Structural‐transformation‐induced Drastic Luminescence Changes in an Organic‐Inorganic Hybrid [ReN(CN)4]2− Salt Triggered by Chemical Stimuli

We synthesized a (1‐propylpyridinium)2[ReN(CN)4]‐type organic–inorganic hybrid exhibiting water‐vapor‐induced drastic structural changes of the [ReN(CN)4]2− assemblies. Specifically, upon exposure to water vapor, dehydrated nitrido‐bridged chains were converted to hydrated cyanido‐bridged tetranucle...

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Published in:Angewandte Chemie International Edition 2023-08, Vol.62 (32), p.e202306853-n/a
Main Authors: Ohtani, Ryo, Xu, Jianeng, Yanagisawa, Junichi, Iwai, Yuudai, Ehara, Takumi, Miyata, Kiyoshi, Onda, Ken, Pirillo, Jenny, Hijikata, Yuh, Hiraoka, Tomoaki, Hayami, Shinya, Le Ouay, Benjamin, Ohba, Masaaki
Format: Article
Language:English
Subjects:
Chemical Responsivity
Chemical stimuli
Chemical synthesis
Crystals
Dehydration
Doppler effect
Emission
Emissions
Luminescence
Metal Complex
Near infrared radiation
Organic-Inorganic Hybrid
Physical properties
Red shift
Thermal Expansion
Water vapor
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Summary:We synthesized a (1‐propylpyridinium)2[ReN(CN)4]‐type organic–inorganic hybrid exhibiting water‐vapor‐induced drastic structural changes of the [ReN(CN)4]2− assemblies. Specifically, upon exposure to water vapor, dehydrated nitrido‐bridged chains were converted to hydrated cyanido‐bridged tetranuclear clusters via rearrangements of large molecular building units in the crystals. These switchable assembly forms display substantially different photo‐physical properties, although in both cases the emission is caused by a metal‐centered d–d transition. The nitrido‐bridged chain exhibited a near‐infrared (749 nm) emission, which blue‐shifted as the temperature increased, while a visible (561 nm) emission and its red shift was demonstrated by the cyanido‐bridged cluster. The large shift in luminescent properties between near‐infrared and visible emissions without any loss in quantum yield was achieved by massive structural changes of an organic–inorganic luminescent hybrid.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202306853