†Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
‡Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Emil-Fischer-Straße 42, 97074 Würzburg, Germany.
J Am Chem Soc. 2015 Jun 3;137(21):6750-3. doi: 10.1021/jacs.5b03805. Epub 2015 May 22.
Reduction of 2-(BMes2)pyrene (B1) and 2,7-bis(BMes2)pyrene (B2) gives rise to anions with extensive delocalization over the pyrenylene bridge and between the boron centers at the 2- and 2,7-positions, the typically unconjugated sites in the pyrene framework. One-electron reduction of B2 gives a radical anion with a centrosymmetric semiquinoidal structure, while two-electron reduction produces a quinoidal singlet dianion with biradicaloid character and a relatively large S0-T1 gap. These results have been confirmed by cyclic voltammetry, X-ray crystallography, DFT/CASSCF calculations, NMR, EPR, and UV-vis-NIR spectroscopy.
2-(BMe2)pyrene（B1）和 2,7-双（BMe2）pyrene（B2）的还原导致阴离子在芘桥和硼中心之间广泛离域，这些硼中心位于芘框架的 2-和 2,7-位置，通常是非共轭的。B2 的单电子还原产生具有中心对称半醌结构的自由基阴离子，而双电子还原则产生具有双自由基特征和相对较大 S0-T1 能隙的醌型单重态二阴离子。这些结果已经通过循环伏安法、X 射线晶体学、DFT/CASSCF 计算、NMR、EPR 和 UV-vis-NIR 光谱得到证实。
