyses (C, H, N, and S) were
performed on a Thermo Science Flash 2000 element analyzer
(Madison, WI, USA). The infrared spectra (4000–600 cm–1)
were recorded on a NICOLET 6700 FT-IR spectrometer (Madi-
son, WI, USA). The crystal determination was performed on
a Bruker SMART APEX II CCD diffractometer (Madison,
WI, USA) equipped with graphite-monochromatized Mo Kα
radiation (λ = 0.71073 Å). The photoluminescent properties
were measured on a F-4500 FL spectrophotometer (HITACHI,
Japan).
In the past decade, hydro- and solvothermal methods, featur-
ing chemical reactions in a sealed solution at elevated tempera-
ture and pressure, have been widely adopted in the preparations
new metal-organic frameworks (MOFs) with diverse structural
architectures although the mechanism is not completely clear so
far.[1–5] Hydro- and solvothermal in situ ligand reactions have
been extensively investigated due to the preparation of unpre-
dicted coordination polymers as well as for the discovery of
new organic reactions.[6–10] According to the previous reports,
4,4ꢀ-dipyridyldisulfide (dpds) may also lead to fascinating ar-
chitectures with interesting properties not only because of its
Synthesis of Complex 1
A mixture of H2mip (17.8 mg, 0.1 mmol), dpds (22.4 mg,
0.1 mmol), Zn(OAc)2·2H2O (24 mg, 0.1mmol), and KOH
(5.6 mg, 0.1 mmol) was added into water (12 mL) in a Teflon-
Received 29 March 2012; accepted 13 October 2012.
This work was supported by the Natural Science Foundation lined stainless steel vessel. The mixture was heated at 433 K
of Henan province (122102310455), the Natural Science Foundation of
for 3 days, and then slowly cooled down to room temperature.
Henan Province Educational Committee (12B150019), and the Youth
Colorless block crystals of I were obtained. Anal. Calcd. (%) for
Foundation of Luoyang Normal University (2011-QNJJ-003).
C19H14N2O4SZn: C, 52.86; H, 3.27; N, 6.49; S, 7.43. Found:
Address correspondence to Min-Le Han, College of Chemistry and
C, 52.81; H, 3.24; N, 6.54; S, 7.40. IR (cm–1): 3080w, 1694s,
Chemical Engineering, Luoyang Normal University, Luoyang 471000,
P. R, China. E-mail: minle han@163.com
1615s, 1573s, 1465m, 1442m, 1205s, 812s, 674s.
479

480
M.-L. HAN ET AL.
TABLE 2
Crystallographic Data Collection
and Structure Determination
Selected bond distances and angles for 1
Zn(1)-O(4)#1a
Zn(1)-N(1)
1.944(2) Zn(1)-O(1)
2.057(3) Zn(1)-N(2)#2
1.959(2)
2.063(3)
117.61(12)
A single crystal of 1 was put on a Bruker SMART APEX
II CCD diffractometer (Madison, WI, USA) equipped with a
graphite monochromated MoKα radiation (λ = 0.71073 Å) by
using a θ/ω scan technique at room temperature.The structures
were solved by direct methods with SHELXS-97.[25] The hy-
drogen atoms were assigned with common isotropic displace-
ment factors and included in the final refinement by use of ge-
ometrical restrains, while the non-hydrogen atoms were treated
with common anisotropic displacement factors and included in
the final refinement with geometrical restrains. A full-matrix
least-squares refinement on F2 was carried out using SHELXL-
97.[26] The final agreement factor values are R = 0.0380 and
wR = 0.1050 (w = 1/[σ2(Fo)2 + (0.0516P)2 + 0.5883P] where
O(4)#1-Zn(1)-O(1) 102.48(10) O(4)#1-Zn(1)-N(1)
O(1)-Zn(1)-N(1)
O(1)-Zn(1)-N(2)#2 106.99(11) N(1)-Zn(1)-N(2)#2
113.80(11) O(4)#1-Zn(1)-N(2)#2 100.27(11)
114.09(11)
aSymmetry transformations used to generate equivalent atoms: #1:
x – 1/2, –y – 1/2, z – 1/2; #2: x – 1/2, –y + 1/2, z + 1/2.
details and the selected bond lengths and bond angles are sum-
marized in Tables 1 and 2, respectively.
RESULTS AND DISCUSSION
2
2
Crystal Structure Description
P = (Fo +2Fc )/3) for 1. Crystallographic and experimental
The asymmetric unit of 1 contains one Zn2+ ion, one mip
ligand, and one dps ligand. The starting dpds ligand was con-
verted into dps in the resulting complex. The Zn2+ ion is four-
coordinated with a distorted tetrahedral geometry, as shown in
Figure 1. Each Zn2+ ion is coordinated to two carboxylate oxy-
gen atoms of two mip anions and a pair of pyridyl nitrogen
atoms of dps. The Zn-O bond lengths are 1.944(2) and 1.959(2)
Å and the Zn-N ones are 2.057(3) and 2.063(3) Å, respectively.
The adjacent Zn2+ ions are linked by mip ligands to form a
chain (Figure 2). These 1D motifs are further connected through
dps ligands to generate a 3D network (Figure 3). In order to
minimize the big void cavities and stabilize the framework, the
potential voids formed by a single 3D network show incorpora-
tion of other three identical ones, thus affording a 4-fold paral-
lel interpenetrating diamondoid network with a Schla¨fli symbol
of (66) (Figure 4). Interestingly, the structure of 1 is similar
to [Zn(isop)(dps)]n (H2isop = benzene-1,3-dicerboxylic acid,
dps = 4,4ꢀ-dipyridyl sulfide).[27]
TABLE 1
Crystallographic data and details of the experiment and
refinement for 1
Parameter
Value
Color/shape
Formula weight
Temperature, K
Crystal system
Space group
a (Å)
Colorless/block
431.75
295(2) K
monoclinicꢀ
P21/n
12.0091(12)
10.9122(11)
13.4699(14)
95.1890(10)
1757.9(3)
b (Å)
c (Å)
β(◦)
V (Å3)
Z
4
Dcalc(g·cm–3)
1.631
1.545
μ(mm–1)
F(000)
880
Crystal size, mm3
θ range (◦)
Limiting indices
0.40 × 0.25 × 0.13
2.38–25.50
–14 ≤ h ≤ 14, –13 ≤ k ≤ 13,
–15 ≤ l ≤ 16
11043
Reflections collected
Independent reflections
Reflections with I > 2σ(I)
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices (I > 2σ(I))
R indices (all data)
3240 (Rint = 0.0237)
2758
3240/162/245
1.045
R1 = 0.0380, wR2 = 0.1050
R1 = 0.0459, wR2 = 0.1105
1.540 and –0.597
Largest diff. peak and
hole, e Å–3
FIG. 1. Coordination environment of Zn(II) ion in 1. Hydrogen atoms are
omitted for charity. Symmetry codes: A, x – 1/2, –y – 1/2, z – 1/2; B, x – 1/2, –y
+ 1/2, z + 1/2.
ꢀ
ꢀ
ꢀ
ꢀ
2
R = [ eˆeˆF0 eˆ –eˆFceˆeˆ/
eˆF0 eˆ], RW
=
[eˆF0 –Fc2 eˆ2/
W
W
(eˆFweˆ2) 2]1/2
.

METAL-ORGANIC FRAMEWORKS
481
FIG. 2. Polyhedron view of the 1D chain in 1.
Photoluminescent Properties
Coordination polymers with d10 metal centers and organic
ligands are promising candidates for photoactive materials
with potential applications such as chemical sensors and pho-
tochemistry.[28] The solid-state photoluminescent property of
compound 1 has been investigated at room temperature. The
fluorescence and emission peaks are shown in Figure 5 The
measurement of photoluminescence spectra of 1 shows a flu-
orescence emission at 458 nm and 543 nm upon excitation at
288 nm. Compared with H2mip ligands and Na2mip (excitation
at ca. 280 nm for H2mip and 300 nm for Na2mip, which show
the emissions at ca. 380 nm for H2mip and 328 nm for Na2mip),
the emission maximums of 1 show red shift. Since the Zn(II)
ions are difficult to oxidize or reduce, these bands should be
assigned to the intraligand fluorescent emissions that are tuned
by the metal-ligand interactions.[29]
FIG. 4. The 3D 4-fold interpenetrating structure in 1.
FIG. 5. The fluorescent emission spectra of 1 in the solid state at room tem-
FIG. 3. 3D polyhedron view in 1.
perature.

482
M.-L. HAN ET AL.
situ ligand formation from 4,4ꢀ-dipyridyldisulfide. CrystEngComm 2009,
CONCLUSIONS
11, 2593–2596.
In summary, a new complex, [Zn(mip)(dps)]n (1) (H2mip =
5-methylisophthalic acid, dps = 4,4ꢀ-dipyridylsulfide), has been
synthesized under hydrothermal conditions and characterized
by elemental analysis, FT-IR spectroscopy, and X-ray single-
crystal diffraction. The title complex has a 3-D 4-fold inter-
penetrating diamondoid network with (66) topology. Photolu-
minescence measurement show that 1 has medium fluorescent
emission.
12. Han, L.; Bu, X.; Zhang, Q.; Feng, P. Solvothermal in situ ligand synthesis
through disulfide cleavage: 3D (3,4)-connected and 2D square-grid-type
coordination polymers. Inorg. Chem. 2006, 45, 5736–5738.
13. Wang, J.; Zhang, Y.H.; Li, H.X.; Lin, Z.J.; Tong, M.L. Construction of
pyridinethiolate-bridged 2D and 3D coordination networks of d10 metal
halides via solvothermal in situ disulfide cleavage reactions. Cryst. Growth
Des. 2007, 7, 2352–2360.
14. Ma, L.F.; Wang, Y.Y.; Wang, L.Y.; Lu, D.H.; Batten, S.R.; Wang, J.G.
Two coordination polymers involving triangular and linear trinuclear Co(II)
clusters created via in situ ligand synthesis. Cryst. Growth Des. 2009, 9,
2036–2038.
SUPPLEMENTARY MATERIALS
15. Zhu, H.B.;Gou, S.H. Insituconstructionofmetal–organic sulfur-containing
heterocycle frameworks. Coord. Chem. Rev. 2011, 255, 318–338.
16. Mu¨ller, U.; Schubert, M.; Teich, F.; Puetter, H.; Schierle-Arndt, K.; Pastre´,
J. Metal-organic frameworks: prospective industrial applications. J. Mater.
Chem. 2006, 16, 626–636.
The atomic coordinates and other parameters of struc-
ture 1 have been deposited with the Cambridge Crystallo-
graphic Date Centre (no. 867730; deposit@ccdc.cain-ac.uk or
http://www.ccdc.cam.ac.uk).
17. Czaja, A.U.; Trukhan, N.; Mu¨ller, U. Industrial applications of metal-
organic frameworks. Chem. Soc. Rev. 2009, 38, 1284–1293.
18. Ma, L.F.; Li, C.P.; Wang, L.Y.; Du, M. CoII and ZnII coordination frame-
works with benzene-1,2,3-tricarboxylate tecton and flexible dipyridyl co-
ligand: a new type of entangled architecture and a unique 4-connected
topological network. Cryst. Growth Des. 2011, 11, 3309–3312.
19. Volkringer, C.; Loiseau, T.; Guillou, N.; Fe´rey, G.; Haouas, M.; Taulelle,
F.; Elkaim, E.; Stock, N. High-throughput aided synthesis of the porous
metal-organic framework-type aluminum pyromellitate, MIL-121, with ex-
tra carboxylic acid functionalization. Inorg. Chem. 2010, 49, 9852–9862.
20. Ma, L.F.; Li, X.Q.; Wang, L.Y.; Hou, H. W. Syntheses and charac-
terization nickel(II) and cobalt(II) coordination polymers based on 5-
bromoisophthalate anion and bis(imidazole) ligands. CrystEngComm 2011,
13, 4625–4634.
REFERENCES
1. (a) Liu, J.Q.; Liu, B.; Wang, Y.Y.; Liu, P.; Yang, G.P.; Liu, R.T.; Shi,
Q.Z.; Batten, S.R. An unusual 3D entangled Co(II) coordination poly-
mer directed by ferromagnetic molecular building block. Inorg. Chem.
2010, 49, 10422–10426. (b) Liu, J.Q.; Wang, Y.Y.; Huang, Y.S. Structural
variability of Co(II) and Ni(II) entangled metal–organic frameworks: ef-
fect of N-donor ligands and metal ions. CrystEngComm 2011, 13, 3733–
3740.
2. Zou, H.H.; He, Y.P.; Gui, L.C.; Liang, F.P. A new 8-connected porous
coordination polymers: crystal structure and selective adsorption properties.
CrystEngComm 2011, 13, 3325–3329.
21. Ma, L.F.; Wang, L.Y.; Du, M.; Batten, S.R. Unprecedented 4- and 6-
connected 2D coordination networks based on 44-subnet tectons, showing
unusual supramolecular motifs of rotaxane and helix. Inorg. Chem. 2010,
49, 365–367.
3. Fu, F.; Li, D.S.; Wu, Y.P.; Gao, X.M.; Du, M.; Tang, L.; Zhang, X.N.; Meng,
C.X. A versatile V-shaped tetracarboxylate building block for constructing
mixed-ligand Co(II) and Mn(II) complexes incorporating various N-donor
co-ligands. CrystEngComm 2010, 12, 1227–1237.
22. Tian, C.B.; He, Z.Z.; Li, Z.H.; Lin, P.; Du, S.W. Two new ferromag-
netic MnII-carboxylate coordination polymers constructed from 5-tert-butyl
isophthalic acid with (5/2, 15/2) and (5/2, 10/2) spin topologies. CrystEng-
Comm 2011, 13, 3080–3086.
23. Zang, S.Q.; Fan, Y.J.; Li, J.B.; Hou, H.W.; Mak, T.C. W. Halogen bonding
in the assembly of coordination polymers based on 5-iodo-isophthalic acid.
Cryst. Growth Des. 2011, 11, 3395–3405.
4. (a) Fu, A.Y.; Jiang, Y.L.; Wang, Y.Y.; Gao, X.N.; Yang, G.P.; Hou, L.; Shi,
Q.Z. DMF/H2O volume ratio controls the syntheses and transformations of
a series of cobalt complexes constructed using a rigid angular multitopic
ligand. Inorg. Chem. 2010, 49, 5495–5502. (b) Liu, J.Q.; Huang, Y.S.; Zhao,
Y.Y.; Jia, Z.B. Molecular tectonics of entangled metal−organic frameworks
based on different conformational carboxylates mixed with a flexible N,Nꢀ-
type ligand. Cryst. Growth Des. 2011, 11, 569–574.
24. Chen, J.; Li, C.P.; Du, M. Substituent effect of R-isophthalates (R = -H,
-CH3, -OCH3, -tBu, -OH, and –NO2) on the construction of CdII coordi-
nation polymers incorporating a dipyridyl tecton 2,5-bis(3-pyridyl)-1,3,4-
oxadiazole. CrystEngComm 2011, 13, 1885–1893.
25. Sheldrick, G.M. SHELXS 97, Program for the Solution of Crystal Structure;
University of Go¨ttingen, Germany, 1997.
26. Sheldrick, G.M. SHELXL 97, Program for the Crystal Structure Refinement;
University of Go¨ttingen, Germany, 1997.
27. Zhang, W.Y.; Yuan, S.; Tang, K.; Xie, Y.F.; Zhang, J.C.; Synthesis, crys-
tal structure and fluorescent properties of a 4-fold interpenetrating Zn(II)
polymer. Chin. J. Struct. Chem. 2010, 29, 138–141.
28. Santis, G.D.; Fabbrizzi, L.; Licchelli, M.; Poggi, A.; Taglietti, A. Molecular
recognition of carboxylate ions based on the metal-ligand interaction and
signaled through fluorescence quenching. Angew. Chem., Int. Ed. Engl.
1996, 35, 202–204.
29. Li, B.; Yang, F.; Li, G.; Liu, D. Zhou, Q.; Shi, Z.; Feng, S. Construction of
coordination polymers based on bent 4-amino-3,5-bis(3-carboxyphenyl)-
1,2,4-triazole ligand: diverse structural topology and photoluminescent and
magnetic properties. Cryst. Growth Des. 2011, 11, 1475–1485.
5. (a) Stock, N.; Biswas, S. Synthesis of metal-organic frameworks (MOFs):
routes to various MOF topologies, morphologies, and composites. Chem.
Rev. 2012, 112, 933–969. (b) Liu, J.Q.; Wang, Y.Y.; Jia, Z.B. An unusual
3D metal-organic framework with multiform helical chains. Inorg. Chem.
Comm. 2011, 14, 519–521.
6. Evans, O.R.; Lin, W. Crystal engineering of NLO materials based on metal-
organic coordination networks. Acc. Chem. Res. 2002, 35, 511–522.
7. Lu, J.Y. Crystal engineering of Cu-containing metal–organic coordination
polymers under hydrothermal conditions. Coord. Chem. Rev. 2003, 246,
327–347.
8. Zhang, X.M. Hydro(solvo)thermal in situ ligand syntheses. Coord. Chem.
Rev. 2005, 249, 1201–1219.
9. Zhang, J.P.; Chen, X.M. Crystal engineering of binary metal imidazolate
and trizolate frameworks. Chem. Commun. 2006, 1689–1699.
10. Chen, X.M.; Tong, M.L. Solvothermal in situ metal/ligand reactions: a new
bridge between coordination chemistry and organic synthetic chemistry.
Acc. Chem. Res. 2007, 40, 162–170.
11. Ma, L.F.; Wang, L.Y.; Du, M. A novel 3D Mn(II) coordination polymer
involving 4,4ꢀ-dipyridylsulfide and 4,4ꢀ-dipyridyltrisulfide obtained by in