Lu Zhou, Archambault Cynthia M, Li Shan, Syed Umar, Wang Sicheng, Kumar Abinaya, Shen Guoyin, Liu Zhenxian, Omary Mohammad A, Yan Hao
Department of Chemistry, University of North Texas, 1155 Union Circle #305070, Denton, Texas76203, United States.
Department of Materials Science and Engineering, University of North Texas, 1155 Union Circle #305310, Denton, Texas76203, United States.
J Phys Chem Lett. 2023 Jan 19;14(2):508-515. doi: 10.1021/acs.jpclett.2c03284. Epub 2023 Jan 10.
Metallophilicity has been widely studied as a fundamental supramolecular interaction. However, the extent and directionality thereof remain controversial. A major obstacle lies in the difficulty to separately control the geometry and chemical composition. Herein, we address this challenge by modulating metallophilicity with mechanical pressure. Using a multinuclear Cu(I) complex as model system, we report anomalous anisotropies of (supra)molecular structures, vibrations, and interaction energies upon isotropic compression as well as concomitant (essentially turn-on) piezochromic luminescence enhancement with ∼10 modulation. The characterizations indicate opposite behaviors of contact distances and cuprophilic interactions for intermolecular vs intramolecular Cu-Cu pairs under pressure. Theoretical calculations break down the attractive and repulsive forces associated with cuprophilicity, its spontaneous 4p-3d hybridization origin, and direction-dependent interaction strength. The use of isotropic mechanical force reveals the intrinsic anisotropy of metallophilicity in multinuclear systems.
亲金属性作为一种基本的超分子相互作用已得到广泛研究。然而，其程度和方向性仍存在争议。一个主要障碍在于难以分别控制几何结构和化学成分。在此，我们通过机械压力调节亲金属性来应对这一挑战。使用多核Cu(I)配合物作为模型系统，我们报道了在各向同性压缩下（超）分子结构、振动和相互作用能的异常各向异性，以及伴随的（本质上是开启的）压致变色发光增强，调制率约为10倍。表征结果表明，在压力下，分子间与分子内Cu-Cu对的接触距离和铜亲性相互作用表现出相反的行为。理论计算剖析了与铜亲性相关的吸引力和排斥力、其自发的4p-3d杂化起源以及方向依赖性相互作用强度。各向同性机械力的使用揭示了多核系统中亲金属性固有的各向异性。
