Černý Jiří, Dokládalová Lenka, Horáková Petra, Lyčka Antonín, Mikysek Tomáš, Bureš Filip
Centre of Organic Chemistry Ltd., Rybitví 296, 53354, Rybitví, Czech Republic.
Department of Analytical Chemistry, University of Pardubice, Faculty of Chemical Technology, Studentská 573, 53210, Pardubice, Czech Republic.
Chem Cent J. 2017 Apr 5;11(1):31. doi: 10.1186/s13065-017-0260-x.
A series of rare-earth bisphthalocyanines of praseodymium, samarium and gadolinium bearing 5-bromo-2-thienyl substituents were prepared for the first time.
Three bis[octakis(5-bromo-2-thienyl)] rare-earth metal(III) bisphthalocyanine complexes (Pr, Sm, Gd) were synthesized for the first time. The new compounds were characterized by UV-vis, NIR, FT-IR, mass spectroscopy and thermogravimetry as well as elementary analysis and electrochemistry. Production of singlet oxygen was also estimated using 9,10-dimethylanthracene method.
The bromine substituent causes significant changes in molecule paramagnetism, singlet oxygen production, HOMO position and spectral characteristics. The compounds in solutions exist in two forms (neutral and/or reduced) depending on the solvent and rare-earth metal. Moreover, the compounds exhibit much increased stability under acid conditions compared with non-brominated derivatives. Graphical abstract Prepared compounds for the study of their chemical and other properties.
首次制备了一系列带有5-溴-2-噻吩基取代基的镨、钐和钆稀土双酞菁。
首次合成了三种双[八（5-溴-2-噻吩基）]稀土金属（III）双酞菁配合物（Pr、Sm、Gd）。通过紫外可见光谱、近红外光谱、傅里叶变换红外光谱、质谱、热重分析以及元素分析和电化学对新化合物进行了表征。还使用9,10-二甲基蒽法估算了单线态氧的产生。
溴取代基导致分子顺磁性、单线态氧产生、最高占据分子轨道（HOMO）位置和光谱特性发生显著变化。根据溶剂和稀土金属的不同，溶液中的化合物以两种形式（中性和/或还原态）存在。此外，与未溴化的衍生物相比，这些化合物在酸性条件下表现出大大提高的稳定性。图形摘要 为研究其化学性质和其他性质而制备的化合物。
