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Unusual Attractive Au–π Interactions in Small Diacetylene‐Modified Gold Clusters
Author(s) -
Iwasaki Mitsuhiro,
Shichibu Yukatsu,
Konishi Katsuaki
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201814359
Subject(s) - diacetylene , chemistry , gold cluster , cluster (spacecraft) , acetylene , crystallography , valence (chemistry) , porphyrin , valence electron , photochemistry , electronic structure , electron , computational chemistry , organic chemistry , polymerization , physics , quantum mechanics , computer science , programming language , polymer
Abstract It is well known that alkynes act as π‐acids in the formation of complexes with metals. We found unprecedented attractive Au–π interactions in diacetylene‐modified [core+ exo ]‐type [Au 8 ] 4+ clusters. The 4‐phenyl‐1,3‐butadiynyl‐modified cluster has unusually short Au–C α distances in the crystal structure, revealing the presence of attractive interactions between the coordinating C≡C moieties and the neighboring bitetrahedral Au 6 core, which is further supported by IR and NMR spectra. Such weak interactions are not found in mono‐acetylene‐modified clusters, which indicates that they are specific for diacetylenic ligands. The attractive Au–π interactions are likely associated with the low energy of the π* orbital in the diacetylenic moieties, into which the valence electrons of the gold core may be back donated. The [Au 8 ] 4+ clusters show clear red‐shifts of >10 nm with respect to the corresponding mono‐acetylenic clusters in UV/Vis absorption bands, which indicates substantial electronic perturbation effects of the Au–π interactions.