Porous Supramolecular Assembly of Pentiptycene-Containing Gold(I) Complexes: Persistent Excited-State Aurophilicity and Inclusion-Induced Emission Enhancement
Journal
Inorganic chemistry
Journal Volume
61
Journal Issue
30
Pages
11981
Date Issued
2022-08-01
Author(s)
Hsu, Ying-Feng
Wu, Ting-Wei
Kang, Yu-Hsuan
Wu, Cheng-Yun
Liu, Yi-Hung
Abstract
We report herein a porous supramolecular framework formed by a linear mononuclear Au(I) complex (1) via the tongue-and-groove-like joinery between the pentiptycene U-cavities (grooves) and the rod-shaped π-conjugated backbone and alkyl chains (tongues) with the assistance of C-H···π and aurophilic interactions. The framework contains distorted tetrahedral Au4 units, which undergo stepwise and persistent photoinduced Au(I)-Au(I) bond shortening (excited-state aurophilicity), leading to multicolored luminescence photochromism. The one-dimensional pore channels could accommodate different solvates and guests, and the guest inclusion-induced luminescence enhancement (up to 300%) and/or vapochromism are characterized. A correlation between the aurophilic bonding and the luminescence activity is uncovered by TDDFT calculations. Isostructural derivatives 2 and 3 corroborate both the robustness of the porous supramolecular assembly and the mechanisms of the stimulation-induced luminescence properties of 1. This work demonstrates the cooperation of aurophilicity and structural porosity and adaptability in achieving novel supramolecular photochemical properties.
Subjects
CRYSTAL PHASE-TRANSITION; FREE-VOLUME; LUMINESCENCE; AU; VAPOCHROMISM; FLUORESCENCE; THERMOCHROMISM; COORDINATION; FRAMEWORKS; MOLECULES
Publisher
AMER CHEMICAL SOC
Type
journal article