Structure and properties of radical anion and dianion salts of organic dye trans-perinone and its mixed salt with gallium(iii ) phthalocyanine
| Autor: | Alexey V. Kuzmin, Salavat S. Khasanov, Nikita R. Romanenko, Maxim V. Mikhailenko, Maxim A. Faraonov, Dmitri V. Konarev |
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| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
Heisenberg model Dimer Cryptand Gallium chloride General Chemistry 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences law.invention chemistry.chemical_compound Crystallography chemistry law Excited state Perinone Materials Chemistry Phthalocyanine Electron paramagnetic resonance |
| Zdroj: | New Journal of Chemistry. 45:13599-13607 |
| ISSN: | 1369-9261 1144-0546 |
| DOI: | 10.1039/d1nj01636a |
| Popis: | Reduction of organic dye trans-perinone (its abbreviation is perinone) in different experimental conditions allows us to obtain and characterize radical anion {cryptand(K+)}[perinone˙−] (1) and dianion {PPN+}2[perinone2−]·2C6H4Cl2 (2) salts of this dye. The salts have layered structures. Perinone˙− radical anions form π–π stacked dimers in 1 with an effective interaction between them, whereas perinone2− dianions are isolated in 2. Reduction of perinone is accompanied by an essential red shift of the absorption bands of the starting dye and, as a result, the salts have absorption nearly in the whole visible range. Strong coupling of spins is observed in the π-stacking [perinone˙−]2 dimers of 1, which are described by the Heisenberg model for isolated pairs of antiferromagnetically interacting spins with J/kB = −38 K. The triplet excited state of the dimers is populated above 50 K. The EPR signal of 1 shows features characteristic of triplets, and the average separation of spins within the dimers estimated in the point-dipole approximation is 8.7 A. The dimers manifest an intense charge transfer band with a maximum at 1356 nm. A mixed {cryptand(K+)}[(perinone)0.5(GaIIIClPc)]−·3C6H4Cl2 (3) salt with two anionic chromophores – perinone and gallium chloride phthalocyanine – is also obtained in the crystalline form. It has only one negative charge and spin per [(perinone)0.5(GaIIIClPc)] unit. As a result, the magnetic behavior of 3 is described well by contributions from isolated perinone˙− radical anions and {GaIIIClPc}2˙− dimers with effective π–π stacking between phthalocyanines and one negative charge and S = 1/2 spin per dimer. |
| Databáze: | OpenAIRE |
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