| In this dissertation, we used four conjugated thiophene-based ligands, 5,5’-bis(4-pyridyl)-2,2’-bithiophene (BPBP), 5,5’-Bis(1H-imidazol-1-yl)-2,2’-bithiophene (BIBP), 2,8-di(1H-imidazol-1-yl)dibenzothiophene (DIDP) and 3,3’-(thiophene-2,5-diyl)dibenzoic acid (H2L), as main organic ligands to react with different transition metal ions and successfully constructed twenty coordination polymers under hydrothermal conditions. Their syntheses, crystal structures and physical properties were investigated and discussed in detail. This dissertation includes the following four parts:1. Solvothermal reactions of 5,5’-bis(4-pyridyl)-2,2’-bithiophene (BPBP) with 4,4’-(hexafluoroisopropylidene) (H2hfipbb),trans-1,4-cyclohexanedicarboxylic acid (trans-H2chdc),4,4’-sulfonyldicarboxylic acid (4,4’- H2sdb),4,4’-oxybis(benzoic acid) (H2oba), in the presence of different transition metal ions yielded six coordination polymers, namely,{[Cd(BPBP)0.5(hfipbb)]·0.5DMF}n (1),{[Zn(BPBP)0.5(hfipbb)]}n (2), [Co(BPBP)0.5(hfipbb)·0.5DMF]}n (3),{[Zn(BPBP)(trans-chdc)]·H2O}n (4), {[Zn2(BPBP)(4,4’-sdb)2]}n (5),{[Zn2(BPBP)(oba)2]·H2O·DMA}n(6). Compounds 1-3 are isostructural and display 3D 2-fold interpenetrating frameworks with rare {44.610.8}-mab topologies. Compound 4 exhibits a 3D diamond-type (dia,66) framework of 6-fold interpenetration. Compound 5 shows a 2D network with {44.62}-sql topology, which consists of 1D [Zn2(4,4’-sdb)2]n chains. Interestingly, it exhibits 2D+2D→2D polyrotaxane entanglements structure characteristics. Compound 6 possesses a 3-fold interpenetrating 3D framework with 6-connected {4l2.63} pcu topology. Thermal stabilities for compounds 1-6 and photoluminescence properties of the compounds 1,2,4,5, and 6 have been examined. Furthermore, the UV-vis absorption spectra and semiconductive properties of compound 3 were also investigated.2. Solvothermal reactions of 5,5’-bis(1H-imidazol-1-yl)-2,2’-bithiophene (BIBP) with five carboxylate ligands with different rigidity, namely 4,4’-(hexafluoroisopropylidene)bis(benzoic acid) (H2hfipbb), 1,3,5-benzenetricarboxylic acid (H3btc), isophthalic acid (H2bdc), 5-hydroxyisophthalic acid (5-OH-H2bdc), and D-camphor acid (D-H2ca), as co-ligands in the presence of different transition metal ions yielded seven coordination polymers, namely,{[Co(BIBP)(hfipbb)]}n (7),{[Co(BIBP)(Hbtc)]}n (8), {[Zn(BIBP)(5-OH-bdc)]}n (9),{[Cd(BIBP)(bdc)]}n (10), {[Zn2(BIBP)o.5(hfipbb)2]·H20}n (11), [Zn4(BIBP)4(bdc)4]}n (12), {[Zn(BIBP)(DL-ca)]H2O}n(13). Compound 7 exhibits a 2D→3D framework with unusual parallel polycatenation of corrugated 2D (4,4) nets. Compounds 8-10 are structurally similar and display 2D layer structures, in which 8 and 9 extend into 3D supramolecular frameworks through interlayer O-H…O hydrogen-bonding interactions. Compound 11 displays a 3D 2-fold interpenetrating framework with a rare{44.66}-sqp topology, containing interesting …RLR… double helical layer structure. Compound 12 is a 2D network with{44.62}-sql topology and further extends via C-H…O hydrogen bonds into the 3D supramolecular framework. Compound 13 possesses a rare 3D non-interpenetrated cds-type framework with the Schlafli symbol{65.8}. Thermal stabilities for compounds 7-13 and photoluminescence properties of the compounds 9-13 have been examined. Furthermore, the UV-vis absorption spectra and semiconductive properties of compounds 7-13 were also investigated.3. Solvothermal reactions of a V-shaped ligand 2,8-di(1H-imidazol-1-y1) dibenzothiophene (DIDP) and different aromatic dicarboxylic acids, namely, isophthalic acid (m-H2bdc), terephthalic acid (p-H2bdc), 4,4’-(hexafluoroisopropylidene)bis(benzoic acid) (H2hfipbb), and 4,4’-sulfonyldicarboxylic acid (4,4’-H2sdb), in the presence of different transition metal ions yielded five coordination polymers, namely, {[Ni(DIDP)(m-bdc)(H2O)]·5H2O}n (14),{[Zn(DIDP)(hfipbb)]·2DMA}n (15), {[Zn(DIDP)(4,4’-sdb)]·H2O}n (16),{[Co(DIDP)(p-bdc)]}n (17), and {[Co2(DIDP)(hfipbb)2]·H2O}n (18). Compound 14 is a 1D chain structure containing one-dimensional channel along the a direction and further extended via O-H…S hydrogen bonds and C-H…π stacking interactions into a 3D network. Compound 15 exhibits a quasi 2D+2D→2D with parallel polycatenation of 2D (4,4) nets. Compound 16 displays an unusual 2D+2D→3D parallel polycatenated framework based on a 2D 63-hcb network. Compound 17 shows a 2D 4-connected{44.62}-sql network containing one-dimensional channel along the b direction. The adjacent 2D networks are further extended via C-H…O hydrogen bonds into a 3D supramolecular framework. Compound 18 features a 2-fold interpenetrating 3D framework with 6-connected{412.63}-pcu topology. Thermal stabilities for compounds 14-18, luminescent properties of compounds 15 and 16 have been studied. Furthermore, the UV-vis absorption spectra and semiconductive properties of compounds 14-18 were also investigated.4. Solvothermal reactions of a π-conjugated thiophene-containing carboxylic acid ligand 3,3’-(thiophene-2,5-diyl)dibenzoic acid (H2L), two N-containing ligands, namely, 1,4-di(pyridin-4-yl)benzene (dpyb) and 4,4’-di(1H-imidazol-l-yl)-1,1’-biphenyl (dipb) and Zn(Ⅱ) ions yielded two coordination polymers, namely,{[Zn2(L)2(dpyb)]}n (19) and{[Zn(L)(dipb)]·2H2O}n (20). In compound 19, the spacer ligand dpyb from the adjacent layer penetrates the [Zn2(L)2] metallamacrocycle and forms a rotaxane structure. Due to rotaxane type arrangement, it generates a rare 2-fold polyrotaxane entanglement. Furthermore, adjacent two sets of the entanglements are connected through C-H…π stacking, generating a 3D supramolecular motif. Compound 20 features a 2-fold interpenetrating 3D framework with 4-connected{66}-dia topology. Thermal stabilities and luminescent properties for compounds 19 and 20 have been studied. Furthermore, their sensitive detections of nitroaromatic explosives through photoluminescen quenching were investigated in detail. The present work provides a new strategy to rational design and synthesis MOF-based sensors for selective detection of one nitro explosive from other nitro explosives. |
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