State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Centre of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, 361005, Xiamen, China.
State Key Laboratory of Molecular Vaccinology and Molecular Diagnostics, Centre for Molecular Imaging and Translational Medicine, School of Public Health, Xiamen University, 361102, Xiamen, China.
Nat Commun. 2019 Apr 2;10(1):1488. doi: 10.1038/s41467-019-09367-8.
Polydentate complexes containing combinations of nitrogen and carbon (N and C) ligating atoms are among the most fundamental and ubiquitous molecules in coordination chemistry, yet the formation of such complexes with planar high-coordinate N/C sites remains challenging. Herein, we demonstrate an efficient route to access related complexes with tetradentate CCCN and pentadentate CCCCN and NCCCN cores by successive modification of the coordinating atoms in complexes with a CCCC core. Combined experimental and computational studies reveal that the rich reactivity of metal-carbon bonds and the inherent aromaticity of the metallacyclic skeletons play key roles in these transformations. This strategy addresses the paucity of synthetic approaches to mixed N/C planar pentadentate chelating species and provides valuable insights into the synthesis of carbon-based high-coordinate complexes. Furthermore, the resulting complexes are the examples of organometallic species with combined photoacoustic, photothermal, and sonodynamic properties, which makes them promising for application in related areas.
含氮和碳（N 和 C）配位原子的多齿配合物是配位化学中最基本和最普遍的分子之一，但具有平面高配位 N/C 位点的此类配合物的形成仍然具有挑战性。在此，我们展示了一种通过连续修饰具有 CCCC 核的配合物中的配位原子，从而有效获得具有四齿 CCCN 和五齿 CCCCN 和 NCCCN 核的相关配合物的方法。实验和计算研究表明，金属-碳键的丰富反应性和金属环骨架的固有芳香性在这些转化中起着关键作用。该策略解决了混合 N/C 平面五齿螯合物种合成方法的缺乏问题，并为基于碳的高配位配合物的合成提供了有价值的见解。此外，所得配合物是具有光声、光热和超声动力学特性的有机金属物种的实例，这使得它们有望在相关领域得到应用。
