Noncentrosymmetric Organic Solid and Its Zinc Coordination Polymer with Diamonded Network Prepared from an Ionothermal Reaction: Syntheses, Crystal Structures, and Second-Order Nonlinear Optics Properties

Abstract

An organic ligand 4-(1,2,4-triazol-1-yl) benzoic acid (Htzbc) with a nonlinear optical (NLO) chromophore has been synthesized. Reaction of Zn(NO3)2 with Htzbc ligand in 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid afforded compound Zn(tzbc)2 (1). The Htzbc organic solid and 1 crystallize in the acentric Pn and Cc space groups, respectively. The tetrahedral Zn2+ center in 1 coordinates to two triazole nitrogen atoms and two carboxylate oxygen atoms from four tzbc– ligands, leading to a noncentrosymmetric 5-fold interpenetrating diamondoid network. Second-harmonic generation (SHG) measurements revealed the Htzbc solid and 1 have SHG activities. The Htzbc compound has a large SHG effect, which is approximately 3 times that of KDP and is type-I phase matchable, while 1 also belongs to phase-matchable class with a SHG response of about 1.2 times that of KDP. The SHG active of the organic solid can be derived from the inherently dipolar Htzbc molecule as well as the optimal relative orientation of the molecular NLO-phores in the crystal packing. The odd number-fold interpenetrated diamondoid network with dipolar NLO chromophoric units based on asymmetrical bridging ligands and metal centers results in the SHG activity of 1. In addition, elemental analysis, IR spectra, powder X-ray diffraction patterns (PXRD), and thermogravimetric analysis of both compounds are described.

Crystal Structure, Spectroscopy and Photocatalytic Properties of a Co(II) Complex Based on 5-(1,2,4-triazol-1-yl)pyridine-3-carboxylic Acid

“…In the last few years, many metal-organic coordination compounds constructed by triazole ligands have been reported; some of them not only have charming molecular structures, but also promising physical properties [1][2][3]. In addition, the structure of coordination complexes will be influenced by the position of substituent groups in the ligands [4].…”

Crystal structure of catena-poly[hexakis(μ2-chlorido)-hexakis(4-(1H-pyrazol-5-yl)pyridine-κN)tricadmium(II)], Cd3C48H42Cl6N18

“…Coordination polymers (CPs) have attracted worldwide attention not only for their potential applications in the fields of photochemical areas [1], gas adsorption and separation [2], molecular magnetism [3], heterogeneous catalysis [4,5], and nonlinear optics [6] but also for their intriguing topologies and crystal packing motifs [7][8][9]. However, it is still a challenge to exactly predict the structure of CPs.…”

Bis(dimethylamine-κN)bis[4-(1,2,4-triazol-1-yl)benzoato-κO]copper(II)

“…Different polymers based on 4-(1,2,4-triazol-1-yl)benzoic acid complexes have been reported (Du et al, 2014). They not only feature structural varieties, but also can be applied in gas storage (Wang et al, 2012). In this context we have investigated crystals formed from a copper(II) solution and 4-(1,2,4-triazol-1-yl)benzoic acid under solvothermal conditions.…”