Synthesis, structures, luminescent and magnetic properties of four coordination polymers based on biphenyl-2,4′,5-tricarboxylic acid and different N-donor ligands

    Synthesis, structures, luminescent and magnetic properties of four coordination polymers based on biphenyl-2,4 ,5-tricarboxylic acid and different N-donor ligands Xuzhao Liao, Wujuan Sun, Dandan Zhai, Xiaoling Wang, Jiemin Dong, Xuwu Yang PII: DOI: Reference:

S1387-7003(16)30149-6 doi: 10.1016/j.inoche.2016.05.010 INOCHE 6320

To appear in:

Inorganic Chemistry Communications

Received date: Revised date: Accepted date:

1 April 2016 27 April 2016 15 May 2016

Please cite this article as: Xuzhao Liao, Wujuan Sun, Dandan Zhai, Xiaoling Wang, Jiemin Dong, Xuwu Yang, Synthesis, structures, luminescent and magnetic properties of four coordination polymers based on biphenyl-2,4 ,5-tricarboxylic acid and different N-donor ligands, Inorganic Chemistry Communications (2016), doi: 10.1016/j.inoche.2016.05.010

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ACCEPTED MANUSCRIPT Synthesis, structures, luminescent and magnetic properties of four coordination polymers based on biphenyl-2,4',5-tricarboxylic acid

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and different N-donor ligands

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Xuzhao Liaoa, Wujuan Suna, Dandan Zhaia, Xiaoling Wanga, Jiemin Donga, Xuwu Yanga a

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of

Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and

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Materials Science, Northwest University, Xi’an, 710069, P. R. China

∗Corresponding author: Xuwu Yang

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College of Chemistry and Material Science, Northwest University

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University avenue NO.1, Xi'an 710069, Shaanxi prov., P. R. China. E-mail address: [email protected]

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Tel: +86 29 88302054

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fax: +86 29 88303798

ACCEPTED MANUSCRIPT Abstract Four new coordination polymers [Zn(HL)(bibp)]n (1: H3L = biphenyl-2,4',5-tricarboxylic acid, bibp = 4,4'-bis(imidazolyl)biphenyl), [Co(HL)(bibp)]n (2), [Co(HL)(bib)]n·4nH2O (3: bib =

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1,4-bis(1-imidazoly)-benzene), [Co1.5(L)(bib)1.5(H2O)]n·3nH2O (4), have been synthesized under solvo/hydrothermal conditions, and have been fully characterized by single-crystal X-ray powder

X-ray

diffraction

(PXRD),

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spectra,

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diffraction,

elemental

analysis

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thermogravimetric analysis (TGA). Structural analyses reveal that both 1 and 2 display a 4-fold interpenetrated framework. Complex 3 possesses a 2D (4,4) network. Complex 4 exhibits a 3D

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framework with the point symbol of {32·4·67}2{32·610·72·8}. Moreover, photoluminescence

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interpenetration,

coordination

polymers,

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Keywords: isostructural, biphenyl-2,4',5-tricarboxylic acid

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properties of 1 and magnetic properties of 2-4 have also been studied in detail.

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Recently, coordination polymers (CPs) have acquired extensive attention due to their novel topologies and intriguing architectures [1-3], and which can be potentially applied in various areas

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such as photoluminescence, magnetism, heterogeneous catalysis, gas and hydrocarbon separation and storage, ion exchange and so on [4-13]. However, the construction of CPs is affected by a variety of factors, like organic ligands, metal ions, solvent, temperature and ratio of reactants etc

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[14-22]. To be noted, appropriate organic ligand can extend the diversities of the CPs due to whose great difference in the lengths, flexibility and steric arrangement. In addition, the aromatic multicarboxylate ligands play a crucial role in tuning the framework among the alternative organic ligands, owing to its abundant coordination modes. Furthermore the desired geometric of metal centers can be facilely obtained with these modes, and leading to fascinating structural architectures with interpenetration networks [23, 24]. So currently, CPs with interpenetrated networks are widely investigated. A number of individual nets of interpenetrating with each other will give an interpenetrated framework. What’s more, long and flexible ligands were widely adapted in most case of the entangled structure due to the strong affinity to the entangled mode by the length and flexibility of the spacer ligands, especially those long N-heterocycle ligands, like 1,4-bis(1-imidazoly)-benzene (bib), 4,4'-bis(imidazolyl)biphenyl (bibp) and so on [25-39]. Herein, considering mentioned factor above, a new rigid and asymmetric ligand,

ACCEPTED MANUSCRIPT biphenyl-2,4',5-tricarboxylic acid (H3L) was chosen to construct the coordination architecture in this work. The selection of the ligand is based on the following considerations: (i) Three carboxyl groups can be completely or partially deprotonated, producing various structural modes. (ii) The

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carboxyl can act as a hydrogen bond donor and receptor. (iii) The π-π conjugated effect produced by two aromatic rings of ligand can improve the stability of the framework, and also show great

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expectation for optical phenomena [40-45]. Fortunately, four new CPs [Zn(HL)(bibp)]n (1), [Co(HL)(bibp)]n (2), [Co(HL)(bib)]n·4nH2O (3), [Co1.5(L)(bib)1.5(H2O)]n·3nH2O (4), have been successfully synthesized based on H3L, bibp and bib (Fig.1) via solvo/hydrothermal approach.

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The photoluminescent properties of 1 and magnetic properties of 2-4 have also been studied in detail, respectively.

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(Here inset Fig.1)

Complex 1 was synthesized by ZnSO4, bibp and H3L ligand in EtOH/H2O (1:2, v/v) solution

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under solvothermal conditions at 160 ℃. Complex 2 was synthesized in a similar way to 1 except

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that ZnSO4 was replaced by CoSO4. As 1 and 2 are isostructural, we chose 1 to describe the crystal structure of both polymers in this article. X-ray crystallographic studies reveal that the 1

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crystallizes in the P21/c space group of the monoclinic system and possessing a 3D and 4-fold interpenetrated framework. The asymmetric unit contains one Zn(II) ion, one HL2- ligand and one bibp ligand. The Zn(II) ion is four coordinated with two nitrogen atoms from two bibp ligands

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[Zn-N = 1.980(4)-2.019(4) Å] and two carboxylic oxygen atoms from two HL2- ligands [Zn-O = 1.943(4)-1.978(3) Å] (Fig. 2a). The four-coordinated Zn(II) ion exhibits a slightly distorted square tetrahedral geometry. In this complex, the carboxyl groups of H3L ligand have been partially deprotonated and adopt μ2-η0:η0:η0:η1:η1:η0 coordination mode. As depicted in Fig 2, each adjoining Zn(II) ion connect with bibp ligands to form an infinite one-dimensional chain [Zn(bibp)]n. Then, through the bridged HL2-, the adjacent chains are linked by HL2- to form a two-dimensional network [Zn(HL)(bibp)]n extending in the ac plane. Changing the view direction, we can obviously find out the existence of channels in this framework. Topologically, the HL2ligand and bibp ligand both can be simplified as 2-connected linkers and the Zn(II) ion act as a 4-connected node, thus the structure is simplified as a dia network. Furthermore, four identical nets are interpenetrating, resulting into the final 4-fold network with each six-membered ring interpenetrating with other three six-membered rings. At last, the 4-fold interpenetrated topology

ACCEPTED MANUSCRIPT with the point symbol of 66 is generated. (Here inset Fig. 2) Complex 3 was synthesized by CoSO4, bib and H3L ligand under hydrothermal conditions at

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180 ℃, which crystallizes in the monoclinic system, P21/c space group, possessing a 2D layered

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structure. The asymmetric unit contains one Co(II) ion, one partially deprotonated HL2- ligand,

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one bib ligand and four lattice water molecules. The Co(II) ion is five coordinated with two nitrogen atoms from two bib ligands [Co-N = 2.030(4)-2.036(4) Å] and three carboxylic oxygen atoms from two HL2- ligands [Co-O = 1.970(3)-2.276(3) Å]. The five-coordinated Co(II) ion

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exhibits a slightly distorted square-pyramidal coordination geometry. As depicted in Fig 3, each adjoining Zn(II) ion connected with bib ligands to form an infinite one-dimensional chain

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[Co(bib)]n. Then, through the bridged HL2-, the adjacent chains are linked by HL2- to form a two-dimensional network [Co(HL)(bib)]n extending in the bc plane. The channels can be easily

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found, which is estimated to be 447.3 Å3 using the PLATON software, almost 16.5% of the per

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unit cell volume 2723.7(8) Å3, the yellow sphere represents the large pore defined within the frameworks. In complex 3, the carboxyl groups of H3L ligand have been partially deprotonated

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and adopt μ2-η0:η0:η0:η1:η1:η1 coordination mode. From a topological view, the Co(II) ion act as a 4-connected node, the HL2- ligand and bib ligand both can be simplified as 2-connected linkers,

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the overall topology can be described as a 2D (4,4) network. (Here inset Fig. 3)

Complex 4 was synthesized in a similar way to 3, except that CoSO4 was replaced by Co(OAc)2. X-ray crystallographic studies reveal that the 4 crystallizes in monoclinic system with P21/c space group and possessing a 3D network. The asymmetric unit contains one and a half Co(II) ion, one wholly deprotonated L3- ligand, one and a half bib ligand, a coordinated water molecular and three lattice water molecules. As showed in Fig 4a, The Co1#1 is six coordinated with two nitrogen atoms from two bib ligands, two carboxylic oxygen atoms from two L3- ligands and two water oxygen atoms to form a slightly distorted CoO4N2 octahedral geometry; While Co2 is five coordinated with three carboxylic oxygen atoms from three L3- ligands and two nitrogen atoms from two bib ligands to form a distorted CoO3N2 hexahedral geometry. The Co-O bond lengths are in the range of 1.932(7)-2.404(8) Å, and the Co-N bond lengths are in the range of 2.015(9)-2.151(9) Å. In this complex, the carboxyl groups of H3L ligand have been completely

ACCEPTED MANUSCRIPT deprotonated and adopt μ3-η1:η1:η0:η1:η1:η0 coordination mode. As depicted in Fig 4b, each adjoining Co2 ion connected with bib ligands to form an infinite one-dimensional chain [Co(bib)]n. The chains are parallel to each other. Through the bridging effect of L3- ligands and bib ligands,

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the adjacent chains are linked to form a 3D network. To simplify the intricate structure of 4, the

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Co1 and Co2 both can be simplified as 4-connected nodes, L3- ligand can be simplified as

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3-connected nodes and the bib ligand can be reduced to 2-connected nodes, Consequently, a 3D topological network with the point symbol of {32·4·67}2{32·610·72·8} is generated. (Here inset Fig. 4)

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In order to better understand the effect of metal ions and auxiliary ligands on the structures, complex [Zn(HL)(bib)]n·2nH2O (5), which reported in our previous report were compared with

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the title complexes [46]. Complexes 1 and 2 are isostructural, and complexes 3 and 5 also exhibit a isostructural structure. It indicates that the Zn(II) and Co(II) ions have similar isostructural

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coordination in specific conditions. In comparison with these two kinds of structures, the auxiliary

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ligands play a crucial role in the construction of frameworks. The longer bibp makes bigger channels than the shorter bib. In result, complexes 1 and 2 exhibit a 3D and 4-fold interpenetrated

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frameworks, complexes 3 and 5 show a 2D layered network. As to the synthesis of 3 and 4, the reaction conditions are the same except for the different anions of same metal ion. As a result, complex 4 exhibits a 3D framework, which is more intricate than 3. The structural differences of 3

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and 4 reveal that the anions of metal salt also make great influence in the generation of the crystal structure.

To study the thermal stability of complexes 1-4, thermogravimetric analysis (TGA) were measured on a polycrystalline sample under nitrogen atmosphere from 30 ℃ to 800 ℃, and the TGA curves are shown in Fig. S1. For 1, there is only one weight loss process was observed. The stable structure of the compound can be observed before 400 ℃. Upon further heating, the framework starts to collapse, and the 2 shows the same curve as 1. For 3, the first weight loss was observed from 60 ℃ to 150 ℃, corresponding to the loss of water molecules. Then the skeleton of 3 begins to collapse when the temperature reach 300 ℃. Complex 4 exhibits a weight loss in the range of 80-150 ℃, corresponds to loss of water molecules. The framework of 4 begins to collapse from 350 ℃. The X-ray powder diffraction (PXRD) measurement displayed that the diffraction peaks of both

ACCEPTED MANUSCRIPT the simulated and experimental patterns match well in relevant positions, indicating a good phase purity of these products (Fig. S2). MOFs with d10 ions have became potential fluorescent materials for widely applied in the

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optical field. [47]. Therefore, in this work, the photoluminescent properties of H3L, bibp and 1 were investigated in the solid state under room temperature (Fig. 5). The main emission peaks of

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H3L and bibp showed at 427 nm (λex = 330 nm) and 421 nm (λex = 320 nm)，respectively. The emission bands of these free ligands are probably caused by the π* → π or π* → n transitions [48]. 1 display emission peak at 452 nm upon excitation at λ = 400 nm. Comparing with the emission

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spectrum of free ligands, red shift of emission bands for 1 had been observed which can be ascribed to the difficulty of d10 configuration ions (Zn(II)) to oxidize or to reduce. Therefore, the

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emissions of these complexes are neither metal-to-ligand charge transfer (MLCT) nor ligand-to-metal transfer (LMCT) in nature. Thus, the emission of 1 is probably assigned to

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intraligand (π* → π or π* → n) emission [49-51].

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(Here inset Fig. 5)

The variable-temperature magnetic susceptibility of 2-4 was investigated in the range 1.8-300 K

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with a field of 1000 Oe. The χM and χMT versus T plots of complexes 2-4 are shown in Fig. 6. The χMT values at 300 K are 2.65 cm3 K mol-1, 2.41 cm3 K mol-1, 3.94 cm3 K mol-1 respectively, which are higher than the value expected for an isolated Co(II) ion (1.87 cm3 K mol-1) [52-54]. As the

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temperature decreases, the χMT values also decrease. The 1/χM vs T plots obey the Curie-Weiss law χM = C/(T - θ) with C = 2.63 cm3 K mol-1, θ = -5.13 K (2), C = 2.39 cm3 K mol-1, θ = -4,81 K (3), C = 3.96 cm3 K mol-1, θ = -6.98 K (4) (Fig. 6). The Weiss constant θ are all negative values, which indicate the presence of antiferromagnetic coupling from the Co(II) system. Taking into consideration, the structure suggests that magnetic interactions between adjacent cobalt (d(Co… Co) = 10.708 Å, 10.692 Å and 8.475 Å at a minimum respectively) are likely to be comparatively weak. Hence, the magnetic behavior of 2-4 is mainly caused by single-ion properties. (Here inset Fig. 6) In summary, four new coordination polymers based on biphenyl-2,4',5-tricarboxylic acid (H3L), 4,4'-bis(imidazolyl)biphenyl (bibp) and 1,4-bis(1-imidazoly)-benzene (bib) have successfully synthesized under solvo/hydrothermal conditions. 1 and 2 are isomorphic, and show a 3D four coordinated and 4-fold interpenetrated framework with the point symbol of 66. Complex 3 shows a

ACCEPTED MANUSCRIPT 2D (4,4) network. Complex 4 exhibits a 3D topological network with the point symbol of {32·4·67}2{32·610·72·8}. The photoluminescence emissions show that the 1 may be a good candidate for optical material. The 2-4 show weak antiferromagnetic coupling properties. 1 and 2

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display high thermal stabilities because interpenetration networks may enhance the thermal stability of the materials. Moreover, metal ions and auxiliary ligands act as curial role on the

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structures of complexes.

ACCEPTED MANUSCRIPT Acknowledgments This work was supported by the Agricultural Research Program of Shaanxi province (No.

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202040009).

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Fig. 1. Structures of H3L and the auxiliary ligands. Fig. 2. (a) Coordination environment of the Zn(II) atom in 1, symmetry codes: #1, x+1, -y-1/2, z+1/2; #2, x-1, -y-1/2, z-1/2; (b) View of 2D network; (c) A single diamond unit cage of 1; (d) The space filling mode of a single 3D dia net; (e) Topology of a single framework; (f) Left: Topological representation of the 4-fold frameworks. Right: View of 4-fold interpenetrated nets. Fig. 3. (a) Coordination environment of the Co(II) atom in 3, (b) View of 1D chain in complex 3; (c) View of 2D network of 3; (d) Schematic representation of the pores in the framework of 3; (e) Topology framework of 3. Fig. 4. (a) Coordination environment of the Co(II) atoms in 4, symmetry codes: #1, -x+1, -y+1, -z+1; #2, -x+1, -y, -z; (b) View of 1D chain in complex 4; (c) Schematic representation of the 3D framework of 4; (d) View of the topological net of 4. Fig. 5. The Solid-state emission spectra of the H3L ligand, bibp ligand and 1.

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Fig. 6. (a) Temperature dependence of χM, χMT and 1/χM (inset) for 2. The red line shows the best-fit curve to the Curie–Weiss law; (b) Temperature dependence of χM, χMT and 1/χM (inset) for 3. The red line shows the best-fit curve to the Curie–Weiss law; (c) Temperature dependence of χM, χMT and 1/χM (inset) for 4. The red line shows the best-fit curve to the Curie–Weiss law.

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Highlights Synthesis of four new coordination polymers based on biphenyl-2,4',5-tricarboxylic acid. photoluminescence properties of 1 and magnetic properties of 2-4 have been studied. Zn(II) and Co(II) ions are easily to construct isostructural coordination polymers in specific conditions.