Reversible Luminochromism of an N‐Heterocyclic Carbene‐Protected Carbon‐Centered Hexagold(I) Cluster by Solvent and Mechanical Stimuli

Author:

Foianesi‐Takeshige Leonardo Hayato1ORCID,Pei Xiao‐Li1ORCID,Zhao Pei2ORCID,Ube Hitoshi1ORCID,Lei Zhen1ORCID,Ehara Masahiro2ORCID,Shionoya Mitsuhiko1ORCID

Affiliation:

1. Department of Chemistry Graduate School of Science The University of Tokyo 7‐3‐1 Hongo, Bunkyo‐ku Tokyo 113‐0033 Japan

2. Research Center for Computational Science Institute for Molecular Science and SOKENDAI 38 Nishigo‐Naka, Myodaiji Okazaki 444‐8585 Japan

Abstract

AbstractLuminochromic gold clusters have potential applications in sensing due to the unique optical properties arising from their geometric and electronic structures. However, the rational design of such clusters is extremely challenging, especially when the goal is to impart reversible stimuli‐responsive properties to gold clusters. Herein, the reversible multi‐stimuli responsiveness of a carbon‐centered hexagold(I) CAuI6 cluster protected by N,N’‐dibenzylbenzimidazolylidene (BIBn) ligands is reported. Two types of crystals emitting blue (λemmax = 479 nm) and turquoise (λemmax = 497 nm) photoluminescence (PL) are obtained and found to be interconvertible by the addition and removal of solvent. Single‐crystal X‐ray structure analysis has revealed significant differences between the crystal structures, including the conformation of the BIBn ligands. Theoretical calculations suggest that these conformational differences directly affect the photophysical properties and that the flexibility of the BIBn ligands attached to the CAuI6 core makes this possible. Furthermore, when these crystals are grounded with a spatula, they are found to emit green PL (λemmax = 520 nm) following a partial loss of crystallinity. This is a remarkable example of both vapoluminochromism and mechanoluminochromism in an N‐heterocyclic carbene (NHC)‐protected gold cluster and holds promise as a model compound for understanding the principles governing stimuli‐responsiveness in metal clusters.

Funder

Japan Society for the Promotion of Science

Ministry of Education, Culture, Sports, Science and Technology

Japan Science and Technology Agency

Publisher

Wiley

Subject

Atomic and Molecular Physics, and Optics,Electronic, Optical and Magnetic Materials

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