Shuaifeng Hu

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@C_s(17 490)-C₇₆, Lu₃N@C₂(22 010)-C₇₈, and Lu₃N@D_3h(5)-C₇₈. The three lutetium-based nitride clusterfullerenes (NCFs) with small C_76-78 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 C_s(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@D_3h(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 C_s(17 490)-C₇₆ to D_3h(5)-C₇₈, is dramatically opposite to the cluster expansion with cage elongation found in La₂C₂- or Y₂C₂-based metallofullerenes.

Abstract:

Perovskite/perovskite tandem solar cells have recently exceeded the record power conversion efficiency (PCE) of single-junction perovskite solar cells. They are typically built in the superstrate configuration, in which the device is illuminated from the substrate side. This limits the fabrication of the solar cell to transparent substrates, typically glass coated with a transparent conductive oxide (TCO), and adds constraints because the first subcell that is deposited on the substrate must contain the wide-bandgap perovskite. However, devices in the substrate configuration could potentially be fabricated on a large variety of opaque and inexpensive substrates, such as plastic and metal foils. Importantly, in the substrate configuration the narrow-bandgap subcell is deposited first, which allows for more freedom in the device design. In this work, we report perovskite/perovskite tandem solar cells fabricated in the substrate configuration. As the substrate we use TCO-coated glass on which a solution-processed narrow-bandgap perovskite solar cell is deposited. All of the other layers are then processed using vacuum sublimation, starting with the charge recombination layers, then the wide-bandgap perovskite subcell, and finishing with the transparent top TCO electrode. Proof-of-concept tandem solar cells show a maximum PCE of 20%, which is still moderate compared to those of best-in-class devices realized in the superstrate configuration yet higher than those of the corresponding single-junction devices in the substrate configuration. As both the top and bottom electrodes are semitransparent, these devices also have the potential to be used as bifacial tandem solar cells.

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@I_h(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@I_h(7)-C₈₀ with one electron shared by three metals, and thus, its exceptional electronic structure can be expressed as (Er₃)⁸⁺(C₂)^2-@C₈₀^6-. Interestingly, with the further observation on the geometry configurations of the encapsulated clusters in M₃C₂@C_2n (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.