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From {AuI···AuI}‑Coupled Cages to the Cage-Built 2‑D {AuI···AuI} Arrays: AuI···AuI Bonding Interaction Driven Self-Assembly and Their AgI Sensing and Photo-Switchable Behavior
journal contribution
posted on 2014-08-06, 00:00 authored by Xuan-Feng Jiang, Franky
Ka-Wah Hau, Qing-Fu Sun, Shu-Yan Yu, Vivian Wing-Wah YamMetal–metal
bonding interactions have been used to generate
a number of unique supramolecular assemblies with fascinating functions.
We presented here a new class of gold(I)-containing metallosupramolecular
cages and cage-built two-dimensional (2-D) arrays of {Au8L2}n (n =
1 or ∞, L = tetrakis-dithiocarbamato-calix[4]arene, TDCC), 1–3, which are constructed from the self-assembly
of deep-cavitand calix[4]arene-based supramolecular cages consisting
of octanuclear Au(I) motifs. Synchrotron radiation X-ray diffraction
structural analyses of 1–3 revealed
their quadruple-stranded helicate dimeric cage structure and the presence
of 2-D arrays of cages linked together by inter- and intramolecular
AuI···AuI interactions. Electronic
absorption and emission studies of complexes 1–3 indicated the occurrence of a programmable self-assembly
process in a concentration-dependent stepwise manner with the links
built via aurophilic interactions. These novel gold(I) supramolecular
cages exhibited green phosphorescence and have been shown to serve
as highly selective proof-of-concept luminescent sensors toward AgI cation among various competitive transition-metal ions.