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

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Polyhedron Pub Date : 2025-03-15 Epub 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

{"title":"Soluble peripherally tert-butylphenoxy/tert-butylcarbazole substituted zinc phthalocyanines and their photophysical properties","authors":"E.N. Ovchenkova, N.G. Bichan, M.S. Gruzdev, V.A. Mozgova, U.V. Chervonova, T.N. Lomova","doi":"10.1016/j.poly.2025.117447","DOIUrl":null,"url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117447"},"PeriodicalIF":2.6000,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polyhedron","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0277538725000610","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/2/10 0:00:00","PubModel":"Epub","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

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.

Abstract Image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

可溶性外周叔丁基苯氧基/叔丁基咔唑取代酞菁锌及其光物理性质

在正戊醇和干喹啉中，通过DBU激活的邻苯二腈四聚反应，分别以20%左右的收率得到了在分子外围含有8个叔丁基苯氧基和叔丁基咔唑基团(ZnPc（tBuPhO)8和ZnPc(Carb)8）的锌（II）酞菁。用MALDI-TOF质谱、IR、1H/13C NMR和电子吸收/荧光光谱对其结构进行了确证。建立了ZnPc(tBuPhO)8/ZnPc(Carb)8/H2Pc(tBuPhO)8在有机溶剂中的光物理参数，包括q波段波长、荧光/单态氧量子产率、荧光寿命和辐射/非辐射跃迁常数。fs-TA数据证实了ZnPc(tBuPhO)8和ZnPc(Carb)8长寿命激发态的存在。与ZnPc(tBuPhO)8相比，外周咔唑取代略微降低了荧光量子产率和荧光寿命（约0.6 ns），但同时增加了单线态氧生成的可能性。在二甲基甲酰胺中形成H2Pc(tBuPhO)8质子转移配合物，使单线态氧产率提高3倍以上。有吸引力的光物理参数，溶液中的非聚集态，以及深色定位的Q吸收带，使我们认为ZnPc(Carb)8是一种有前途的光敏剂。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

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.