Coordination Polymers Based on OrganicâInorganic Hybrid Rigid Rod

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Coordination Polymers Based on Organic-Inorganic Hybrid Rigid-rod Comprising a Backbone of Anderson-Evans POMs Mao-Chun Zhu, Ying-Ying Huang, Jian-Ping Ma, Sheng-Min Hu, Yue Wang, Jun Guo, Yan-Xi Zhao, and Long-Sheng Wang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01467 • Publication Date (Web): 31 Dec 2018 Downloaded from http://pubs.acs.org on January 1, 2019

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Crystal Growth & Design

Coordination Polymers Based on Organic-Inorganic Hybrid Rigid-rod Comprising a Backbone of Anderson-Evans POMs Mao-Chun Zhu,1, ǂ Ying-Ying Huang,1, ǂ Jian-Ping Ma,2 Sheng-Min Hu,3 Yue Wang,1 Jun Guo,4,* Yan-Xi Zhao,5 Long-Sheng Wang,1,3,5,* 1

School of Materials and Chemical Engineering, Hubei Provincial Key Laboratory of Green

Materials for Light Industry, Hubei University of Technology, Wuhan, 430068, PR China 2

College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation

Center of Functionalized Probes for Chemical Imaging, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan 250014, PR China 3

State Key Laboratory of structural chemistry, Fujian Institute of Research on the Structure of

Matter, CAS, Fujian Fuzhou, 350002, PR China 4 College

of Chemistry, Central China Normal University, Key Laboratory of Pesticide &

Chemical Biology of Ministry of Education, Wuhan, 430079, PR China 5

Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission &

Ministry of Education, South-Central University for Nationalities, Wuhan, 430074, PR China

ACS Paragon Plus Environment

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Dedicated to the 80th birthday of Professor Xin-Tao Wu KEYWORDS: Coordination Polymer, Polyoxometalates; Pyridine, Luminescence, Copper (I) ABSTRACT To construct polyoxometalates coordination polymers (PCPs), we prepared two pyridine ligand functionalized Anderson POMs: (TBA)3[MnMo6O18((OCH2)3CN=CH-4-Py)2]·DMF ((TBA)3POM-1,

TBA

=

tetrabutyl

ammonium,

Py

=

pyridine)

and

(TBA)3[MnMo6O18((OCH2)3CN=CH-3-Py)2] ((TBA)3POM-2) via the post-functionalization of (TBA)3[MnMo6O18((OCH2)3CNH2)2]

(Anderson-NH2)

by

4-pyridinealdehyde

and

3-

pyridinealdehyde, respectively. They are characterized using X-ray single crystal diffraction, MALDI-TOF MS, ESI MS, FT-IR, UV-Vis and 1H NMR . The self-assembly of (TBA)3POM-1 and [Cu(PPh3)2(CH3CN)2]ClO4 (CuP2) in the mole ratios of 1 : 2 and 1 : 3, both gave the same 1D double chain with the molecular formula of (NBu4)n{[Cu(PPh3)2]2(POM-1)}n (7.5DMF)n (1). On the contrary, the self-assembly of (TBA)3POM-2 and CuP2 in the mole ratio of 1:2 yields a 2D coordination polymer of (TBA)n{[Cu(PPh3)2]2(POM-2)}n·(2DMF)n (2), while that selfassembly process in the mole ratio of 1:3 results in different 2D coordination polymer of {[Cu(PPh3)2]3(POM-2)·(CH3CN)}n·(5CH3CN)n (3). Compounds 1-3 can keep their skeleton structures below 230oC. They exhibit intense green emission (496nm for 1; 537nm for 2; 530nm for 3) by ultra-violet irradiation (327nm for 1; 303nm for 2; 331nm for 3), which can be tentatively ascribed as ILCT with metal perturbation.

Introduction


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During the past fifty years, the research on coordination polymers (CPs) had made an amazing advance owing to enriched coordination modes of metal ions and availability of ligands with various symmetries.1, 2 The directionality associated with metal ions and the tunable structures of organic ligands not only result in the multifarious structures (from 1D infinite chain to 3D porous framework), but also afford different functions (i.e. gas adsorption, luminescence, magnetism or catalysis).3, 4 Recently, polyoxometalates (POMs), as a novel type of inorganic ligands with high stabilities and versatile coordination modes, provide platforms for the design and preparation of highly complexed POMs coordination polymers (PCPs). POMs are a kind of anionic cluster with diverse structures and compositions comprising earlytransition metal (V, Mo, W) in their high oxidation state (+5, +6) and oxide.5,

6

POMs have

claimed broad applications in fields of magnetism,7 medicine,8,9 catalysis,10 non-volatile storage devices11 owing to their redox properties. Incorporation of POMs into CPs to build PCPs can not only introduce the functions of POMs into CPs, but also possibly engender synergetic interaction between the POMs and CPs.12,13 To date, three strategies have been developed to construct PCPs. The first is utilizing polyoxometalates as building blocks to build PCPs.14,15 The second is the capture of polyoxometalates cluster in the pores of MOFs.16 For example, Lu et. al reported a MOF consisting of sextuple intercatenation of isolated adamantane-like cages using [PW12O40]3– generated in situ as template;17 Zubieta et. al. had prepared a porphyrin metal organic framework (PMOF) including hexamolybdates as anionic template using tetrapyridylporphyrin as linkers with the solvothermal technique.18 Both strategies had been very successful, however, the assembled result is difficult to predict owing to the difficulty controlling the coordination mode of POMs and the unpredictable synthetic conditions involved, which may result in structural change of POMs.


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The third method is to utilize organic derivatized POMs with remote functional groups as linkers, which processes the flexible coordination ability of organic ligand while retaining the structure and function of the POMs. For instance, Hasenknopf et. al. had demonstrated a supramolecular

triangles

utilizing

(TBA)2[V6O13{(OCH2)3CNHC(O)-3-C5H4N}2]

and

a

transparent gel with birefringence using (TBA)3[MnMo6O18{(OCH2)3CNHC(O)-4-C5H4N}2];19, 20

Izzet et. al. has reported several POMs-based supramolecular polygons (trigon and tetragon)

using a pyridine group or a terpyridine functionalized Dawson/Keggin POMs;21-23 however, only few examples of crystalline coordination polymers based on organic hybrid POMs have been reported

up

to

now.24,25

Hill

et.

al

have

built

a

coordination

network

using

[V6O13{(OCH2)3C(NH-CH2C6H4-4-CO2)}2]4- as linker, which can oxidize PrSH into PrSSPr using O2 as oxidizing agent.26 Yang et. al had reported heterometallic cluster organic frameworks using [MnMo6O18{(OCH2)3C-4-C5H4N)}2]3– as linker and cubic [Cu4I4] cluster as node, which can catalyze three-component azide–alkyne cycloaddition reaction.27 The construction of CPs using organic derivatized POMs is still a challenge owing to the complicated coordination mode of POMs and stability of organic derivatized POMs. We had devoted to the construction of organic derivatized POMs with different functional groups28 and in the post-functionalization of POMs.29 Recently, we prepared two organic derivatized Anderson-Evans POMs with pyridyl groups: (TBA)3[MnMo6O18((OCH2)3CN=CH-4Py)2]·DMF ((TBA)3POM-1) and (TBA)3[MnMo6O18((OCH2)3CN=CH-3-Py)2] ((TBA)3POM-2). Three luminescent PCPs (TBA)n·{[Cu(PPh3)2]2(POM-1)}n·(7.5DMF)n (1), (TBA)n{[Cu(PPh3)2]2 -(POM-2)}n·(2DMF)n (2) and {[Cu(PPh3)2]3(POM-2)·(CH3CN)}n·(5CH3CN)n (3) were obtained using them as building blocks to assemble with [Cu(PPh3)2(CH3CN)2]ClO4 (CuP2). Herein, we reported their preparations, structures, characterizations and luminescence.


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RESULTS AND DISSCUSIONS Syntheses and Structures of (TBA)3POM-1 and (TBA)3POM-2. Two pyridine functionalized Anderson-Evans POMs, (TBA)3POM-1 and (TBA)3POM-2, were conveniently obtained by the imidization reaction of Anderson-NH2 with 4-pyridinealdehyde and 3-pyridinealdehyde (Scheme S1), respectively, using the similar synthetic procedure in the literature.30 In the UV-vis spectra (Figure S7), the maximum absorption band in (TBA)3POM-1 (239 nm) and (TBA)3POM-2 (236 nm) have a hypochromatic shift (26 nm for (TBA)3POM-1 and 23 nm for (TBA)3POM-2) compared to that of Anderon-NH2 (216 nm), indicating the formation of C=N double bond in (TBA)3POM-1 and (TBA)3POM-2.30,

31

The 1H NMR of

(TBA)3POM-1 (Figure S5) shows the pyridine ring (7.64 ppm and 8.76 ppm), TBA signals (0.93 ppm, 1.32 ppm, 1.57 ppm, 3.17 ppm) and DMF (2.73 ppm, 2.89 ppm, 7.95 ppm). Similarly, the 1H

NMR of (TBA)3POM-2 (Figure S6) shows signals of pyridine ring (7.57 ppm, 8.05 ppm, 8.43

ppm and 8.83 ppm), the signals of TBA (0.93 ppm, 1.31 ppm, 1.56 ppm, 3.16 ppm) and DMF (2.73 ppm, 2.89 ppm, 7.95 ppm). Their chemical shifts and integrals are well matched with their presupposed structures. Their ESI-MS spectra (Figure S1-S2) give the characteristic peak of (M + 2H)2+ (1030.41 for (TBA)3POM-1; 1030.04 for (TBA)3POM-1; calcd. 1030.26), the characteristic peak of (M + H+ - 2TBA)- (1576.85 for (TBA)3POM-1; 1576.57 for (TBA)3POM2; calcd. 1576.37), the characteristic peak of (M - TBA)- (1818.88 for (TBA)3POM-1; 1819.07 for (TBA)3POM-2; calcd. 1818.03). In their MALDI-TOF MS (Figure S3-S4), the molecular peak of [M + TBA]+ (calcd. 2311.581) is found at 2311.584 in (TBA)3POM-1, 2311.584 in (TBA)3POM-2, respectively, which further confirmed their presupposed structures. The structure analysis by single crystal X-ray diffraction indicates that the asymmetric unit of (TBA)3POM-1 possess two half an Anderson-Evans anionic cluster of type B, three TBA cations


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and a DMF solvent molecule. ORTEP drawing and polyhedron diagram of POM-1 is shown in Figure 1.

Figure 1. ORTEP (30% ellipsoid) diagram (a) and polyhedron diagram (b) of POM-1, hydrogen atoms and TBA cations are omitted for concision. One Mn(III) atom in the symcenter of POM-1 is six-coordinated with six oxygen atoms from two TRIS-4-pyridine ligands to form a slightly distorted octahedron. There are six molybdenum atoms around the central Mn(III) atom to form a planar hexagonal metal skeleton. Each molybdenum atom is coordinated with two μ3 oxygen atoms (Oc), two bridged oxygen atoms (Ob) and two terminal oxygen atoms (Ot) to form a slightly distorted octahedron. The bond lengths of Mo-Ot, Mo-Ob and Mo-Oc are in the range of 1.695(3) ~ 1.704(3) Å, 1.909(3) ~ 1.938(3) Å and 2.310(3) ~ 2.429(3) Å, respectively. The nitrogen atom on TRIS-ligand is connected with 4-pyridinecarboxaldehyde via the C=N double bond (1.252(6) Å/1.217(8) Å).


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POM-1 is a rigid molecular rod consisting of a backbone of type-B Anderson-Evans cluster capped by two bilateral TRIS-4-pyridine ligands, which also can be viewed as the analogue of 4,4’-bipydine with the rod length of 1.89 nm. The crystal of (TBA)3POM-2 is easily to lost solvent and X-ray data is difficult to collect. Preliminary structural analysis by X-ray single crystal diffraction indicates that there are two half an Anderson-Evans anionic cluster and three TBA in the asymmetric unit of (TBA)3POM-2. It cannot be refined owing to the poor data quality. ORTEP drawing and polyhedron diagram of one POM-2 are shown in Figure S23. The cluster structure of POM-2 resemble that of POM-1 with different ligand of 3-pyridine. The molecular rod length of POM-2 is about 1.89 nm and the separation between the two nitrogen atom in pyridine ligands is about 1.80 nm, which can be viewed as the analogue of 3,3’-bipyridine containing a POMs backbone of Anderson-Evans cluster. Syntheses and Crystal Structures of Compounds 1-3 Using the technique of layer-layer diffusion, self-assembly of (TBA)3POM-1 and CuP2 in the mole ratios of 1 : 2 and 1 : 3 give lots of orange block crystals. Structure study by X-ray single crystal diffraction reveals that both products crystallize in the crystal system of triclinic, P-1 space group with same cell parameters. This indicates that despite the different moles ratio, they are the same compound of (TBA)n{[Cu(PPh3)2]2(POM-1)·4DMF}n (1). In the asymmetric unit of 1, there are two half POM-1 anions, two Cu(PPh3)2 units, one disordered TBA cation and four DMF solvent molecules. ORTEP drawing of POM-1 with 30% thermal ellipsoids is shown in Figure 2. O1 in one POM-1 is coordinated with Cu(1), which is bonded with two P atoms from PPh3 and one nitrogen atom (N4) from one pyridine of adjacent POM-1 cluster (symmetry code: -x + 1, -y + 2, -z +1). The pyridine N atom (N2) of POM-1 is


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bonded to Cu(2), which is four-coordinated to form another ONP2 tetrahedron. POM-1 can be viewed as four-connected polyoxometalates ligands coordinated with four building blocks of CuP2 to form a 1D wave-like double chain. The bond lengths of Cu-N are 2.063(4) Å and 2.071(4) Å, respectively. The bond lengths of Cu-P are 2.2249(13) Å and 2.2640(13) Å. The CuO bond lengths are 2.080(3) Å and 2.087(3) Å. The bond angles of P-Cu-P (133.27(5)o, 133.27(5)o) and N-Cu-O (96.13(15)o, 96.13(14)o) in the tetrahedron of CuP2NO are deviated from 109o28ˊ, indicating the distorted nature in the CuP2NO tetrahedron.

Figure 2. ORTEP diagram (30% thermal ellipsoid) of the anion in compound 1. Those CuP2 units are linked by POM-1 to form an infinite spiral wave-like double chain consisting of the building block of Cu2(POM-1)2 (Figure 3a, 3b). Those adjacent chains are further packed into a 2D network with the grid of 8.3 nm ×15.2 nm via Van de Waal interaction (Figure 3c, 3d). Those disordered TBA cations and crystallized DMF solvents are filled within these grids. Calculation using PLATON gives a potential solvent-accessible volume of ca. 24.3%, 1973.6 Å3. Other disordered solvent molecules are treated using SQUEEZE.


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Figure 3. Polyhedron viewing (a) and space filling diagram (b) of the 1-D double anionic chain in compound 1 (phenyl ring of PPh3 omitted for clarity); Polyhedron viewing (c) and space filling diagram (d) of 2-D network in compound 1 (Solvent molecules and TBA omitted for concision). Self-assembly of (TBA)3POM-2 and CuP2 in the ratios of 1:2 and 1:3 using a similar procedure also yielded orange block crystals. Structural study by single crystal X-ray diffraction reveals that the former crystallizes in the crystal system of monoclinic, C2/c space group with the molecular formula of (TBA)n{[Cu(PPh3)2]2(POM-2)}n (2); while the later crystallizes in the system of triclinic, P-1 space group with the molecular formula of {[Cu(PPh3)2]3(POM-1)}n (3). Therefore, different ratio results in different assembled products for (TBA)3POM-2.


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Figure 4. a) ORTEP diagram (50% thermal ellipsoid) of compound 2; b) ORTEP diagram (30% thermal ellipsoid) of compound 3; TBA and DMF molecules are omitted for concision. The asymmetric unit of compound 2 has half a POM-2 anion, one Cu(PPh3)2 unit, half disordered TBA cation and two DMF solvent molecules. The anionic ORTEP diagram (50% thermal ellipsoids) is given in Figure 4a. As shown in Figure 4a, one terminal atom (O1) in one POM-2 is coordinated with Cu(1), which in turn is coordinated one nitrogen atom (N4) from one pyridine ligand of adjacent POM2 cluster (symmetry code: -x + 1/2, y – 1/2, -z +1/2) and with two PPh3 ligands to form a tetrahedron. POM-2 in compound 2 can be viewed as a four-connected polyoxometalates ligand


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linked by the building blocks of CuP2 to form a 2D network. The major reason for the different assembly result for POM-1 and POM-2 with CuP2 in the same ratio of 1 : 2 possibly arises from the larger NPyridine-Mn-Axis angle in POM-2 (7.543o) compared to that of POM-1 (4.731o). The bond length of Cu-N is 2.096(4) Å, the one of Cu-P are 2.2542(14) Å and 2.2581(14) Å, respectively. The bond length of Cu-O is 2.096(4) Å. The bond angles of P-Cu-P (125.38(5)o) and N-Cu-O (102.90(15)o) in the tetrahedron of CuP2NO are deviated from 109o28′ in the ideal tetrahedron, showing the distorted nature in the CuP2NO tetrahedron.

Figure 5. Polyhedron graph (omitted benzene ring) (a) and spatial filling graph (b) of 2D anionic network of compound 2. The copper phosphorus units (CuP2) are linked by four-connected POM-2 to form a 2D network with the grid of 10.38 nm ×13.38 nm (Figure 5a, 5b). Those disordered TBA cations and DMF solvents fit between the layers of the 2D network. In the asymmetric unit of compound 3, there are two half Anderson-Evans clusters of [MnMo6O18((OCH2)3CN=CH-3-Py)2]3- (POM-2), three [Cu(PPh3)2]+ building blocks, one acetonitrile molecule coordinated with Cu(3) and five acetonitrile solvent molecules. ORTEP drawing with 30% thermal ellipsoid of compound 3 is shown in Figure 4b. One half POM-2 is coordinated with three CuP2 building block (Cu1, Cu2, Cu3) via one N atom (N4) of its pyridine ligand and two terminal oxygen atoms (O14, O15) (Figure 4b), while


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another half POM-2 is coordinated with two CuP2 building block (Cu1, Cu2#1, symmetry code, #1:

x - 1, y - 1, z) via one pyridine N atom (N2) and two terminal oxygen atoms(O1) from POM-

2. All copper atoms (Cu1, Cu2 Cu3) are four-coordinated with two P atoms, one N atom and one terminal O atom to from a distorted CuP2NO tetrahedron, which is evidenced by the bonds lengths of Cu-P (2.229(3) ~ 2.271(3) Å), Cu-N (2.029(9) ~ 2.105(8) Å) and Cu-O (2.075(6) ~ 2.170(7) Å); the bond angle of P-Cu-P (120.85(10) ~ 129.73(12)o), N-Cu-P (104.5(3) ~ 115.7(2)o) and N-Cu-O (97.9(3) ~ 110.5(3)o).

Figure 6. Polyhedron graph (omitted benzene ring) (a) and spatial filling graph (b) of 2D anionic network of compound 3. The copper phosphorus units (CuP2) are connected by POM-2 to form a 2D network with two kinds of grids with the size of 13.94 ×14.56 nm and 13.35 ×13.36 nm (Figure 6a, 6b). The structural difference between compounds 2 and 3 is that there are six-coordinated POM-2 in compound 3 compared to four-coordinated POM-2. Calculations of bond valence sum (BVS)32, 33 (Table S2) indicate that BVS of Mn atoms and Mo atoms in compounds (TBA)3POM-1, 1-3 are in the range of 3.282 ~ 3.370 and 5.925 ~ 6.082, respectively. Therefore, the oxidation state of the Mn atoms and the Mo atoms is +6 and + 3, respectively. BVS results of the Cu in compounds 1-3 ranged from 0.555 to 0.632, and the


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oxidation state of Cu atoms in 1-3 is ascribed as +1. X-ray photoelectron spectroscopy (XPS) of compounds 1-3 was performed to further validate the oxidation state of metal. XPS spectra (Figure S16-S18) of compounds 1-3 show the characteristic Mo(3d) doublet (Mo3d3/2, Mo3d5/2) at ca. 231.15, 234.44 eV in compound 1, 231.63 eV, 234.89 eV in compound 2, and 231.25 eV, 234.47 eV in compound 3, in accordance with the literature values for Mo(VI) (231.3 eV, 235.8 eV).34 The doublets of Mn(3d) are found ca. 638.66 eV, 649.46 eV in compound 1, 638.14 eV, 648.0 eV in compound 2, and 638.34 eV, 648.36 eV in compound 3, respectively, in line with the literature value of Mn(III) (638.7 eV, 649.7 eV). The doublets of Cu(3d) are found ca. 932.28 eV, 952.45 eV in compound 1, 932.83 eV, 952.48 eV in compound 2, and 932.67 eV, 952.62 eV in compound 3. These are consistent with the literature value of Cu(I) (932.8 eV, 952.2 eV). Therefore, the oxidation state of metals ions derived from XPS are consisted with that from BVS. Powder X-ray diffractions (PXRD) of 1-3 (Figure S13-S15) are performed to validate their phase purity. These peaks of their measured PXRD spectra are in agreement with their theoretical PXRD pattern obtained from their single crystal data (Figure S13-15), indicating that compounds 1-3 are phase pure. Their intensity difference is possibly originated from the preferred orientation in the powder samples.35 To explore thermal stability, TGA of 1-3 (Figure S19-S21) were carried out with the temperature rate of 10 oC/min at the N2 atmosphere. Compound 1 has a slow weight loss between 20-127 ºC (ca. 16.4%), corresponds to lose 7.5 DMF solvent molecules (16.61%), meaning that there are extra 3.5 DMF molecules besides these solved four DMF molecules. A rapid weight loss (ca. 39.15%) between 211 - 381ºC is associated with the loss of one TBA cation four PPh3 ligands (39.14%). Compound 2 has a weight loss (ca. 7.7%) between 80-199.6 ºC. This corresponds losing two DMF molecules (5.05%), a rapid weight loss (ca. 49.02%)


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appeared between 227.1 - 394.6 ºC, which is associated with the loss of one TBA and four triphenylphosphine ligands (44.62%).. Compound 3 is stable before 100 ºC, a weight loss of 9.4% is found between 100-230 ºC, which is associated with the loss of five crystallized acetonitrile molecules and one coordinated acetonitrile molecule (7.37%); a rapid weight loss (37.1%) corresponding to the loss of six PPh3 (calc. 42.0%) between 230-333 ºC. TGA analysis shows that compounds 2 and 3 (2D) are more stable than compound 1 (1D) with the increase of dimensionality.

Figure 7. Luminescence diagram of CuP2 in the acetonitrile solution (10-5 mol/L) (a), luminescence diagram of 1 (b), 2 (c) and 3 (d) in the solid state. Owing to their insolubility in common solvent, solid-state luminescence of compounds 1-3 were performed at room temperature. For comparison, the luminescence of (TBA)3POM-1, (TBA)3POM-2 and CuP2, their parents, were investigated in acetonitrile solution at a concentration of 1.0 × 10-5 mol/L. (TBA)3POM-1 and (TBA)3POM-2 exhibit a weak emission


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(λmax = 331 nm) upon the excitation of 300 nm (Figure S22). CuP2 has a green emission (λmax = 508 nm) upon the excitation of 327nm (Figure 7a). The photoluminescence of compounds 1-3 (Figure 7b - 7d) are different from that of (TBA)3POM-1 and (TBA)3POM-2, but similar to that of CuP2. They have a broad green emission with the maximum of 496 nm for compound 1 (λex = 327nm), 537nm for compound 2 (λex = 303nm) and 530nm for compound 3 (λex = 331nm), respectively. They can be tentatively attributed to ILCT with metal perturbation owing to their similar emission to that of triphenylphosphine ligands.36-38 Compounds 1-3 are a class of potential green-emissive hybrid materials consisting of polyoxometalates coordinate polymers (PCPs). Conclusion In summary, we have prepared two organic-inorganic hybrid rigid molecular rods: (TBA)3[MnMo6O18((OCH2)3CN=CH-4-Py)2]·DMF ((TBA)3POM-1) and (TBA)3[MnMo6O18((OCH2)3CN=CH-3-Py)2] ((TBA)3POM-1) by the post-functionalization of Anderson-NH2. X-ray single crystal diffraction shows that they are of a type-B Anderson POMs capped by two TRISpyridine ligands on both sides, which can be viewed as the analogue of 4,4’-bipy and 3,3’-bipy containing a polyoxometalates backbone. Using (TBA)3POM-1 and (TBA)3POM-2 as linkers to assemble with CuP2, different mole ratios of (TBA)3POM-1:CuP (1 : 2 and 1 : 3) give the same wave-like chain of (TBA)n{[Cu(PPh3)2]2(POM-1)}n (7.5DMF)n (1); however, (TBA)3POM-2 and CuP2 in the mole ratio of 1 : 2 yields a 2D network of (TBA)n{[Cu(PPh3)2]2(POM2)}n·(2DMF)n (2), but the ratio of 1 : 3 ((TBA)3POM-2:CuP2) results in another 2D coordination polymer of

{[Cu(PPh3)2]3(POM-2)·(CH3CN)}n·(5CH3CN)n (3). TGA of

compounds 1 - 3 indicate that their skeleton can stable up to approximately 230 oC. Luminescence studies indicate that compounds 1 - 3 are a kind of potential green-emissive


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hybrid materials. Our current research not only provides a rationally strategy to build PCPs, but also yields several potential green-luminescence materials. ASSOCIATED CONTENT Supporting Information Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.xxxxxx. Crystallographic data, BVS, FT-IR, UV-Vis spectra, XPS, PXRD, 1H NMR, ESI-MS, MALDITOF MS and TGA (PDF) Accession Codes CCDC NO.: 1870067 − 1870070 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/ cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. AUTHOR INFORMATION Corresponding Author * J. Guo, Email: [email protected], Fax: +86-27-67867953. *L.-S. Wang, Email: [email protected], Fax: +86-27-59750482. ORCID Jun Guo: 0000-0002-2097-5054 Longsheng Wang: 0000-0002-3340-0081 Author Contributions


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‡

Both authors contributed equally to this work.

Funding Sources We thank the financial support of the National Natural Science Foundation of China (21101062, 21772056, 21771120), Science and Technology Department of Hubei Province (2014CFB600, 2015CFA131), Youth Chutian Scholar Fund of Hubei Province (4032401), State Key Laboratory of structural chemistry (20180023), Hubei Provincial Key Laboratory of Green Materials for Light Industry (201710A11). Notes The authors declare no competing financial interest. ACKNOWLEDGMENT The authors thank Prof. Hai-bin Xu and Mr. Dao-bing Guan in Hubei University for their help in the measurement and discussion of luminescence; Dr. Gearóid ó Máille, Prof. Panchao Yin and Miss Toni-Jade Chin for their help in English. ABBREVIATIONS POMs, polyoxometalates; CPs, coordination polymers; PCPs, polyoxometalates coordination polymers; TBA, Tetrabutylammonium; REFERENCES (1) Leong, W. L.; Vittal, J. J., One-Dimensional Coordination Polymers: Complexity and Diversity in Structures, Properties, and Applications. Chem. Rev. 2011, 111, 688. (2) Yamada, T.; Otsubo, K.; Makiura, R.; Kitagawa, H., Designer coordination polymers: dimensional crossover architectures and proton conduction. Chem. Soc. Rev. 2013, 42, 6655. (3) Batten, S. R.; VanEldik, R.; Turner, D. R., Coordination Polymers: Design, Analysis and Application. 1st ed.; Royal Society of Chemistry: Cambridge CB4 0WF, UK 2008. (4) Hong, M.-C.; Chen, L., Design and Construction of Coordination Polymers 1st ed.; John Wiley & Sons, Inc.: Hoboken, New Jersey, 2009.


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For Table of Contents Use Only

Coordination Polymers Based on Organic-Inorganic Hybrid Rigid-rod Comprising a Backbone of Anderson-Evans POMs Mao-Chun Zhu,1, ǂ Ying-Ying Huang,1, ǂ Jian-Ping Ma,2 Sheng-Min Hu,3 Yue Wang,1 Jun Guo,4,* Yan-Xi Zhao,5 Long-Sheng Wang,1,3,5,* SYNOPSIS

Assembly of organic-inorganic hybrid molecular rod consisting of a backbone of AndersonEvans cluster and copper phosphorous building blocks in different ratio yield several luminescent polyoxometalates coordination polymers (PCPs).


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Coordination Polymers Based on OrganicâInorganic Hybrid Rigid Rod

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