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Luminescent Cu4I4-cubane clusters based on N-methyl-5,10-dihydrophenarsazines
Milyausha F Galimova1, Ekaterina M Zueva2, Alexey B Dobrynin1
1Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 8 Arbuzov Street, Kazan 420088, Russian Federation. milya1949@mail.ru.
Abstract:
Two luminescent Cu4I4-cubane tetramers with N-methyl-10-(p-halogenophenyl)-5,10-dihydrophenarsazine ligands were synthesized and characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction analysis. The UV-Vis absorption and emission properties were studied and rationalized by DFT and time-dependent DFT calculations. The luminescence behavior was found to be rather different from that of recently reported tetranuclear copper iodide cubane clusters based on As,O-analogues - 10-(aryl)phenoxarsines. The crystalline powders of both complexes exhibit the temperature-dependent dual-band emission: the low-energy emission originates from the cluster-centered (3CC) triplet state, whereas the high-energy emission was attributed to the intraligand (3IL) triplet state.
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