Metal-organic frameworks of tetrahedral, tripodal, and dipodal carboxylic acids and dinuclear complexes of acetylacetonato ligands.

摘要

1. Tetrakis(4-carboxyphenyl)silane and tetrakis(4-carboxyphenyl)germanium reacted with zinc nitrate hexahydrate in combinatory solvents of DMF/water/ethanol to form crystalline frameworks, Si4A-Zn and Ge4a-Zn, respectively. Though the organic ligands were quite similar, Si4A-Zn crystallized in space group Pnna and zinc ions took the form of zinc-oxo chains while Ge4A-Zn crystallized in space group Pnnn and zinc ions formed linear trinuclear clusters with a local connectivity of eight.;2. Tris(4-carboxyphenyl)phenylsilane reacted with zinc nitrate hexahydrate in combinatory solvents DMF/water/ethanol to form a layered metal-organic framework (MOF), SiPh3A-Zn. The framework crystallized in space group P-1 and the zinc ions formed tetranuclear zinc-oxo clusters with a local connectivity of six. The topology of SiPh3A-Zn is a metal-organic replica of CdI2 (space group P3-m1).;3. Dipodal carboxylic acids, bis(4-carboxyphenyl)bisphenylsilane, bis(4-carboxylphenyl)-bistolylsilane, and 4,4'-(hexafluoroisopropylidene)bis(benzoic acid), reacted with zinc nitrate hexahydrate in combinatory solvents of DMF/water/ethanol to form three-dimensional metal-organic frameworks. Their pore volumes were calculated by Platon, and the percentages were 30.1%, 23.4%, and 9.4%, respectively. Dipodal carboxylic acids, 4,4'-(methylene)bis(benzoic acid) and bis(4-carboxyphenyl)sulfone reacted with zinc nitrate and cadmium nitrate, respectively, to form layered MOFs with one-dimensional channels.;4. Growing single crystals of bidentates of acetylacetonato ligands and copper(II) ions was not successful. Copper perchlorate reacted with 3,3'-(4-phenylene)bisacetylacetone and tetramethylethane-1,2-diamine, 3,3'-p-phenylene-bisacetylacetone and bipyridine, and 3,3'-(4,4'-biphenylene)bisacetylacetone and bipyridine to form dinuclear complexes. 4-Hydroxy-3-(pyridin-4-yl)pent-3-en-2-one reacted with 1,10-phenanthroline and copper perchlorate to form one-dimensional chains. 4-(2-hydroxy-4-oxopent-2-en-3-yl)benzoic acid was synthesized but its chelation with copper(II) was failed to get single crystals.;5. (E)-Prop-1-enylbis(2,4,6-triisopropylphenyl)phosphine was synthesized and reacted with triethylsilylium or trityl tetrakis(pentafluorophenyl)borate (TPFPB). Bis(2,6-bis(4-methylphenyl)-phenyl)chlorophosphine was reacted with anhydrous aluminum trichloride. Judging from 31P NMR spectra, none of the products is the target phosphenium ions without directly attached heteroatoms.