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Abstract The assembly of cluster-based π-stacked porous supramolecular frameworks presents daunting challenges, including the design of suitable cluster building units, control of the sufficient C-H···π interactions, trade-off between structural dynamics and stability as well as understanding the resulting collective properties. Herein, we report a cluster-based C-H···π interaction-stacked porous supramolecular framework, namely, Cu12a-π, consisting of Cu12 nanocluster as a 6-connected node, which is further propagated to a dynamic porous supramolecular frameworks via dense intralayer C-H···π interactions, yielding permanent porosity. In addition, Cu12a-π can be transformed into cluster-based nonporous adaptive crystals (Cu12b-NACs) via ligand-exchange following a dissociation-reassembly mechanism. Moreover, Cu12a-π can efficiently remove 97.2% of iodine from saturated iodine aqueous solutions with a high uptake capacity of 2.96 g·g−1. These prospective results positioned at cluster-based porous supramolecular framework and enlighten follow-up researchers to design and synthesize such materials with better performance.

Arylation of gold holds paramount importance in the domain of organometallic chemistry; however, the exploration of arylgold nanoclusters remains in its infancy primarily due to the synthetic challenge. Here, we present a facile and effective arylation strategy to directly synthesize two arylgold nanoclusters (Au44a and Au44b), by using tetraarylborates, capable of transferring aryl fragments to metal centers. X-ray crystallography reveals that both Au44 nanoclusters contain an Au44 kernel co-protected by six aryl groups, two tetrahydrothiophene, and 16 alkynyl-ether ligands, the latter is generated in situ through Williamson ether reaction during the assembly processes. Notably, Au44 nanoclusters exhibit near-infrared (NIR) phosphorescence (λmax = 958 nm) and microsecond radiative relaxation at ambient condition, which is a thermal-controlled single/dual-channel phosphorescent emission revealed by temperature-dependent NIR, time-resolved emission, and femtosecond/nanosecond transition absorption spectra. This work represents a breakthrough in using aryl as protective ligands for the construction of gold nanoclusters, which is poised to have a transformative impact on organometallic nanoclusters. [ABSTRACT FROM AUTHOR]

The article presents a study which reported an all-alkynyl-protected gold nanocluster, Au20, showing a prolate Au12 tri-octahedral kernel surrounded by two Au2(CZ-PrA) Au3 dimers, four Au(CZ-PrA) Au2 monomers, and two CZ-PrA- bridges. Topics include X-ray crystal structure of Au Au20, dual emission and excitation-state dynamic of Au20, and dual emission (DE) response to multiple environment parameters.