Bartkowski Krzysztof, Pawlicki Miłosz
Department of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50383, Wrocław, Poland.
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30387, Kraków, Poland.
Angew Chem Int Ed Engl. 2021 Apr 12;60(16):9063-9070. doi: 10.1002/anie.202011848. Epub 2021 Mar 5.
A strong conjugation present in fused systems plays a crucial role in tuning of the properties that would be showing a dependence on the efficiency of π-electrons coupling. The π-cloud available in the final structure can be drastically influenced by a side- or a linear fusion of unsaturated and conjugated hydrocarbons. The linear welding of naphthalene/anthracene or quinoxaline/benzo[g]quinoxaline with triphyrin(2.1.1) gives structures where the competition between local and global delocalization is distinguished. The aromatic character observed in skeletons strongly depends on the oxidation state of the macrocyclic flanking and is either extended over the whole system or kept as a composition of local currents (diatropic and paratropic) of incorporated units. The hybrid systems show the properties derived from the π-conjugations that interlace one another but also show a significant independence of (aza)acene subunits reflected in the observed spectroscopic properties.
稠合体系中存在的强共轭作用在调节性质方面起着关键作用，这些性质将依赖于π电子耦合效率。最终结构中的π云会受到不饱和和共轭烃的侧链或线性稠合的显著影响。萘/蒽或喹喔啉/苯并[g]喹喔啉与三卟啉(2.1.1)的线性连接产生的结构中，局部离域和全局离域之间的竞争得以区分。在骨架中观察到的芳香性很大程度上取决于大环侧翼的氧化态，并且要么扩展到整个体系，要么作为并入单元的局部电流（抗磁和顺磁）的组合而保留。杂化体系展现出源自相互交织的π共轭作用的性质，但也显示出（氮）并苯亚基的显著独立性，这反映在观察到的光谱性质中。
