A Gold Quartet Framework with Reversible Anisotropic Structural Transformation Accompanied by Luminescence Response

Abstract

Hierarchy and chirality are the fundamental characteristics of biomolecules. Chemistry on hierarchical self-assembly and spontaneous symmetry breaking helps to uncover the mechanism of living activities and the origin of chirality in nature. Herein is described an unprecedented chiral gold quartet framework (GQF) with C4-symmetric structure hierarchically aggregated from an achiral anionic [Au10(dpptrz)4S4]2− (dpptrz-Au10), which was acquired via click-reaction-induced and Au(I)···Au(I)-interaction-directed cluster-to-cluster transformation (CCT) from the rationally designed [(dppa)6Au18S8]2+ (dppa-Au18). Inter-cluster hydrogen bonding and alkali ion coordination are observed to assist the hierarchical self-assembly and chiral self-organization of the GQF. Upon exposing the crystal to vacuum, the bottom-up constructed GQF shows an anisotropic structural transformation accompanied by a visual luminescence change in a single-crystal-to-single-crystal (SCSC) manner that becomes reversible upon removal of vacuum. This research largely advances the potential of polynuclear gold(I)-sulfido clusters in hierarchical self-assembly and luminescent materials.1 References: 1. Yao, L.-Y.; Yam, V. W.-W. Chem 2019, under revision. †Areas of Excellence Scheme (AoE), University Grants Committee (Hong Kong)