Experimental and theoretical investigation of structures and relative reactivity of Pr@C-74 and Pr@C-74(C6H3Cl2)

摘要

Pr@C-74(C6H3Cl2), a novel dichlorophenyl-functionalized derivative of the Pr-containing monometallofullerene Pr@C-74, was successfully prepared and isolated. Its molecular-structure was determined as Pr@D-3h(14246)C-74(C6H3Cl2) by a combined mass spectrometry (MS), UV-visible-near-infrared (UV-vis-NIR) absorption spectroscopy, and quantum-mechanics characterization. Using the computed theoretical data, we evaluated the isomeric structures, metal-to-cage electron transfer, and metal-cage interactions of Pr@C-74(C6H3Cl2) and the pristine Pr@C-74. Furthermore, the relative reactivity of C-74, Pr@C-74, and Pr@C-74(C6H3Cl2) was estimated by the calculated electronic structures and band gaps, and the results indicated that the open-shell structure and relatively small gap should be responsible for the unsuccessful isolation of C-74 and Pr@C-74.