Synthesis of a Ru(II) Complex with a Naphthoquinone-Annelated Imidazole Ligand Exhibiting Proton-Responsive Redox and Luminescent Behavior

A mononuclear ruthenium complex, [RuII(L)(bpy)2](PF6), with a naphthoquinone-annelated imidazole ligand HL (2-(pyridin-2-yl)-1H-naphtho[2,3-d]imidazole-4,9-dione) was synthesized and structurally characterized. Electrochemical study reveals that the Ru complex shows four reversible redox waves at +0.98 V, −1.13 V, −1.53 V, and −1.71 V versus SCE in acetonitrile, which are assigned to Ru(II)/Ru(III), L−/L•2−, and two bpy/bpy•− redox couples, respectively. The redox potential of Ru(II)/Ru(III) was positively shifted upon the addition of trifluoromethanesulfonic acid due to protonation of the L− moiety, leading to stabilization of the Ru 4d orbital. In UV-vis absorption measurements for the Ru complex in acetonitrile, a metal-to-ligand charge transfer (MLCT) band was observed at 476 nm, which was shifted to 450 nm by protonation, which might be due to a decrease in the electron delocalization and stabilization of the π orbitals in L−. The blue shift of the MLCT band by protonation was associated with a shift of an emission band from 774 nm to 620 nm, which could be caused by the decreased electronic delocalization in the MLCT excited state. These electrochemical and spectroscopic changes were reversible for the protonation/deprotonation stimuli.

Alcohol-soluble bis(tpy)thiophenes: new building units for constitutional dynamic conjugated polyelectrolytes

Constitutional dynamics and spectral properties of conjugated ionic unimers and their metallo-supramolecular dynamers with Zn(ii) and Fe(ii) ion couplers are presented together with new knowledge on the MLCT band of bis(tpy)Fe(ii) units.

Influence of TiO2Nanocrystals Fabricating Dye-Sensitized Solar Cell on the Absorption Spectra of N719 Sensitizer

The absorption spectra of N719 sensitizer anchored on the films prepared by TiO2nanocrystals with different morphology and size were investigated for improving the performance of dye-sensitized solar cell (DSC). We find that the morphology and size of TiO2nanocrystals can affect the UV-vis and FT-IR spectra of the sensitizer anchored on their surfaces. In particular, the low-energy metal-to-ligand charge-transfer transitions (MLCT) band in the visible absorption spectra of N719 is strongly affected, and locations of these MLCT bands revealed larger differences. The results indicate that there is a red shift of MLCT band in the spectra obtained by using TiO2nanocrystals with long morphology and large size compared to that in solution. And it produced a larger red-shift on the MLCT band after TiO2nanocrystals with small size mixed with some long nanocrystals. Accordingly, the utilization rate to visible light is increased. This is a reason why the DSC prepared by using such film as a photoelectrode has better performance than before mixing.

Charge Transfer Interaction in (Riboflavin)tricarbonylrhenium(I) Chloride

[Re(riboflavin)(CO)3Cl] shows intraligand (λmax = 476 and 518 nm) and Re(I) to π* (riboflavin) metal-to-ligand charge transfer, MLCT, (λmax = 556 nm, in CH3CN) absorptions in close proximity. The MLCT band undergoes a moderate solvent-dependent shift (negative solvatochromism) indicating a partial charge separation in the excited state. The complex is not photoluminescent.