Synthesis, Crystal Structure, DFT Studies and Optical/Electrochemical Properties of Two Novel Heteroleptic Copper(I) Complexes and Application in DSSC

New copper(I) compounds of compositions [Cu(HL)(PPh3)2]·H2O (1) and [Cu(HL)POP]·CH2Cl2 (2), where HL = monoanion of pyridine-2,5-dicarboxylic acid, PPh3 = triphenylphosphine and POP = bis [2-(diphenylphosphine)phenyl]ether), are documented. The complexes were characterized by elemental analysis, spectroscopic techniques (IR, 1H/31P RMN and UV–VIS), cyclic voltammetry, and thermogravimetric analysis. Single-crystals for 1 and 2 enabled X-ray diffraction analysis, revealing distorted tetrahedral geometries for Cu(I) centers embedded in NOP2 environments. The crystal structures are stabilized by O−H∙∙∙O, C−H∙∙∙O, C−H∙∙∙π and π∙∙∙π interactions that were analyzed by inspection of the Hirshfeld surfaces and fingerprint plots. Compounds 1 and 2 show interesting optical/electrochemical properties, which were studied experimentally in solution by UV–Vis spectroscopy and cyclic voltammetry, as well as theoretically using Time-Dependent Density Functional Theory (TD-DFT). Additionally, in combination with the ruthenium complex N719, their efficiency as co-sensitizers in dye-sensitized solar cells (DSSCs) was assessed, showing good activity

Four-Coordinate Monoboron Complexes with 8-Hydroxyquinolin-5-Sulfonate: Synthesis, Crystal Structures, Theoretical Studies, and Luminescence Properties

8-Hydroxyquinolin-5-sulfonic acid (8HQSA) was combined with 3-pyridineboronic acid (3PBA) or 4-pyridineboronic acid (4PBA) to give two zwitterionic monoboron complexes in crystalline form. The compounds were characterized by elemental analysis, single-crystal X-ray diffraction studies, and IR, 1H NMR, UV-Visible, and luminescence spectroscopy. The analyses revealed compounds with boron atoms adopting tetrahedral geometry. In the solid state, the molecular components are linked by charge-assisted (B)(O−H⋯−O(S) and N+−H⋯O(S) hydrogen bonds aside from C−H⋯O contacts and π⋯π interactions, as shown by Hirshfeld surface analyses and 2D fingerprint plots. The luminescence properties were characterized in terms of the emission behavior in solution and the solid state, showing emission in the bluish-green region in solution and large positive solvatofluorochromism, caused by intramolecular charge transfer. According to TD-DFT calculations at the M06-2X/6-31G(d) level of theory simulating an ethanol solvent environment, the emission properties are originated from π-π * and n-π * HOMO-LUMO transitions