Soluble peripherally tert-butylphenoxy/tert-butylcarbazole substituted zinc phthalocyanines and their photophysical properties

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Polyhedron Pub Date : 2025-02-10 DOI:10.1016/j.poly.2025.117447

E.N. Ovchenkova, N.G. Bichan, M.S. Gruzdev, V.A. Mozgova, U.V. Chervonova, T.N. Lomova

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Abstract

Zinc(II) phthalocyanines containing eight tert-butylphenoxy and tert-butylcarbazole groups at the molecule periphery (ZnPc(^tBuPhO)₈ and ZnPc(Carb)₈, respectively) were obtained with about 20 % yield by the DBU activated phthalonitrile tetramerization in pentanol and dry quinoline, respectively. Their structure was confirmed using MALDI-TOF mass spectrometry, IR, ¹H/¹³C NMR, and electronic absorption/fluorescence spectroscopy. The ZnPc(^tBuPhO)₈/ZnPc(Carb)₈/H₂Pc(^tBuPhO)₈ photophysical parameters, including the Q-band wavelength, fluorescence/singlet oxygen quantum yields, fluorescence lifetime, and radiative/non-radiative transition constant in organic solvents, were established. The presence of ZnPc(^tBuPhO)₈ and ZnPc(Carb)₈ long-life excited states is confirmed by the fs-TA data. The peripheral carbazole substitution decreases slightly both the fluorescence quantum yield and fluorescence lifetime (by ∼0.6 ns) relative to that for ZnPc(^tBuPhO)₈, but simultaneously increases the possibility of singlet oxygen generation. The formation of the H₂Pc(^tBuPhO)₈ proton transfer complex in dimethylformamide leading to the increase in singlet oxygen yield more than 3 times was established. Attractive photophysical parameters, non-aggregated state in solutions, and the bathochromically located Q absorption band allow us to consider ZnPc(Carb)₈ as a promising photosensitizer.

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.