Issue 20, 2021

Novel noncentrosymmetric polar coordination compounds derived from chiral histidine ligands

Abstract

Crystals of chiral coordination compounds, [L-C6H10N3O2ZnBr3] (L-ZnBr), [D-C6H10N3O2ZnBr3] (D-ZnBr), [L-C12H20N6O4Cd2Cl5] (L-CdCl), and [D-C12H20N6O4Cd2Cl5] (D-CdCl), have been grown in high yields by using MX2 (M = Zn or Cd; X = Br or Cl) and L- or D-histidine by a slow evaporation method in acidic media. Single crystal X-ray diffraction reveals that while the structures of L-ZnBr and D-ZnBr crystallizing in the polar space group, P21, consist of slightly distorted ZnOBr3 tetrahedra and the respective chiral histidine ligands, those of L-CdCl and D-CdCl with the triclinic noncentrosymmetric (NCS) space group, P1, are composed of distorted CdOCl4 trigonal bipyramids and the corresponding histidine ligands. Whereas the structures of L-ZnBr and D-ZnBr can be extended to pseudo-1D chains via hydrogen bonds, those of L-CdCl and D-CdCl can be assembled to pseudo-3D frameworks through hydrogen bonds and π–π interactions. UV-vis diffuse reflectance spectra suggest that the title compounds have large optical band gaps of ca. 5 eV. The powder second-harmonic generation (SHG) measurements indicate that the new materials with NCS structures have mild SHG efficiencies of ca. 0.2 times that of KH2PO4, and type-I phase-matching behaviors. Circular dichroism spectra have confirmed the absolute configurations of the title compounds further. The synthesis approach suggests a systematic method toward the discovery of novel coordination compounds with NCS structures.

Graphical abstract: Novel noncentrosymmetric polar coordination compounds derived from chiral histidine ligands

Supplementary files

Article information

Article type
Research Article
Submitted
13 juil. 2021
Accepted
20 août 2021
First published
20 août 2021

Inorg. Chem. Front., 2021,8, 4536-4543

Novel noncentrosymmetric polar coordination compounds derived from chiral histidine ligands

W. Seo and K. M. Ok, Inorg. Chem. Front., 2021, 8, 4536 DOI: 10.1039/D1QI00869B

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