| The contents of this dissertation are as follows:(1) Reactions of series of hexazamacrocycle derivatives [Ni(hto)]Cl2·2H2O (1)(hto=1,3,6,9,11,14-hexaazatri-cyclo[12.2.1.16,9]octadecane),[Ni(CHA)](ClO4)2(2)(CHA=1,3,-6,8,11,14-hexaazatri-cyclo[12.2.1.18,11]octadecane),[Ni(PCHA)](C104)2(3) and [Cu(PCHA)](ClO4)2(4)(PCHA=4-methyl-1,3,6,8,11,14-hexaazatricyclo[12.2.1.18,11]octadecan-e), with a flexible hexapodal ligand H6TTHA (H6TTHA=1,3,5-triazine-2,4,6-triamine hexaacetic acid) resulted in eight co-crystals, formulated as a-[Ni(hto)][H4TTHA]·5H2O (5), β-[Ni(hto)][H4TTHA]·4H2O (6),[Ni(CHA)][H4TTHA]·2H2O (7),[Ni(PCHA)][H4TTHA]·3H2O (8),[Cu(PCHA)][H4TTHA]·1.5H2O (9),[Ni(PCHA)][H5TTHA](ClO4)·4H2O (10),[Ni(PCHA)][H4TTHA]·DMSO·H2O (11) and [Ni(PCHA)][H4TTHA]·DMF (12). These compounds are structurally characterized by X-ray diffraction analyses. The predominant driving forces that connect macrocyclic metallic tectons with hexaacetic acid ligand in those compounds5-12are hydrogen bonds, by which the compounds assemble into co-crystals with versatile structures. The single-crystal X-ray diffraction analysis reveals that compounds5and6contain a rhombic2-D layer network structure constructed of hydrogen bonds. Compound7exhibits a3-D supramolecular network with12×10.4A21-D brick wall net structure along the e-axis, and all the water molecular guests adorned the brick wall net. Compounds8and9show a nonporous3-D framework also stabilized by the hydrogen bonds. Tuning by solvents, in compound10, an elliptical2-D network was found to accommodate water molecules and perchlorate in the channels, with grid dimensions of11×10A2; compounds11and12show2-D honeycomb-like networks with diameter12A.(2) Two microporous coordination polymers,[NiL][(NiL)5(TATAB)4]·48H2O (13) and (NiL)3(BTCMT)2·DMF·16H2O (14)(L=1,3,6,9,11,14-hexaazatri-cyclo[12.2.1.16,9]octadecane, H3TATAB=4,4’,4"-triazine-1,3,5-triyltriaminobenzoate acid and H3BTCMT=4,4’,4"-[1,3,5-benzenetriyltris(carbonylimino)]trisbenzoic acid), were constructed by two tripodal carboxylic ligands and macrocyclic metallic tecton. The results of single crystal X-ray diffraction analyses reveal that both compounds possess two dimension (2D)63network basic layer, and three63layers interweave in parallel to give rise to either a2D Borromean layer for compound13or a3-fold interpenetrating2D sub-layer for compound14. In13,2D Borromean layers are further connected by interlayers π…π interactions. Compound14shows an unusual2Dâ†'3D parallel polycatenation entanglement architecture built on threefold parallel interwoven sub-layer, thus resulting in a novel3D network contains both2Dâ†'2D interpenetration and2Dâ†'3D polycatenation. The comparison of13and14indicates that the degree of63monolayer corrugation has a significant effect on its formation of an overall2D or3D network. These two compounds consist of large solvent accessible voids, in which only compound14possesses permanent porosity as confirmed by gas adsorption measurements and X-ray powder diffractions. In particular, the compound14shows a high selective adsorption for CO2.(3) Solvent-induced revisable single-crystal to single-crystal transformation of macrocycle-based coordination polymers [NiL][(NiL)5(TATAB)4]·4.29CH3OH·30.12H2O (15) and [(NiL)3(TATAB)2]·2DMF (16)(L=1,3,6,9,11,14-hexaazatri-cyclo[12.2.1.16,9]octadecane, H3TATAB=4,4’,4"-triazine-1,3,5-triyltriaminobenzoate, DMF=Dimethylformamide) is studied and those structures are determined by single crystal X-ray diffraction. Interestingly, during the extremely fast bidirectional transformation, solvatochromic behavior is observed and confirmed by UV-Vis, which provides an effective strategy for identifying colorless DMF and H2O solution. |
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