Steering Lu3N clusters in C76-78 cages: cluster configuration dominated by cage transformation.
Nanoscale 14:46 (2022) 17290-17296
Abstract:
While the strong interaction between the internal unit and the fullerene cage inside metallofullerenes is widely acknowledged, how the cage transformation interacts with the cluster configuration remains elusive. For this purpose, we herein synthesized three metallofullerene molecules with an easy-to-compare cluster configuration and cage arrangement, namely Lu3N@Cs(17 490)-C76, Lu3N@C2(22 010)-C78, and Lu3N@D3h(5)-C78. The three lutetium-based nitride clusterfullerenes (NCFs) with small C76-78 carbon cages were synthesized by a modified arc-discharge method and their structures were unambiguously confirmed by X-ray crystallography. Notably, the cage transformation from Cs(17 490)-C76 to C2(22 010)-C78via a simple C2-unit insertion leads to a remarkable configuration change of the encapsulated Lu3N cluster from an unusual asymmetric plane to a common symmetric one. This close correlation between the cluster configuration and cage transformation is further confirmed by the pyramidal Lu3N cluster in Lu3N@D3h(5)-C78 other than the symmetric planar Lu3N unit in Lu3N@C2(22 010)-C78, as a result of an even larger difference in the cage arrangement. Astonishingly, such a cluster shrinkage, accompanied by an increase in the cage size from Cs(17 490)-C76 to D3h(5)-C78, is dramatically opposite to the cluster expansion with cage elongation found in La2C2- or Y2C2-based metallofullerenes.Operational stability, low light performance, and long-lived transients in mixed-halide perovskite solar cells with a monolayer-based hole extraction layer
Solar Energy Materials and Solar Cells Elsevier 245 (2022) 111885
Materials to Improve the Performance of Sn-Based Perovskite Solar Cells
Institute of Electrical and Electronics Engineers (IEEE) 00 (2022) 10-11
Cluster-Geometry-Associated Metal-Metal Bonding in Trimetallic Carbide Clusterfullerenes.
Inorganic chemistry 61:29 (2022) 11277-11283
Abstract:
Geometry configurations of the metallic clusters play a significant role in the involved bonding nature. Herein, we report the crystallographic characterization of unprecedented erbium-based trimetallic clusterfullerenes, namely, Er3C2@Ih(7)-C80, in which the inner Er3C2 cluster presents a lifted bat ray configuration with the C2 unit elevated by ∼1.62 Å above the Er3 plane. Within the plane, the Er···Er distances for Er1···Er2, Er1···Er2A, and Er2···Er2A are 3.4051(15), 3.4051(15), and 3.3178(15) Å, respectively, falling into the range of the metal-metal bonding. Density functional theory calculations unveil the three-center-one-electron Er-Er-Er bond in Er3C2@Ih(7)-C80 with one electron shared by three metals, and thus, its exceptional electronic structure can be expressed as (Er3)8+(C2)2-@C806-. Interestingly, with the further observation on the geometry configurations of the encapsulated clusters in M3C2@C2n (M = Sc, Y, and Lu) series, we find that the lifted bat ray configuration of the inner cluster is explicitly associated with the formation of the bonding interactions between the inner metals. This finding provides insights into the nature of metal-metal bonding and gives guidelines for the design of the single-molecule magnet.An unprecedented C 80 cage that violates the isolated pentagon rule
Inorganic Chemistry Frontiers Royal Society of Chemistry (RSC) 9:10 (2022) 2264-2270