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Tuning Structural Topologies of a Series of Metal–Organic Frameworks: Different Bent Dicarboxylates

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posted on 01.05.2013, 00:00 by Ling Qin, Jinsong Hu, Mingdao Zhang, Qingxiang Yang, Yizhi Li, Hegen Zheng
Five new metal–organic frameworks incorporating the angular tetratopic ligand with different transition metal ions and bent coligands have been synthesized: [Zn4(L)2(4,4′-sdb)4(H2O)2]·3H2O (1), [Zn2(L)2(hfipbb)2(H2O)3] (2), [Zn­(L)­(oba)]·H2O (3), [Cd2(L)2(4,4′-sdb)2]·2H2O (4), [Cd2(L)­(hfipbb)­(H2O)3]·2H2O (5), [L = 1,1′-oxybis­[3,5-dipyridine-benzene, 4,4′-H2sdb = 4,4′-sulfonyldibenzoate, H2hfipbb = 4,4′-(hexafluoroisopropylidene)­bis­(benzoic acid), H2oba = 4,4′-oxybis­(benzoate)]. Structural analysis reveals that the mixed ligands display versatile coordination modes to manage the metal ions to form homochiral, inclined polycatenation (1D → 2D), 3-fold interpenetrating nets. However, the different coordinated modes, geometry, and flexibility of ligands around metal ions result in subtle differences in the final architecture. Bulk materials for 1 and 3 have a second-harmonic generation activity, approximately 0.4 and 0.8 times that of urea.

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