Time-resolved single-crystal diffraction performed with synchrotron radiation shows that the 53(1) micros phosphorescent state, generated in the crystalline phase of trimeric {[3,5-(CF3)(2)Pyrazolate]Cu}(3) molecules by exposure to 355 nm of light at 17 K, is due to the formation of an excimer rather than the shortening of the intramolecular Cu...Cu distances within the trimeric units, or the formation of a continuous chain of interacting molecules. One of the intermolecular Cu...Cu distances contracts by 0.56 Angstroms from 4.018(1) to 3.46(1) Angstroms;, whereas the interplanar spacing of the trimers is reduced by 0.65 Angstroms; from 3.952(1) to 3.33(1) Angstroms. Density-functional theory calculations support the formation of a Cu...Cu bond through the intermetallic transfer of a Cu 3d electron to a molecular orbital with a large 4p contribution on the reacting Cu atoms.

Antimony and bismuth ⟨111⟩ layered perovskites have recently attracted significant attention as possible, nontoxic alternatives to lead halide perovskites. Unlike lead halide perovskites, however, ⟨111⟩ halide perovskites have shown limited ability to tune their optical and electronic properties. Herein, we report on the metal alloying of manganese and copper into the family of materials with formula Cs 4 Mn 1−x Cu x Sb 2 Cl 12 (x = 0−1). By changing the concentration of manganese and copper, we show the ability to modulate the bandgap of this family of compounds over the span of 2 electron volts, from 3.0 to 1.0 eV. Furthermore, we show that in doing so, we can also adjust other relevant properties such as their magnetic behavior and their electronic structure.

Time-resolved crystallography and density functional theory calculations are used to analyze the geometric and electronic changes that occur upon photoexcitation of [Cu(I)(dmp)(dppe)](+) in crystalline [Cu(I)(dmp)(dppe)][PF(6)] [dmp = 2,9-dimethyl-1,10-phenanthroline; dppe = 1,2-bis(diphenylphosphino)ethane]. In the pump-probe experiment, laser and X-ray pulses are synchronized to capture an image of the instantaneous molecular distortions in the transient triplet state. Parallel theoretical calculations, with the phenyl groups replaced by methyl groups, yield information on the distortion of the isolated cation and the change in electron density upon excitation. The experimental distortions are significantly less than the calculated values and are different for the two independent molecules in the asymmetric unit; these findings are attributed to the constraining influence of the crystal matrix. The calculations indicate that the electron transfer upon excitation is mostly from the dmpe ligand to the dmp ligand, while the Cu atomic charge changes by only approximately +0.1e, although the charge distribution on Cu is significantly affected. As found for homoleptic [Cu(I)(dmp)(2)](+), the change in the population of the Cu atom is close to the calculated difference between the corresponding Cu(II) and Cu(I) complexes. Charge density difference maps confirm these conclusions and show a large rearrangement of the electron density on the Cu atom upon excitation.