Bis‐NHC‐Diarylethene Palladium Complexes: Dynamic Behavior and Self‐Tuning Photoswitching

Bis‐NHC‐Diarylethene Palladium Complexes: Dynamic Behavior and Self‐Tuning Photoswitching Научная публикация

Журнал

Angewandte Chemie International Edition
ISSN: 1433-7851 , E-ISSN: 1521-3773

Вых. Данные

Год: 2026, Номер статьи : e22849, Страниц : DOI: 10.1002/anie.202522849

Авторы

Shnigirev Rustam B. ^1,2 , Surzhikova Iana I. ³ , Danshina Anastasia A. ^4,3 , Burykina Julia V. ³ , Ushakov Igor A. ¹ , Li Kaisu ² , Meng Xinyue ⁵ , Nelyubina Yulia V. ⁴ , Ananikov Valentine P. ³ , Munz Dominik ⁵ , Lvov Andrey G. ^1,2

Организации

1	A. E. Favorsky Irkutsk Institute of Chemistry Siberian Branch of the Russian Academy of Sciences 1 Favorsky Street Irkutsk 664033 Russia
2	Irkutsk National Research Technical University 83, Lermontov Street Irkutsk 664074 Russia
3	N. D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences 47, Leninsky prosp Moscow 119991 Russia
4	A. N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences Vavilova str., 28, bld.1 Moscow 119334 Russia
5	Coordination Chemistry Saarland University Campus C4.1 D‐66123 Saarbrücken Germany

Light offers a unique means of controlling matter with high precision, yet the development of robust photoresponsive transition-metal complexes remains a challenge. Here we report a self-tuning photochromic system based on a diarylethene-derived bis-NHC-palladium complex. The trans-anti complex (1oo) undergoes efficient stepwise photocyclization as well as unprecedented light-induced trans/cis isomerization at the metal center. Isolation and crystallographic characterization of the cis-anti isomer (2oo) reveal a thermodynamically more stable structure with enhanced photochromic performance and reversible multistate switching. Thermal studies uncover interconversion with additional rotamer, establishing a dynamic equilibrium among several photoactive palladium species. Spectroscopic and computational investigations elucidate the electronic transitions that drive both diarylethene cyclization and Pd─NHC geometric rearrangements. We demonstrate that the catalytic activity in the Suzuki-Miyaura coupling reaction can be reversibly switched by light, with the photocyclized catalyst forms showing negligible catalytic activity, while the open forms achieve high efficiency. This establishes a direct link between photoisomerization and predicted catalytic performance. Pre-catalyst evolution demonstrates that the geometry of the complex controls the balance between nanoparticle-mediated and homogeneous reactivity, delineating a novel strategy for adaptive catalysis.

Shnigirev R.B. , Surzhikova I.I. , Danshina A.A. , Burykina J.V. , Ushakov I.A. , Li K. , Meng X. , Nelyubina Y.V. , Ananikov V.P. , Munz D. , Lvov A.G.
Bis‐NHC‐Diarylethene Palladium Complexes: Dynamic Behavior and Self‐Tuning Photoswitching
Angewandte Chemie International Edition. 2026. e22849 . DOI: 10.1002/anie.202522849 WOS Scopus OpenAlex

Поступила в редакцию:	17 окт. 2025 г.
Опубликована в печати:	19 янв. 2026 г.

Web of science:	WOS:001663357700001
Scopus:	2-s2.0-105027766951
OpenAlex:	W7124737116

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