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Hypercarbon-Centered Gold(I)-Copper(I) Clusters Exhibiting a Dissolution/Crystallization-Induced Photoluminochromism.

Zhen Lei^1,2, Pei Zhao³, Soichi Kikkawa⁴

¹Department of Chemistry, Graduate School of Science, The University of Tokyo, Bunkyo-ku, Japan.

Chemistry (Weinheim an Der Bergstrasse, Germany)

|February 24, 2026

Summary

Metal clusters show photoluminochromism (PLC) upon dissolution. Ligand choice dictates color change, with phosphine ligands inducing a significant red shift in emission, offering insights for stimuli-responsive materials.

Keywords:

chromism copper dissolution/crystallization gold cluster photoluminescence

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Area of Science:

Materials Science
Inorganic Chemistry
Photochemistry

Background:

Molecular properties differ between solid and solution states due to structural variations.
Metal cluster molecules with photoluminescence (PL) are valuable for studying dissolution/crystallization dynamics.
PL sensitivity to coordination geometry and electronic structure enables monitoring of state changes.

Purpose of the Study:

Investigate dissolution/crystallization-induced photoluminochromism (PLC) in carbon-centered Au6Cu2 clusters.
Explore the influence of pyridylphosphine and pyridyl N-heterocyclic carbene (NHC) ligands on PLC.
Understand the structural transformations driving the observed photophysical changes.

Main Methods:

Synthesis and characterization of Au6Cu2 clusters with different ligands.
Photoluminescence spectroscopy to monitor emission changes in solid and solution states.
X-ray absorption spectroscopy and theoretical calculations to elucidate structural changes.

Main Results:

Clusters exhibit greenish-yellow emission in the solid state.
NHC-protected clusters show minimal PL change in solution.
Phosphine-protected clusters display a reversible red PL shift (>100 nm) upon dissolution.
Structural transition from octahedral to triangular prismatic geometry observed in solution.

Conclusions:

Ligand choice significantly impacts dissolution/crystallization-induced PLC in Au6Cu2 clusters.
Observed photophysical changes are linked to reversible structural rearrangements.
Findings provide design principles for novel stimuli-responsive chromic materials.