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.

Novel Ferrocene-Appended ß-Ketoimines and Related BF2 Derivatives with Significant Aggregation-Induced Emission and Second-Order Nonlinear Optical Properties.

A series of new ß-ketoimines containing a ferrocene moiety and their BF2 complexes have been synthesized and structurally characterized. The solvatochromism of the ß-ketoimines was studied, putting in evidence a redshift with increasing solvent polarity. This positive solvatochromism can be attributed to a more polarized excited state compared with the ground state, due to intramolecular charge transfer (ICT) transitions. The ß-ketoimines exhibited weak emission, attributable to the excited-state intramolecular proton transfer (ESIPT) phenomenon. This ESIPT effect is suppressed upon restriction of the keto-enamine tautomerism, induced upon addition of BF3 ⋅OEt2 , which afforded the related BF2 complexes, characterized by an enhancement of the fluorescence through the ICT effect. Both the ß-ketoimines and BF2 complexes exhibited significant aggregation-induced emission behavior in mixtures of CH3 CN/H2 O, due to restriction of intramolecular rotation in the aggregated state. The frontier molecular orbital levels, ground- and excited-state dipole moments (µg and µe ), and the origin of electronic absorption spectra were studied by time-dependent DFT calculations. The second-order nonlinear optical (NLO) properties were determined by the electric-field-induced second-harmonic generation technique. The µß1907 values of the ß-ketoimines increased upon the formation of the related BF2 complexes, mainly due to an enhancement of the ground-state dipole moment. The results presented here reveal that some of these novel compounds are excellent multifunctional candidates for NLO and luminescence applications.

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.

Y-shaped ferrocene/non-ferrocene conjugated quinoxalines for colorimetric and fluorimetric detection of picric acid.

New Y-shaped ferrocene and non-ferrocene conjugated quinoxaline derivatives {[R-(CH)2-N=CH-)2C10H4], R = C5H5-Fe-C5H5 (1) and R = C6H4-OCH3 (2)} have been synthesized and characterized using analytical and spectroscopic techniques. The thermal stability of the compounds 1 and 2 were examined by thermogravimetric analysis (TGA), both were stable up to 250 °C. The optical properties were studied using UV-Visible and fluorescence spectroscopic methods and Y-shaped ferrocene appended quinoxaline derivative 1 show a weak emission due to the quenching nature of ferrocene. The compound 2 shows enhanced fluorescence intensity in their aggregation state due to Restricted Intramolecular Rotation (RIR). Hence, the compound 2 have further utilized for the detection of picric acid (PA) by fluorimetric method and the detection limit of 1.37 × 10-6 M was obtained. Further, paper sensor was made using compound 2 which resulted in the instant 'naked eye' response for trace detection of picric acid. Consequently, the compound 2 acts as a colorimetric sensor and can be used as a new probe for the detection of nitro aromatic explosives.

Ferrocene-quinoxaline Y-shaped chromophores as fascinating second-order NLO building blocks for long lasting highly active SHG polymeric films.

The first example of a Y-shaped ferrocene quinoxaline derivative with a surprisingly high and stable second harmonic generation (SHG) response in composite polymeric films is reported. The interesting quadratic hyperpolarizability values of different substituted Y-shaped chromophores are also investigated in solution by the EFISH technique.

Inhibitory effect of apocarotenoids on the activity of tyrosinase: Multi-spectroscopic and docking studies.

In this present study, the inhibitory mechanism of three selected apocarotenoids (bixin, norbixin and crocin) on the diphenolase activity of tyrosinase has been investigated. The preliminary screening results indicated that apocarotenoids inhibited tyrosinase activity in a dose-dependent manner. Kinetic analysis revealed that apocarotenoids reversibly inhibited tyrosinase activity. Analysis of fluorescence spectra showed that apocarotenoids quenched the intrinsic fluorescence intensity of the tyrosinase. Further, molecular docking results implied that apocarotenoids were allosterically bound to tyrosinase through hydrophobic interactions. The results of the in vitro studies suggested that higher concentrations of bixin and norbixin inhibited tyrosinase activity in B16F0 melanoma cells. Our results suggested that apocarotenoids could form the basis for the design of novel tyrosinase inhibitors.

Monomeric mixed cadmium-2,2'-dipyridylamine complex derived from ferrocenecarboxylic acid: Structural, electrochemical and biological studies.

A mixed Cd(II) complex {[Cd(FcCOO)2(dpyam)(H2O)][Cd(dpyam)2 (H2O)2]·(ClO4)2·CH3OH} (1) (where FcCOO=ferrocenecarboxylic acid and dpyam=2,2'-dipyridylamine), has been synthesized and characterized by FT-IR, (1)H &(13)C NMR, UV-Vis spectroscopy and elemental analysis. The molecular structure of compound 1 has been determined by the single crystal X-ray diffraction technique, which consists of mixed two different cadmium(II) complexes and two uncoordinated perchlorate ions. The crystal packing shows that the compound 1 self-assembled by intermolecular hydrogen bonding via pyridyl N-H⋯O and coordinated water O⋯H-O-H⋯O, to afford the molecule 2D supramolecular network. Compound 1 exhibits high-energy intraligand (π-π(∗)) fluorescence emission. In electrochemical studies of compound 1 shows negative potential compared with ferrocenecarboxylic acid due to formation of coordination complex with Cd ions. The antibacterial study against the distinct bacterial strains show compound 1 has significant activity.

Sterically encumbered acyclic diphosphazanes: synthesis, conformations and coordination behavior.

The reaction between lambda3-diphosphazane [EtN(PCl2)2] and the sodium salts of substituted phenols affords sterically encumbered diphosphazanes [EtN{P(OR)2}2] (R = -C6H3iPr2-2,6 (1), -C6H3Me2-2,6 (2) and -C6H2Me3-2,4,6 (3)). When the same reaction was carried out with bulky sodium 2,4-di-tert-butyl-4-methylphenoxide, only a monosubstitution takes place to result in the formation of [EtN{PCl(OR)}2] (R = -C6H2tBu2-2,6-Me-4) (4). Further reaction of 2 with [Mo(CO)4(NBD)] produces cis-[(EtN{P(OC6H3Me2-2,6)2}2)Mo(CO)4] (5). Diphosphazanes 1-4 and the metal derivative 5 have been characterized by means of their analytical data and EI-MS, IR and multinuclear NMR (1H and 31P) spectral data. The solid-state structure of the diphosphazanes 1, 2 and 4, and the molybdenum complex 5 have been determined by X-ray diffraction studies. Irrespective of the size of substituent, the bulky groups on the phosphorus and nitrogen are on the same side of the P-N-P skeleton with a local C2v symmetry. The central nitrogen remains almost trigonal planar in all the compounds.