Snaith group

Abstract:

For endohedral metallofullerenes (EMFs), that is, fullerenes encapsulating metallic species, cage size is known to be an important factor for cluster configuration adoption; however, the impact of the cage shape on the cluster geometry fitting remains poorly understood. Herein, for the first time, four dierbium-carbide EMFs with C₉₀ cages, namely, Er₂C₂@C₂(43)-C₉₀, Er₂C₂@C₂(40)-C₉₀, Er₂C₂@C₂(44)-C₉₀, and Er₂C₂@C₁(21)-C₉₀, were successfully synthesized and fully characterized using a combination of mass spectrometry, single-crystal X-ray diffractometry, vis-NIR, Raman and photoluminescence spectroscopies, and cyclic voltammetry. In particular, the fullerene cages of C₂(43)-C₉₀ and C₂(44)-C₉₀ are crystallographically identified for the first time. Interestingly, the ErEr distance of the major sites in Er₂C₂@C₂(43)-C₉₀, Er₂C₂@C₂(40)-C₉₀, Er₂C₂@C₂(44)-C₉₀, and Er₂C₂@C₁(21)-C₉₀ is 3.927, 4.058, 4.172, and 4.651 Å, respectively, which increases gradually with an increase in the major axis of the cage. Moreover, the bond length of the inner C₂-unit decreases progressively with an increase in the ErEr distance, indicating that the inserted C₂-unit can serve as a molecular spring to support the strong metal-cage interactions within cages with the same size but different shapes. Hence, the role of cage shape on the cluster configuration is unveiled safely for the as-obtained Er₂C₂@C₉₀ isomers.

Abstract:

Truxene derivatives, due to their molecular structure and properties, are good candidates for the passivation of defects when deposited onto hybrid lead halide perovskite thin films. Moreover, their semiconductor characteristics can be tailored through the modification of their chemical structure, which allows-upon light irradiation- the interfacial charge transfer between the perovskite film and the truxene molecules. In this work, we analysed the use of the molecules as surface passivation agents and their use in complete functional solar cells. We observed that these molecules reduce the non-radiative carrier recombination dynamics in the perovskite thin film through the supramolecular complex formation between the Truxene molecule and the Pb²⁺ defects at the perovskite surface. Interestingly, this supramolecular complexation neither affect the carrier recombination kinetics nor the carriers collection but induced noticeable hysteresis on the photocurrent vs voltage curves of the solar cells under 1 sun illumination.

Abstract:

Combination of a cryogenic ion-trap machine, operated at 4.7 K, with the free-electron-laser FELIX allows the first experimental characterization of the unusually bright antisymmetric stretch (ν₃) and π-bending (ν₂) fundamentals of the He–X⁺–He (X = H, D) chromophore of the in situ prepared HHe_n⁺ and DHe_n⁺ (n = 3–6) complexes. The band origins obtained are fully supported by first-principles quantum-chemical computations, performed at the MP2, the CCSD(T), and occasionally the CCSDTQ levels employing extended basis sets. Both the experiments and the computations are consistent with structures for the species with n = 3 and 6 being of T-shaped C_2v and of D_4h symmetry, respectively, while the species with n = 4 are suggested to exhibit interesting dynamical phenomena related to large-amplitude motions.