School of Chemistry and Chemical Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China.
State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
Inorg Chem. 2023 Mar 27;62(12):4747-4751. doi: 10.1021/acs.inorgchem.3c00061. Epub 2023 Mar 15.
, a highly robust and antiaromatic rhenium(I) complex of triarylrosarin, is synthesized. The H NMR spectrum of shows upfield-shifted pyrrole protons and highly downfield-shifted inner protons that confirm its antiaromatic nature, with density functional theory calculations strongly supporting this interpretation. Antiaromatic absorbs from the UV to near-IR region of the optical spectrum; cyclic voltammetry, thin-layer UV-vis spectroelectrochemistry, and spin-density distributions clearly reveal that the rosarin backbone of undergoes redox chemistry. The X-ray structure of shows a fully coordinated and protonated inner cavity that effectively prevents proton-coupled electron transfer when treated with an acid. A remarkably negative NICS(0) value, clockwise anisotropy of the induced current density ring current, and the aromatic shielded inner cavity in the 2D ICSS(0) map reveal that the T state of is aromatic based on Baird's rule.
合成了一种高度稳定的三芳基罗沙林反芳香 Re(I)配合物。1H NMR 谱显示，其吡咯质子向低场位移，内环质子向高场位移，证实了其反芳香性质，密度泛函理论计算也强烈支持这一解释。反芳香化合物 1 在紫外光至近红外光谱区有吸收；循环伏安法、薄层紫外可见光谱电化学和自旋密度分布清楚地表明，罗沙林骨架经历了氧化还原化学。1 的 X 射线结构显示出完全配位和质子化的内腔，当与酸处理时，有效地阻止质子耦合电子转移。显著的负 NICS(0)值、诱导电流密度环电流的顺时针各向异性以及 2D ICSS(0)图中芳香屏蔽的内环腔表明，根据 Baird 规则，1 的 T 态是芳香的。
