Enhancement of photovoltaic performance in ferrocenyl π-extended multi donor-π-acceptor (D-D'-π-A) dyes using chenodeoxycholic acid as a dye co-adsorbent for dye sensitized solar cells.

A new set of multi-donor [ferrocene (D) and methoxyphenyl (D')] conjugated D-D'-π-A based dyes [Fc-(OCH3-Ph)C[double bond, length as m-dash]CH-CH[double bond, length as m-dash]CN-R{R[double bond, length as m-dash]COOH (1) and C6H4-COOH (2)}] were synthesized as sensitizers for dye-sensitized solar cell (DSSC) applications. These dyes were characterized with the aid of analytical and spectroscopic techniques such as FT-IR, HR-Mass, and 1H and 13C NMR. The thermal stability of the dyes 1 and 2 were investigated using thermogravimetric analysis (TGA) and was found to be stable around 180 °C for dye 1 and 240 °C for dye 2. The electronic absorption spectra for sensitizers display major bands between 400 and 585 nm that could be ascribed to an intramolecular charge transfer (ICT) between the electron donor and acceptor to create an efficient charge separation. The redox behaviour of the dyes was determined by cyclic voltammetry, which revealed the one-electron transfer from the ferrocene to ferrocenium ion (Fe2+ ⇌ Fe3+), and potential was utilized to determine the band gap of the dyes (2.16 eV for 1 and 2.12 eV for 2). Further, the carboxylic anchor dyes 1 and 2 have been utilized as photosensitizers in TiO2-based DSSCs with and without co-adsorbance of chenodeoxycholic acid (CDCA), and the photovoltaic performances were studied. The obtained photovoltaic parameters of dye 2 are open-circuit voltage (V oc) = 0.428 V, short-circuit current density (J sc) = 0.086 mA cm-2, the fill factor (FF) = 0.432 and the energy efficiencies (η) = 0.015%, the overall power conversion efficiencies were found to be increased in the presence of CDCA as a co-adsorbent. The photosensitizers with the addition of CDCA show higher efficiencies compared to those in the absence of CDCA, which can prevent the formation of aggregation and increased electron injection of the dyes. Among the dyes, the 4-(cyanomethyl) benzoic acid (2) anchor showed higher photovoltaic performance compared with the cyanoacrylic acid (1) anchor due to the introduction of additional π-linkers and acceptor unit, which enables the lowering of the energy barrier and charge recombination process. In addition, the experimentally observed HOMO and LUMO values were in good agreement with the theoretical calculation by the DFT-B3LYP/6-31+G**/LanL2TZf level of theory.

Ferrocene appended 1,8-naphthalimide chromophores: Synthesis, theoretical, the effect of phenyl substitution on aggregation-induced enhanced emission and second-order nonlinear optical studies.

A new ferrocene appended linear donor-π-acceptor (D-π-A) type 1,8-naphthalimide chromophores [FcPhNap-n-butyl (1) and Fc(Ph)2Nap-n-butyl (2)] have been synthesized and characterized using various analytical and spectroscopic techniques. The chromophores 1 and 2 show the one-electron transfer process, which was examined through cyclic voltammetric (CV) method. The solvatochromic studies show red shift by increasing the solvent polarity from non-polar to polar for both the chromophores 1 and 2, due to the better stabilization of the more polarized excited state than the ground state in the polar solvent. The fluorescence studies show low fluorescence emission, which was enhanced by aggregation in THF/water mixture when the water ratio is increased upto 60%, due to the restricted intramolecular rotation (RIR) process in the aggregated state. Also, the quantum yield increases 3.4 (1) and 6.8 (2) times in the aggregation induced enhanced emission (AIEE) state than THF solution for both the chromophores [THF/AIEE = 0.05/0.17 for 1 and 0.03/0.22 for 2]. The second-order non-linear optical properties of the chromophores 1 and 2 were studied using Kurtz and Perry powder technique, chromophore 2 shows 1.2 times higher SHG efficiency than 1, owing to the presence of additional phenyl group in 2, which further supports the effective charge transfer process from donor to acceptor. Furthermore, optical and non-linear optical properties of chromophores 1 and 2 were analyzed by DFT/TD-DFT calculations using different functionals (B3LYP, long-range corrected CAM-B3LYP and LC-BLYP) with 6-31+G** level of theory. The B3LYP functional shows higher hyperpolarizability values [ß0 = 109.2 × 10-30 esu (1), 299.7 × 10-30 esu (2)], due to the overestimation of the dipole moment, polarizability and hyperpolarizabilities between the donor-π-acceptor systems in B3LYP-hybrid functional, which leads to incorrect long-range charge transfer.

NLO-active Y-shaped ferrocene conjugated imidazole chromophores as precursors for SHG polymeric films.

New Y-shaped ferrocene conjugated imidazole chromophores were prepared and fully characterized. The Y-shaped structure was confirmed by the single crystal X-ray diffraction technique. The chromophores show interesting second-order nonlinear optical (NLO) properties in solution, as determined by the Electric-Field Induced Second Harmonic generation (EFISH) technique. Remarkably, the trifluoro substituted compound 3 is characterized by a high µßEFISH value and has good potential as a molecular building block for composite films with Second Harmonic Generation (SHG) properties. For all compounds, the dipole moments and frontier orbital energies were calculated by the Density Functional Theoretical method.