Dual mechanoluminescence system comprising a solid-state di-copper() complex containing N-heterocyclic carbene ligands

A simple N-heterocyclic carbene (NHC) ligand linked to a flexible propylene linker allows the formation of "Cu-Cu"- and "2 Cu"-type geometries inside a molecular framework. The incorporation of two Cu( i ) ions in close proximity was observed in the Cu-Cu-type geometry but not in...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2021-06, Vol.5 (25), p.8845-885
Main Authors: Ogawa, Shigesaburo, Katsuragi, Haruka, Ikeda, Tsukasa, Oshima, Kazumasa, Satokawa, Shigeo, Yamazaki, Yasuomi, Tsubomura, Taro
Format: Article
Language:English
Subjects:
Coordination compounds
Copper
Copper compounds
Crystallites
Crystals
Geometry
Grinding
Ligands
Mechanoluminescence
Photoluminescence
Propylene
Solid state
Stimuli
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Summary:A simple N-heterocyclic carbene (NHC) ligand linked to a flexible propylene linker allows the formation of "Cu-Cu"- and "2 Cu"-type geometries inside a molecular framework. The incorporation of two Cu( i ) ions in close proximity was observed in the Cu-Cu-type geometry but not in the 2 Cu-type geometry. In this study, the ground-state geometries of solid-state di-copper( i ) complexes containing NHC ligands with ethyl substituents were modulated by external stimuli. A crystal with the 2 Cu-type geometry was obtained by the mechanical grinding and heating of a crystal with the Cu-Cu-type geometry, as confirmed by the disappearance of the absorption peak attributed to cuprophilic interaction in the diffuse reflection spectrum. The mechanical grinding of both crystals afforded composite states comprising small crystallites of the corresponding crystalline phases and an amorphous domain. This structural transition was accompanied by tribochromism and chronochromism. The results suggest that these di-copper( i ) complexes show promise for the development of stimuli-responsive photoluminescent Cu( i ) complexes. Multi-chromic luminescence in a di-copper( i ) complex containing NHC ligands, which exhibited dual tribochromism and chronochromism, was observed.
ISSN:1477-9226
1477-9234
DOI:10.1039/d1dt00501d