Molecular Switches Guided by a Reversible Access to Room-Temperature Phosphorescence and ESIPT Fluorescence | Sciact - CRIS-system of Boreskov Institute of Catalysis

Molecular Switches Guided by a Reversible Access to Room-Temperature Phosphorescence and ESIPT Fluorescence Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2025, Volume: 64, Number: 14, Pages: 6964-6976 Pages count : 13 DOI: 10.1021/acs.inorgchem.5c00222

Authors

Olennikov Vyacheslav E. ^1,2 , Zvereva Valentina V. ¹ , Kriventsov Vladimir V. ³ , Konchenko Sergey N. ¹ , Sukhikh Taisiya S. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch Russian Academy of Sciences, Novosibirsk 630090, Russia
2	Department of Natural Sciences, National Research University─Novosibirsk State University, Novosibirsk 630090, Russia
3	Synchrotron Radiation Facility─Siberian Circular Photon Source ≪SKIF≫ Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk 630559, Russia

This paper presents the results of a comprehensive study, including ones of methods implemented on synchrotron radiation, such as XANES and EXAFS, of Zn complexes with α-aminomethylphosphine oxide (L) based on phenylbenzothiazole and isolating them in the form of crystalline phases, α-[ZnL2Cl2], [ZnL- (EtOAc)Cl2], [ZnL2Cl2]•1.5CH2Cl2 and [ZnL2Cl2]•1.5 CHCl3. This work contributes to the creation of luminescent molecular switches with multiple radiation pathways that can be activated by an external stimulus. We have developed complexes of Zn with α-aminomethylphosphine oxide (L) based on phenylbenzothiazole and isolated them in the form of crystalline phases, α-[ZnL2Cl2], [ZnL-(EtOAc)Cl2], [ZnL2Cl2]•1.5CH2Cl2 and [ZnL2Cl2]•1.5 CHCl3. They possess an intramolecular hydrogen bond of medium strength capable of intramolecular excited proton transfer (ESIPT), as well as an intersystem transition between singlet and triplet states. Since none of these processes is predominant, one or the other may occur depending on a slight change in the geometry of the molecules. The crystalline phases exhibit red ESIPT fluorescence, while the metastable amorphous β-[ZnL2Cl2] phase with a similar coordination center structure exhibits yellow phosphorescence at room temperature. A combined experimental and quantum chemical study of TD-DFT clarified the behavior of the double emission of α-[ZnL2Cl2] and β-[ZnL2Cl2] polymorphs, which is explained by the high dependence of the probability of processes in the excited state on the geometry of the phenylbenzothiazole fragment. The reversible phase transition, accompanied by a change in the emission mechanism (ESIPT fluorescence versus phosphorescence), can be controlled by adding CHCl3 and Et2O, respectively. We have demonstrated the good adhesion properties of the polymer-free β-film [ZnL2Cl2] to glass and plastic, the naked eye color response to Et2O exposure, and the ease of recovery with CHCl3.

Olennikov V.E. , Zvereva V.V. , Kriventsov V.V. , Konchenko S.N. , Sukhikh T.S.
Molecular Switches Guided by a Reversible Access to Room-Temperature Phosphorescence and ESIPT Fluorescence
Inorganic Chemistry. 2025. V.64. N14. P.6964-6976. DOI: 10.1021/acs.inorgchem.5c00222 WOS Scopus OpenAlex publication_identifier_short.sciact_skif_identifier_type

Submitted:	Jan 15, 2025
Accepted:	Mar 25, 2025
Published online:	Apr 2, 2025

Web of science:	WOS:001457710500001
Scopus:	2-s2.0-105003088276
OpenAlex:	W4409092020
publication_identifier.sciact_skif_identifier_type:	3951

DB	Citing
Scopus	7
OpenAlex	8
Web of science	8