Tuning Structural Topologies of a Series of Metal–Organic
Frameworks: Different Bent Dicarboxylates
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Abstract
Five
new metal–organic frameworks incorporating the angular
tetratopic ligand with different transition metal ions and bent coligands
have been synthesized: [Zn<sub>4</sub>(L)<sub>2</sub>(4,4′-sdb)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>]·3H<sub>2</sub>O (<b>1</b>), [Zn<sub>2</sub>(L)<sub>2</sub>(hfipbb)<sub>2</sub>(H<sub>2</sub>O)<sub>3</sub>] (<b>2</b>), [Zn(L)(oba)]·H<sub>2</sub>O (<b>3</b>), [Cd<sub>2</sub>(L)<sub>2</sub>(4,4′-sdb)<sub>2</sub>]·2H<sub>2</sub>O (<b>4</b>), [Cd<sub>2</sub>(L)(hfipbb)(H<sub>2</sub>O)<sub>3</sub>]·2H<sub>2</sub>O (<b>5</b>), [L
= 1,1′-oxybis[3,5-dipyridine-benzene, 4,4′-H<sub>2</sub>sdb = 4,4′-sulfonyldibenzoate, H<sub>2</sub>hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic
acid), H<sub>2</sub>oba = 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 <b>1</b> and <b>3</b> have a second-harmonic
generation activity, approximately 0.4 and 0.8 times that of urea
