1,1'-Bis-(diphenylphosphino)ferrocene appended d8- and d10-configuration based thiosquarates: the molecular and electronic configurational insights into their sensitization and co-sensitization properties for dye sensitized solar cells.

Three new d8- and d10-configuration based 1,1'-bis-(diphenylphosphino)ferrocene (dppf) appended thiosquarates complexes with general composition [M(mtsq)2dppf] (M = Ni2+ (NiL2); Zn2+ (ZnL2) and Cd2+ (CdL2)) (mtsq = 3-ethoxycyclobutenedione-4-thiolate) have been synthesized and characterized spectroscopically as well as in case of NiL2 by single crystal X-ray diffraction technique. The single crystal X-ray analysis reveals square planar geometry around Ni(II) in NiL2, where Ni(II) coordinates with two sulfur centres of two mtsq ligands in monodentate fashion and two phosphorus of a dppf ligand in chelating mode. The supramolecular architecture of NiL2 is sustained by intermolecular C-H⋯O interactions to form one-dimensional chain. Further, the application of these newly synthesized complexes as sensitizers and co-sensitizers/co-absorbents with ruthenium based N719 sensitizer in dye-sensitized solar cells (DSSCs) have been explored. The DSSC set-up based on NiL2 offers best photovoltaic performance with photovoltaic efficiency (η) 5.12%, short-circuit current (Jsc) 11.60 mA cm-2, open circuit potential (Voc) 0.690 V and incident photon to current conversion efficiency (IPCE) 63%. In co-sensitized DSSC set-up, ZnL2 along with state-of-the-art N719 dye displays best photovoltaic performance with η 6.65%, Jsc 14.47 mA cm-2, Voc 0.729 V and IPCE 69%, thereby showing an improvement by 15.25% in photovoltaic efficiency in comparison to the photovoltaic efficiency of N719 sensitized DSSC set-up. Variation in co-sensitization behaviour have been ascribed to the differences in the excited state energy level of co-sensitizers. The ZnL2 and CdL2 have a higher energy level position than N719 dye, allowing efficient electron transfer to N719 during light irradiation, while excited state of NiL2 is lower than N719 dye, preventing photoexcited electron transfer to N719, resulting in its lowest overall efficiency among the three co-sensitized DSSC setups.

Enhanced sunlight-driven catalysis for hydrogen generation and dye remediation using synergistic p-Co3O4/n-TiO2 nanocomposites.

In this study, p-Co3O4/n-TiO2 nanocomposites were synthesized using different ratios of cobalt and titanium precursors through a hydrothermal method. These nanocomposites demonstrated notable potential in photocatalytic applications for hydrogen production and orange-red dye degradation under sunlight. Various techniques, including XRD, Raman spectroscopy, XPS, FESEM, TEM, and BET analysis, were used to comprehensively characterize their structural, morphological, and optical properties. The nanocomposites exhibited both cubic and tetragonal phases of Co3O4 and TiO2, and their combined effect resulted in a narrowed band gap. Additionally, the presence of Co3O4 induced surface plasmon resonance on the TiO2 surface, effectively impeding electron-hole recombination. The nanocomposites displayed an average particle size of ∼20 to 30 nm with substantial visible light absorption. High crystallinity and well-dispersed nanocomposites were confirmed by XRD and Raman, with BET surface areas ranging between 49 and 106 m2 g-1. Notably, the p-Co3O4/n-TiO2 nanocomposite showed superior photocatalytic activity, achieving a maximum hydrogen generation rate of 1120 µmol h-1 g-1 and an 83% degradation efficiency of the orange-red dye within 6 minutes under sunlight. This study emphasizes the enhanced performance of the p-Co3O4/n-TiO2 nanocomposite, indicating its potential in photocatalytic applications, conforming to a pseudo-first-order kinetics model.

New 5,5-(1,4-Phenylenebis(methyleneoxy)diisophthalic Acid Appended Zn(II) and Cd(II) MOFs as Potent Photocatalysts for Nitrophenols.

Metal-organic frameworks (MOFs) are peculiar multimodal materials that find photocatalytic applications for the decomposition of lethal molecules present in the wastewater. In this investigation, two new d10-configuration-based MOFs, [Zn2(L)(H2O)(bbi)] (1) and [Cd2(L)(bbi)] (2) (5,5-(1,4-phenylenebis(methyleneoxy)diisophthalic acid (H2L) and 1,1'-(1,4-butanediyl)bis(imidazole) (bbi)), have been synthesized and characterized. The MOF 1 displayed a (4,6)-connected (3.43.52)(32.44.52.66.7) network topology, while 2 had a (3,10)-connected network with a Schläfli symbol of (410.511.622.72)(43)2. These MOFs have been employed as photocatalysts to photodegrade nitrophenolic compounds, especially p-nitrophenol (PNP). The photocatalysis studies reveal that 1 displayed relatively better photocatalytic performance than 2. Further, the photocatalytic efficacy of 1 has been assessed by altering the initial PNP concentration and photocatalyst dosage, which suggest that at 80 ppm PNP concentration and at its 50 mg concentration the MOF 1 can photo-decompose around 90.01% of PNP in 50 min. Further, radical scavenging experiments reveal that holes present over 1 and ·OH radicals collectively catalyze the photodecomposition of PNP. In addition, utilizing density of states (DOS) calculations and Hirshfeld surface analyses, a plausible photocatalysis mechanism for nitrophenol degradation has been postulated.

Alkaline hydrolysis of spent aromatic biomass for production of phenolic aldehydes, lignin, and cellulose.

In order to combat the environmental issues associated with the burning of spent aromatic biomass (SAB), a method for alkaline hydrolysis of SAB has been developed to afford phenolic acids, predominantly the p-coumaric acid, lignin, and cellulose. Lignin (∼15 wt%) from alkaline hydrolysate was separated by precipitation while a mixture of phenolic acids obtained was directly reacted with a green reagent, PhI(OAc)2, under one-pot condition to afford a mixture of p-hydroxybenzaldehyde (>90 wt%) and vanillin (<10 wt%). Unreacted biomass obtained in the process was successfully used as a substrate for the production of cellulose (∼40 wt%). The developed method exhibits potential for application on an industrial scale.

Copper(ii) and cobalt(iii) Schiff base complexes with hydroxy anchors as sensitizers in dye-sensitized solar cells (DSSCs).

Two Schiff base complexes of copper(ii) and cobalt(iii) having the formulae [CuL2] (Cu-Sal) and [CoL3] (Co-Sal) (HL = 2-(((2-hydroxyethyl)imino)methyl)phenol) have been synthesized and characterized microanalytically, spectroscopically and in the case of Cu-Sal using single crystal X-ray diffraction technique. The single crystal X-ray analysis reveals a square planar geometry around Cu(ii) satisfied by phenoxide oxygen and imine nitrogen of the L- ligand to generate a six membered chelate ring. The solid state structure of Cu-Sal is satisfied by varied intermolecular non-covalent interactions. The nature of these interactions has been addressed with the aid of Hirshfeld surface analysis. Both compounds have been used as sensitizers in TiO2 based dye sensitized solar cells (DSSCs) and the DSSC experiments revealed that Co-Sal offers better photovoltaic performance in comparison to Cu-Sal. The Co-Sal exhibited a J sc of 9.75 mA cm-2 with a V oc of -0.648 V, incident photon to current conversion efficiency (IPCE) of 57% and η of 3.84%. The relatively better photovoltaic performance of Co-Sal could be attributed to better light absorption and dye loading than that of Cu-Sal.

A double co-sensitization strategy using heteroleptic transition metal ferrocenyl dithiocarbamate phenanthrolene-dione for enhancing the performance of N719-based DSSCs.

Three new heteroleptic dithiocarbamate complexes with formula [M(Phen-dione)(Fcdtc)]PF6 (where M = Ni(ii) Ni-Fc, Cu(ii) Cu-Fc) and [Co(Phen-dione)(Fcdtc)2]PF6 (Co-Fc) (Fcdtc = N-ethanol-N-methylferrocene dithiocarbamate and Phen-dione = 1,10-phenanthroline-5,6-dione; PF6 - = hexafluorophosphate) were synthesized and characterized using microanalysis, FTIR, electronic absorption spectroscopy and mass spectrometry. The solution state electronic absorption spectroscopy for all three complexes displayed a band at ∼430 nm corresponding to the ferrocene unit and another low-intensity band in the visible region arising because of the d-d transitions. These newly synthesized complexes were used as co-sensitizers for the state-of-the-art di-tetrabutylammonium cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)ruthenium(ii) (N719) dye in dye-sensitized solar cells (DSSCs). Among the three co-sensitizers/co-adsorbent-based DSSC set-ups, the assembly fabricated using Co-Fc/N719 displayed good photovoltaic performance with 5.31% efficiency (η) while a new triple component strategy inculcating N719, Co-Fc and Cu-Fc dyes offered the best photovoltaic performance with 6.05% efficiency (η) with incident photon to current conversion efficiency (IPCE) of 63%. This indicated an upliftment of the DSSC performance by ∼38% in comparison to the set-up constructed by employing only N719 dye (η = 4.39%) under similar experimental conditions.

Synthesis, characterization and light harvesting properties of Sb(III) and Bi(III) ferrocenyl dithiocarbamate complexes.

New Sb(III) and Bi(III) ferrocenyl dithiocarbamate complexes viz. [Sb(FcCH2Bzdtc)3] (Sb) and [Bi(FcCH2Bzdtc)3] (Bi) (Fc=C5H5FeC5H4-; Bz=C6H5CH2-) have been synthesized and characterized by elemental analyses, IR, (1)H and (13)C NMR spectroscopies. The optical, electrochemical and photovoltaic properties of the synthesized complexes were investigated. The light harvesting properties of both of the compounds have been studied using these compounds as photosensitizers in TiO2-based DSSCs. The photovoltaic devices fabricated by Sb and Bi showed a maximum current conversion efficiency of 1.51% and 0.97%, respectively under 1.5 AM illumination (100 mW cm(-2)) and having incident photon to current efficiency (IPCE) of 38% and 31%, respectively. The reason for the higher efficiency of Sb is due its higher dye loading.

Photosensitizing activity of ferrocenyl bearing Ni(II) and Cu(II) dithiocarbamates in dye sensitized TiO2 solar cells.

Biferrocene bearing planar metal dithiocarbamates, namely, [M(FcCH2dtc)2] (dtc = furan-2-ylmethyldithiocarbamate, M = Cu(II) 1, Ni(II) 4; dtc = benzo[d][1,3]dioxol-5-ylmethyl dithiocarbamate, M = Cu(II) 2, Ni(II) 5; dtc = pyridin-2-ylmethyldithiocarbamate, M = Cu(II) 3, Ni(II) 6; Fc = ferrocenyl; Fe(η(5)-C5H5)(η(5)-C5H4-)), have been synthesized and characterized by microanalysis, magnetic susceptibility and cyclic voltammetry. Structures of 1, 2 and 4 have been obtained by single crystal X-ray diffraction. These complexes with pyridyl, piperonyl and furfuryl as heteroaromatic groups in the dithiocarbamate ligands have been exploited as sensitizers in dye sensitized TiO2 solar cells for converting sunlight into electrical energy. Light-to-electrical energy conversion efficiencies achieved using these sensitizers are considerably greater than those obtained with analogous compounds previously reported by us. The overall conversion efficiency (η) is found to be dependent upon the nature of the heteroaromatic conjugated linkers and increases in the order η (ferrocenylfurfuryl) > η (ferrocenylpiperonyl) > η (ferrocenylpyridyl) all values being lower than that obtained in the reference Ru dye N719 under similar experimental conditions. The conversion efficiencies also vary with the metal being higher for Ni (4, 5 and 6) than for Cu complexes (1, 2 and 3). The X-ray structural analyses reveal the existence of rare M···H-C intermolecular anagostic interactions involving the metal atom in chain motifs in 1 and 4, which are retained in solution as evidenced by (1)H NMR spectroscopy.

Synthesis, characterization and light harvesting properties of nickel(II) diimine dithiolate complexes.

Four Ni(II) diimine dithiolato complexes viz. [Ni{(S2C2Ph2)(1,10-Phenanthroline)}] (2), [Ni{(S2C2Ph2)(3,3'-dicarboxy-2,2'-bipyridyl)}] (3), [Ni{(S2C2Ph2)(4,4'-dicarboxy-2,2'-bipyridyl)}] (4) [Ni{(S2C2Ph2)(2,2'-bipyridyl)}] (5) have been prepared from [Ni(S2C2Ph2)2] (1) and characterized by microanalyses, UV-Vis, IR, (1)H and (13)C NMR. Attempts have been made to explain the nature of charge transfer in these molecules through quantum chemical calculations. The light harvesting properties of all the compounds have been studied using these compounds as photosensitizers in TiO2-based DSSC. The change in position of anchoring group on diimine derivative leads to different structural, electronic and light harvesting properties about the Ni(II) diimine dithiolate dyes.

Enhanced light harvesting efficiencies of bis(ferrocenylmethyl)-based sulfur rich sensitizers used in dye sensitized TiO2 solar cells.

In this work, the photosensitizing properties of ferrocene (Fc)-based compounds FcCH(2)CS(3)CH(2)Fc (1) and FcCH(2)SSCH(2)Fc (2) were investigated and significant enhancement in the light harvesting efficiency was observed compared to those achieved with previously reported compounds from our lab. The compounds were fully characterized by spectroscopy and X-ray crystallography, and their electrochemical properties studied. DSSCs based on these dyes display efficiencies comparable to those of a standard cell based on N719 under similar experimental conditions. These studies demonstrate that ferrocenyl-based sulfur rich compounds with proper orientation of the Fc groups assisted via suitable linkers, together with desired redox properties and visible region electronic absorption features could constitute a new class of photosensitizers targeting light driven reactions.

Application of π-extended ferrocene with varied anchoring groups as photosensitizers in TiO2-based dye-sensitized solar cells (DSSCs).

Two new compounds, FcCH=NC(6)H(4)COOH (1) and FcCH=NCH(2)CH(2)OH (2) (Fc=C(5)H(4)FeC(5)H(5)), have been synthesized and characterized by elemental analyses, IR and (1)H NMR spectroscopy, and ESI-MS. Attempt has been made to explain their quasi-reversible redox behavior evidenced by cyclic voltammetry using density functional theory (DFT) calculations. Light-harvesting properties of both the compounds and also the starting material, FcCHO (3), have been studied using these compounds as photosensitizers in TiO(2)-based dye-sensitized solar cells having either a propylene carbonate-based electrolyte or ionic liquid electrolyte, namely, 1-propyl-3-methyl imidazolium iodide (PMII). Long-term stability of the photocurrent output of the cell using compound 1 as photosensitizer has been monitored periodically over 1400 h.

Efficient phenylmercury(II) methylferrocenyldithiocarbamate functionalized dye-sensitized solar cells.

Two new heterobimetallic phenylmercury(ii) dithiocarbamate complexes incorporating the ferrocenyl moiety (C(5)H(5))Fe(C(5)H(4)) (Fc), namely PhHgS(2)CN(CH(2)Fc)CH(2)C(5)H(4)N, (1) and PhHgS(2)CN(CH(2)Fc)CH(2)C(4)H(3)O, (2) have been prepared and characterized by elemental analysis, UV-Vis, IR, (1)H and (13)C NMR spectroscopies. The crystal structures of 1 and 2 showed a linear core at the Hg(ii) centre of the molecule, bound by the sulfur atom of the dithiocarbamate ligand and carbon atom of the aromatic ring. Weak intermolecular HgS interactions form "head-to-tail" dimers in the cases of 1 and 2. The observed quasi-reversible cyclic voltammograms of the complexes have been corroborated by calculating gross natural electron population and gross natural electron spin population at each atom for the neutral as well its oxidized species obtained at density functional level (DFT) of theory, which suggests that the delocalization of electron spin population can affect the magnitude of ΔE(p). The electronic absorption bands of both the complexes were assigned with the help of time dependent density functional theory (TD-DFT) calculations. The light harvesting properties of both 1 and 2 in conjunction with our previously reported compound PhHgS(2)CN(CH(2)Fc)CH(2)C(6)H(5) (3) have been reported.

Synthesis, structure and light-harvesting properties of some new transition-metal dithiocarbamates involving ferrocene.

Nine new transition-metal dithiocarbamates involving ferrocene (Fc), namely, [M(FcCH(2)Bzdtc)(2)] (M=Ni(II) (1), Cu(II) (2), Cd(II) (3), Hg(II) (4), Pd(II) (5), Pt(II) (6) and Pb(II) (7); Bzdtc=N-benzyl dithiocarbamate) and [M(FcCH(2)Bzdtc)(3)] (M=Co(II) (8) and UO(2) (VI) (9)), have been synthesised and characterised by micro analyses, IR spectroscopy, (1)H and (13)C NMR spectroscopy, and in three cases by single-crystal X-ray analysis. The peak broadening in the (1)H spectrum of the copper complex indicates the paramagnetic behaviour of this compound. A square-planar geometry around the nickel and copper complexes and distorted linear geometry around the mercury complex have been found. The latter geometry is attributed to the bulkiness of the methylferrocenyl and benzyl groups. The observed single quasi-reversible cyclic voltammograms for complexes 2, 8 and 9 indicate the stabilisation of a metal centre other than Fe in their characteristic oxidation state. These complexes have been used as a photosensitiser in dye-sensitised solar cells.