DFT study of UV-vis-properties of thiophene-containing Cu(β-diketonato)₂ - Application for DSSC

Experimental and theoretically calculated UV-vis properties of three Cu(β-diketonato)₂ complexes are presented. The Cu(β-diketonato)₂ contains β-diketones without (β-diketone = acetylacetone, (CH₃)COCH₂CO(CH₃), complex (1)), with one (β-diketone = thenoyltrifluoroacetone, (CF₃)COCH₂CO(C₄H₃S), complex (2)) and with two thiophene (β-diketone = (CF₃)COCH₂CO(C₄H₂S) (C₄H₃S), complex (3)) groups. More thiophenes on the β-diketonato ligand of Cu(β-diketonato)₂, lead to a red shift of the experimental absorbance maxima of the UV-vis of the complex, from 295 nm for complex (1), to 340 nm for complex (2) to 390 nm for complex (3). Theoretical time dependant density functional theory calculations indicate that both the two strongest absorbance peaks of the ultraviolet-visible spectrum of Cu(acetylacetonato)₂ are mainly ligand-to-metal charge-transfer excitations. However, the absorbance maxima of the UV-vis of thiophene-containing Cu(β-diketonato)₂ are mainly ligand-to-ligand charge-transfer excitations. Calculated properties such as light harvesting energy (LHE = 0.47, 0.94 and 0.99 for (1)-(3) respectively), driving force for electron injection (ΔG_inject = 1.43, 0.76 and 0.63 for (1)-(3) respectively), and driving force of dye regeneration (ΔG_regenerate = 1.85, 2.16 and 1.49 for (1)-(3) respectively), are favourable for (1)-(3) to be considered as dyes in DSSCs. However, some structural modifications are needed to prevent intramolecular charge recombination after excitation.