Syntheses, Structures And Properties Of Multi-dentate N-Containing Coordination Polymers

This dissertation consists of four parts. Firstly, we design and synthesize a V-shaped bidentated imidazole ligand 4,4'-bis(imidazol-l-yl) diphenyl ether (BIDPE), and synthesized twelve mixed-coordination polymers with novel frameworks and properties by solvothermal or hydrothermal reactions. Secondly, we adopt a flexible tetrakis(4-pyridyloxymethylene)methane (TPOM) synthesized nine coordination compounds with novel structures and properties. Thirdly, a unique containing Zn/O clusters framework with high connections was synthesized by mixed-coordination of 4,4',4"-nitrilotrisbenzoic acid (H3NTB) and 4,4'-nitrilodibenzoic acid (H2NDB). Lastly, a large porous channels cluster-based framework is obtained by steply assemble of fourdentated imidazole ligands N,N',N",N"'-tetrakis(4-imidazol-l-ylphenyl)-4,4'-biphenylenediamine (TIPBPDA) with W/S/Cu cluster monomer.1. Syntheses, Structures, and Properties of Coordination polymers Based on Aromatic Carboxylate Acid and V-shape Imidazole Ligand 4,4'-bis(imidazol-1-yl)diphenyl ether (BIDPE)Solvothermal or hydrothermal reactions of 4,4'-bis(imidazol-1-yl)diphenyl ether (BIDPE) with deprotonated 1,4-benzenedicarboxylic acid (H2bdc), 5-hydroxyisophthalic acid (5-OH-H2bdc), and benzene-1,3,5-tricarboxylic acid (H3btc) in the presence of transition salts in H2O or H2O/DMF yielded twelve new complexes. namely,{[Co(BIDPE)(bdc)]2·(H2O)2(DMF)}n (1), {[Cd(BIDPE)(bdc)]4·(H2O)4(DMF)2}n (2),{[Zn(BIDPE)(bdc)]2·(H2O)2(DMF)}n (3), {[Cd3(BIDPE)2(bdc)3]}n (4),{[Ni(BIDPE)(bdc)(H2O)2]}n (5), {[Mn(BIDPE)(bdc)(H2O)]}n (6),{[Cd(BIDPE)(5-OH-bdc)]·(H2O)}n (7), {[Co(BIDPE)(5-OH-bdc)]·(H2O)}n (8),{[Zn3(BIDPE)3(5-OH-bdc)3]·(H2O)4}n (9), {[Ni(BIDPE)2(5-OH-bdc)(H2O)]·(H2O)3}n (10),{[Mn2(BIDPE)2(5-OH-bdc)2]}n (11), {[Ni(BIDPE)2(Hbtc)(H2O)]}n (12). Complexes 1,2 and 3 are isomorphic, space group of I41/acd, and reveal a 2-fold interpenetrating three-dimensional (3D) framework with self-penetrating {86} topology constructed from BIDPE and H2bdc. Complexes 2 and 4 have same staring materials but possess different 3D frameworks,4 exists two types of Cd ions and forms trinuclear Cd cluster, which are linked by BIDPE and H2bdc to generate 3D framework. Complex 5 is a 2D sheet containing 1D channel, two identical sheets interlocked form a 2D→2D network. While complex 6 also contains 2D→2D interlocked sheet, but consists of two different 2D networks. Compounds 7,8 are isomorphic and reveal 2D sheets with 32-membered [(Cd/Co)2(BIDPE)2] metallocyclic ring constructed from BIDPE and 5-OH-H2bdc with Cd or Co salts, the identical 2D sheets were arranged in -A-B-A-B- model. Compound 9 is a 2D sheet containing 1D channel, by analyzing, six identical 2D sheets are polycatenated in parallel to form a rare 2D→2D framework, this phenomenon is first observed. Furthermore, it displays ferroelectric behavior. In compounds 10, only one carboxyl group coordinates to Ni atom to form 1D double strand chains, which further form 3D supermolecular framework by H-bond. Compound 11 exists binuclear Mn cluster, which is linked by BIDPE and 5-OH-H2bdc to generate a 2D sheet and displays weak antiferromagnetic character. For complex 12, only one carboxyl group coordinates to Ni atom from H3btc to form a 2D wave sheet and two identical networks interlocked each other. The stability of whole crystal structure was very well due to the strong H-bond. The luminescent properties of free ligands BIDPE, H2bdc and 5-OH-H2bdc, with complexes 2,3,4,7 and 9 are investigated. The results reveal that complexes 2,3,4,7 and 9 exhibit their emission characters similar to that of the free ligands, showing a small red shift. The emission decay lifetimes of compounds 7 and 9 were monitored and the curves are best fitted by bi-exponentials in solid, the results reveal that the emission decay lifetimes are short. In addition, the UV-vis absorption spectra of compounds 1-12 are carried out in crystalline state at room temperature. Energy bands of complexes 1,5,8, 10 and 12 are assigned as d-d transitions of metals, while these characteristic bands do not appear in the spectra of the Cd2+, Zn2+ complexes. A possible explanation for Cd2+ and Zn2+ could be found in their d10 electronic states, which are more stable.2. Syntheses, Structures, and Properties of Coordination Polymers Based on Flexible Tetrapyridines and Aromatic Polycarboxylate AcidsNine new coordination complexes, namely {[Cd2(TPOM)(bdc)2]·(H2O)5(DMF)}n (13),{[Zn2(TPOM)(bdc)2]·(H2O)4}n (14),{[Zn2(TPOM)(bdc)2]·(H2O)}n (15), {[Co2(TPOM)(5-OH-bdc)2(H2O)2]·(H2O)5}n (16), {[Cd2(TPOM)(5-OH-bdc)2]·(H2O)2}n (17),{[Cd2(TPOM)(hfipbb)2]-x/y/zslovent}n (18-20),{[Co2(TPOM)(hfipbb)2]}n (21), have been synthesized by solvothermal or hydrothermal reactions of tetrakis(4-pyridyloxymethylene)-methane (TPOM) with deprotonated H2bdc,5-OH-H2bdc or H2hfipbb. Complex 13 reveals a 2-fold interpenetrating three-dimensional architecture, the two pairs of pyridine rings of one TPOM are almost in parallel, which linked two binuclear Cd clusters with bdc2- to form pcu topology. In addition, the experiment of single-crystal-to-single-crystal (SC-SC) structural transformation upon guest exchange is tested. Complexes 14 and 15 are supermolecuar isomers, possessing different 3D frameworks,14 is a non-penetrated (62.84) architecture, space group of C2/c, while 15 was a 3-fold interpenetrating {4.5.62.72} {4.52.6.7.8} {52.62.72} architecture, space group of P21/c. Complex 16 exists two types Co(II) ions, TPOM and 5-OH-H2bdc link Co centers to generate 3D 2-fold interpenetrating framework with bbf topology. Compound 17 was a chiral space group P21212, The 5-OH-bdc2" anions connected Cd(II) ions to generate 1D helical channels, which further coordinated by TPOM to form 2-fold interpenetrating three-dimensional architecture with qtz topology. Compounds 18-20 are supramolecular isomers and have been synthesized by one pot reaction in H2O/DMF system. Complex 18 is a self-penetrating 3D framework containing meso-helix [Cd(hfipbb)]n chains. Complex 19 reavels 2-fold locked 2D→2D network, while complex 20 is a 2D bilayer network which was further polycatenated to form 2D→3D framework. The structure of 21 is similar to compound 18. In addition, the luminescent properties of free ligands and complexes 13,14,15,17,18 and 20 are investigated. The results reveal that complexes 13,14,15,17,18 and 20 exhibit their emission characters similar to that of the free ligands, and showing a small red shift. While the luminescent properties of 19 is too weak to observed. The emission decay lifetimes of compounds 13,14,15 and 17 are monitored and the curves are best fitted by bi-exponentials, the results reveal that the emission decay lifetimes of 13,14,15 and 17 are short. Furthermore, the UV-vis absorption spectra of complex 16 are carried out. Energy bands of complex 16 from 520 to 590 nm are assigned as d-d transition of metals.3. Syntheses, Structures, and Properties of Coordination Polymers Based on Zn/O cluster or W/S/Cu cluster3.1 Synthese and Structure of Metal-Organic Framework Based on 4,4',4"-nitrilotrisbenzoic acid (H3NTB) and 4,4'-nitrilodibenzoic acid (H2NDB){[Zn17O5(NTB)6(NDB)3]·48H2O} (22) is synthesized and characterized by hydrothermal reaction of 4,4',4"-nitrilotrisbenzoic acid (H3NTB),4,4'-nitrilodibenzoic acid (H2NDB) in the presence of zinc salt. 22 is chiral space group R32, with two types of Zn/O clusters, one is Zn4O(COO)6 and another is unique Zn9O3(COO)12. Each NDB2- only linked Zn4O(COO)6 to form 2D wave sheet, which contains left-handed helical chains, while NTB3- linked helical chains and Zn9O3(COO)12 to generate high connected non-penetrating 3D framework.3.2 Synthese, Structure, and Property of Cluster-based Polymer Based on N,N',N",N'''-tetrakis(4-imidazol-1-ylphenyl)-4,4'-biphenylene-diamine (TIPBPDA) with W/S/Cu clusterOne novel non-interpenetrated heterothiometallic cluster-organic framework [WS4Cu6(TIPBPDA)8Br4]n·xsolvents (24) (TIPBPDA=N,N',N",N'''-tetrakis (4-imidazol-1-ylphenyl)-4,4'-biphenylene-diamine) is synthesized by the self-assembly of preformed heterothiometallic cluster monomer with tetradentate N-donor ligand TIPBPDA. Compound 24 contains two types of porous channels with the size of～17×19 ? and～11×24 ?. One of channels is double helical and the hand-directions are reverse. By analyzing,24 is a (4,8) connected sqc topology. Due to 24 exist Cu(Ⅰ), so its catalytic property for huisgen cycloaddition reaction is studied.