Zn[Htma][ddm]: An Interesting Three-Dimensional Chiral Nonlinear Optical-Active Zinc-Trimesate Framework

Abstract

The three-dimensional (3D) chiral helical framework of the new polymeric solid, Zn[Htma][ddm] (1) (tma = trimesate, ddm = p,p′-diamino-diphenyl-methane), has been prepared by the hydrothermal reaction of zinc acetate dihydrate, H3tma, and ddm. X-ray single-crystal structural analysis reveals that 1 (C22H18N2O6Zn) crystallizes in the orthorhombic P212121 space group, Z = 4 (a = 5.4533(3) Å, b = 17.593(1) Å, c = 20.542(1) Å, V = 1970.8(2) Å3). Tetrahedrally coordinated zinc centers in 1 bridged by the rigid trigonal tectonic tma ligands with Δ-configuration plus the flexible ddm molecules give rise to an interesting 3D chiral helical diamondoid network single enantiomer that has been confirmed by solid-state circular dichroism spectra. 1 is stable up to about 297 °C in the ambient environment and exhibits an intense fluorescent emission band at 420 nm upon excitation at 326 nm and the band gap semiconducing character. The theoretical calculations reveal that 1 is a potential nonlinear optical-active material.

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