CCCCC pentadentate chelates with planar Möbius aromaticity and unique properties

本课题充分发挥了厦门大学多学科协同研究优势通讯作者为夏海平教授合成、表征、刘刚教授生物医学应用和吕鑫教授理论计算。合成实验和结构表征由朱从青第一作者目前在麻省理工学院、2005年诺贝尔化学奖得主Richard Schrock教授课题组从事博士后研究完成生物医学应用由杨彩霞共同第一作者、林凎、杨宇惠、王晓勇合作完成理论计算由朱军、王永恒、朱从青完成。美国NIH的陈小元教授参与了生物医学应用的讨论。该研究工作得到国家自然科学基金委、科技部项目的支持。The coordinating atoms in polydentate chelates are primarily heteroatoms. We present the first examples of pentadentate chelates with all binding atoms of the chelating agent being carbon atoms, denoted as chelates. Having up to five metal-carbon bonds in the equatorial plane has not been previously observed in transition metal chemistry. Density functional theory calculations showed that the planar metallacycle has extended Craig-Möbius aromaticity arising from 12-center–12-electron dπ-pπ π-conjugation. These planar chelates have broad absorption in the ultraviolet-visible–near-infrared region and, thus, notable photothermal performance upon irradiation by an 808-nm laser, indicating that these chelates have potential applications in photothermal therapy. The combination of facile synthesis, high stability, and broad absorption of these complexes could make the polydentate carbon chain a novel building block in coordination chemistry.the National Basic Research Program of China (nos. 2012CB821600 and 2014CB744503) , the National Science Foundation of China (nos. 21332002, 81422023, 51273165, 21490573, and 21573179)