School of Chemistry and Chemical Technology and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China.
Inorg Chem. 2009 Nov 2;48(21):10018-23. doi: 10.1021/ic9002675.
Homochiral octupolar metal-organoboron frameworks with the general formula [M(2)L(OH)(MeOH)] x 3 H(2)O [M = Co (1), Mn (2), Ni (3), Cu (4), Zn (5), Cd (6)] have been constructed from racemic C(3)-symmetric tris(4-benzoic acid)tridurylborane and the divalent metal ions. Compounds 1-6 are isostructural and crystallize in the chiral cubic space group F432, and they adopt an eightfold-interpenetrating (10,3)-a network formed by linking bimetal building blocks with three bidentate carboxylate groups of bridging Lambda-L ligands. Bulk crystals of each of the six compounds are not a racemic mixture, and their optical activity and enantiomeric nature were demonstrated by solid-state circular dichroism spectra. Consistent with their polar structures, the colorless compounds 5 and 6 exhibit powder second harmonic generation intensities 3-4 times higher than that of potassium dihydrogen phosphate, making them, to the best of our knowledge, the first two examples of NLO-active, homochiral octupolar metal-organic solids.
具有通式[M(2)L(OH)(MeOH)] x 3 H(2)O [M = Co(1)，Mn(2)，Ni(3)，Cu(4)，Zn(5)，Cd(6)]的手性八极金属有机硼框架已由外消旋 C(3)-对称三(4-苯甲酸)三呋喃硼烷和二价金属离子构建而成。化合物 1-6 是同构的，结晶于手性立方空间群 F432 中，它们采用由双金属构建块与桥联 Lambda-L 配体的三个二齿羧酸盐连接形成的八重互穿(10,3)-a 网络。这六种化合物的块状晶体都不是外消旋混合物，其旋光性和对映性质通过固态圆二色光谱得到证明。与它们的极性结构一致，无色化合物 5 和 6 表现出比磷酸二氢钾高 3-4 倍的粉末二次谐波产生强度，使它们成为我们所知的第一批具有 NLO 活性的手性八极金属有机固体的两个实例。
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