| The aim of this dissertation is to build nineteen coordination complexes withvarious structures and potential application prospects by using(3,5-dicarboxyl-phenyl)-(4-(2?-carboxyl-phenyl)-benzyl) ether (H3L), proper N-donorligands and transition metal ions under hydrothermal conditions. Explore suitableexperimental conditions to prepare these complexes, describe the structures of thesecomplexes in detail and analyse their fascinating topology network, and discuss theeffects of the N-donor ligands and pH values on the framewoks. These complexeshave been characterized by single crystal X-ray diffractions, infrared (IR) spectra,UV vis diffuse reflection spectra, thermogravimetric analysis (TGA) and powderX-ray diffraction spectra (PXRD). Additionally, the optical band gaps, luminescentproperties, photocatalytical behaviors, surface photovoltage and photocurrentproperties of the complexes have also been investigated preliminarily.1. Five coordination polymers (CPs) with different structures were derived fromthe self-assembly of polycarboxylic acid(3,5-dicarboxyl-phenyl)-(4-(2?-carboxyl-phenyl)-benzyl) ether (H3L) and Cu(II),Co(II), Zn(II) and Cd(II) ions. Complex1reveals a two-dimensional (2D)(3,6)-connected net based on tetranuclear [Cu4(?3-OH)2(COO)6(CH3OH)2(H2O)] unitswith kgd (kagome dual) topology. Complexes2and3possess similar2D structures,which are constructed by L anions and rod-shaped secondary building units (SBUs).In complex4, neighboring {Cd9} units are bridged by the carboxylate groups from Lanions to furnish rod-shaped SBUs. These SBUs are further interlinked by L anionsinto a three-dimensional (3D) skeleton. Complex5displays a3D (3,6)-connectedskeleton based on trinuclear [Zn3(?3-OH)(COO)6] units. Additionally, the solid-stateluminescent properties of H3L ligand and complexes3–5and the photocatalyticactivities of complexes1and2under ultraviolet light have been investigatedpreliminarily.[Cu4(L)2(?3-OH)2(CH3OH)2(H2O)](1)[Co2(L)(?3-OH)(H2O)2](2)[Cd2(L)(?3-OH)(H2O)2](3)[Cd9(L)4(?3-OH)4(CH3O)2(H2O)2]·(H2O)·2(CH3OH)(4)(HTEA)[Zn3(L)2(?3-OH)]0.25H2O (5)2. The mixed ligands of (3,5-dicarboxyl-phenyl)-(4-(2?-carboxyl-phenyl)-benzyl) ether (H3L) and N-donor ligands (BIME=1,2-bis(imidazol-1-yl)ethane, BET=1,1?-(2?-oxybis(ethane-2,1-diyl))bis(1,2,4-triazol-1-yl), PBIB=1,4-bis(imidazol-1-ylmethyl)benzene and BTBP=4,4?-bis(1,2,4-triazol-1-ylmethyl)biphenyl) in the presence of Zn(II) cations providedsix CPs with diverse structures. Complexes6and7exhibit unusual2-foldinterpenetrated3D (3,6)-connected skeletons with with a Sch fli notation of(42·6)2(44·62·88·10). Complex8reveals an unprecedented2D (3,8)-connected networkbased on tetranuclear [Zn4(?4-O)(COO)6] units with a Sch fli notation of(3·42)(46·57·68·73·8). Complex9reveals a wavy2D sheet with (44·62) topology.Further, each sheet is interdigitated by two others in a parallel fashion to yield anunusual2D?3D interdigitated structure. Complex10discloses a3D(3,4,6)-connected skeleton with a Sch fli symbol of(3·4·5)2(32·103·11)(32·42·52·103·114·12·13). Complex11displays a3D(3,3,9)-connected framework based on tetranuclear [Zn4(?4-O)(COO)6] clusters with aSch fli symbol of (32·4)(4·62)(34·47·54·616·74·8).[Zn3(L)2(BIME)(H2O)2](6)[Cd3(L)2(BIME)(H2O)2](7)[Zn4(L)2(BET)(?4-O)](8)[Zn2(HL)2(PBIB)]2H2O (9)[Zn3(L)2(PBIB)2]4H2O (10)[Zn8(?4-O)2(L)4(BTBP)3](11)3. We prepared four CPs encompassing polynuclear metal clusters by utilizing(3,5-dicarboxyl-phenyl)-(4-(2?-carboxyl-phenyl)-benzyl) ether (H3L), Zn(II) and Pb(II)ions. Complexes12–15exhibit3D highly connected networks based on multinuclearmetal clusters. Complex12is a (3,12)-connected skeleton based on planar octanuclearzinc cluster [Zn8(?3-OH)8(COO)12(H2O)3]. Complex13displays a (3,12)-connectedskeleton based on decanuclear zinc cluster [Zn10(?3-OH)10(COO)12]. Complex14exhibits a (3,12)-connected skeleton based on bimetallic dodecanuclear clusters[Zn10Na2(?3-OH)8(COO)12(CH3CH2O)2(H2O)4]. Complexes12–15possess(3,12)-connected skeletons with the Sch fli notation of (43)2(420·628·818). Complex15reveals a tetranodal (3,4,8)-connected skeleton based on pentanuclear[Pb5(COO)8(?3-OH)2(H2O)2] units with a Sch fli notation of(43)(4·62)(42·61·83)(46·614·88). In addition, the solid-state fluorescence properties forcomplexes12–15and the degradation of methylene blue (MB) activities forcomplexes12and14under ultraviolet light have been investigated. [Zn4(L)2(?3-OH)2(H2O)1.5]·2H2O (12)Na[Zn5(L)2(?3-OH)5](13)[Zn5Na(L)2(?3-OH)4(CH3CH2O)(H2O)2](14)[Pb7(L)4(H2O)2(H2O)2]·8H2O (15)4. Four high-connected cluster-based CPs based on H3L, Zn(II), Cd(II) andvarious N-donor ligands (1,4-bis(1,2,4-triazol-1-yl)butane,1,1?-(2?-oxybis(ethane-2,1-diyl))bis(1,2,4-triazol-1-yl),4,4?-bipyridine and1,2-bis(imidazol-1-yl)ethane) were prepared under hydrothermal conditions. Complex16is a3D (3,3,14)-connected skeleton constructed by octanuclear zinc clusters[Zn8(?3-OH)4(COO)12], L anions and1,4-bis(1,2,4-triazol-1-yl)butane, and theSchl fli symbol is (43)(32·4)(34·420·514·634·711·88). Complex17is a3D(3,3,14)-connected skeleton, which is afforded by octanuclear zinc clusters[Zn8(?3-OH)4(COO)12(H2O)2], L anions and1,1?-(2?-oxybis(ethane-2,1-diyl))bis(1,2,4-triazol-1-yl). Complex18is also a3D(3,3,14)-connected skeleton fabricated by octanuclear [Cd8(?3-OH)4(COO)12(H2O)4]cadmium cluster, L anions and4,4?-bipyridine. Complex19presents a3D(3,3,14)-connected skeleton constructed by octanuclear [Cd8(?3-OH)4(COO)12(H2O)4]cadmium cluster, L anions and2-bis(imidazol-1-yl)ethane. The3D skeletons ofcomplexes17–19possess the same topology notations to16. Complexes16–19exhibit relative wide optical band gaps, solid-state fluorescence properties and surfacephotovoltage without external electric field have been investigated. Additionally,complex17exhibits a photocurrent response under several on-off cycles ofillumination.[Zn8(?3-OH)6(L)4(BTB)(H2O)2](16)[Zn4(L)2(BET)0.5(?3-OH)2(H2O)](17)[Cd8(?3-OH)4(H2O)4(L)4(4,4?-bpy)] H2O (18)[Cd4(L)2(BIME)0.5(?3-OH)2(H2O)1.5]·2H2O (19)... |
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