TY - JOUR

T1 - Noncovalent Dualism in Perylene-Diimide-Based Keggin Anion Complexes: Theoretical and Experimental studies

AU - Popova, Victoria G

AU - Kulik, Leonid V

AU - Samoilova, Rimma I

AU - Stass, Dmitri V

AU - Kokovkin, Vasily V

AU - Glebov, Evgeni M

AU - Berezin, Alexey S

AU - Novikov, Alexander S

AU - Garcia, Aura

AU - Tuan, Hoang Tran

AU - Rodriguez, Raul D

AU - Sokolov, Maxim N

AU - Abramov, Pavel A

N1 - The NIIC team thanks the Ministry of Science and Higher Education of the Russian Federation for the access to luminescence and analytical equipment. The Raman and AFM investigations were supported by Priority 2030-NIP/extraSP-096-375-2023. A.S.N. is grateful to the RUDN University Strategic Academic Leadership Program for support of quantum-chemical calculations. The authors thank T.S. Sukhikh for providing the data collected at the XRD Facility of NIIC SB RAS, N.B. Kompankov (NIIC SB RAS) for NMR data collection and V.R. Shayapov (NIIC SB RAS) for band gap studies. The authors thank Miss Anna Mukhacheva for the GA preparation. AG thanks financial support by TPU Priority 2030-NIP/extraSP-096-375-2023.

PY - 2023/12/4

Y1 - 2023/12/4

N2 - We report the synthesis and comprehensive characterization of organic-inorganic hybrid salts formed by bis-cationic N,N'-bis(2-(trimethylammonium)ethylene)perylene-3,4,9,10-tetracarboxylic acid bisimide (PTCD2+) and Keggin-type [XW12O40]n- (X = Si, n = 4; X = P, n = 3) polyoxometalates. (PTCD)3[PW12O40]2·3DMSO·2H2O (2) and (PTCD)2[SiW12O40]·DMSO·2H2O (3) were structurally characterized by single crystal X-ray diffraction. The cations in both structures exhibited infinite chainlike arrangements through π-π interactions, contrasting with the previously reported cation-anion stacking observed in naphthalene diimide derivatives. A detailed theoretical study employing topological analysis of the electron density distribution within the quantum theory of atoms in molecules approach provided further insights into this structural dualism. Atomic force microscopy analyses revealed the formation of self-assembled supramolecular structures on graphite from molecular monolayers (3 nm of thick) to submicrometer aggregates for 2. Hyperspectral Raman spectroscopy imaging revealed that such heterostructures are likely formed by an enhanced π-π interactions. Both complexes demonstrated interesting electrochemical behavior, photoluminescence and X-ray-induced luminescence. Electron spin resonance analysis confirmed charge separation in both compounds, with enhanced efficiency observed in compound 2. Our findings of these perylene-based organic-inorganic hybrid salts offer the potential for their application in optoelectronic devices and functional materials.

AB - We report the synthesis and comprehensive characterization of organic-inorganic hybrid salts formed by bis-cationic N,N'-bis(2-(trimethylammonium)ethylene)perylene-3,4,9,10-tetracarboxylic acid bisimide (PTCD2+) and Keggin-type [XW12O40]n- (X = Si, n = 4; X = P, n = 3) polyoxometalates. (PTCD)3[PW12O40]2·3DMSO·2H2O (2) and (PTCD)2[SiW12O40]·DMSO·2H2O (3) were structurally characterized by single crystal X-ray diffraction. The cations in both structures exhibited infinite chainlike arrangements through π-π interactions, contrasting with the previously reported cation-anion stacking observed in naphthalene diimide derivatives. A detailed theoretical study employing topological analysis of the electron density distribution within the quantum theory of atoms in molecules approach provided further insights into this structural dualism. Atomic force microscopy analyses revealed the formation of self-assembled supramolecular structures on graphite from molecular monolayers (3 nm of thick) to submicrometer aggregates for 2. Hyperspectral Raman spectroscopy imaging revealed that such heterostructures are likely formed by an enhanced π-π interactions. Both complexes demonstrated interesting electrochemical behavior, photoluminescence and X-ray-induced luminescence. Electron spin resonance analysis confirmed charge separation in both compounds, with enhanced efficiency observed in compound 2. Our findings of these perylene-based organic-inorganic hybrid salts offer the potential for their application in optoelectronic devices and functional materials.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85178647739&origin=inward&txGid=cccbb6d2e1ac8fbd9abdda2dce948711

UR - https://www.mendeley.com/catalogue/6cf14c4f-bd58-3058-9c6f-d6aebc1f386b/

U2 - 10.1021/acs.inorgchem.3c03030

DO - 10.1021/acs.inorgchem.3c03030

M3 - Article

C2 - 37977192

VL - 62

SP - 19677

EP - 19689

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 48

ER -