Heterodimetallic Ferrocenyl Dithiophosphonate Complexes of Nickel(II), Zinc(II) and Cadmium(II) as Sensitizers for TiO₂‐Based Dye‐Sensitized Solar Cells

Abstract

The formation, characterization, and dye sensitized solar cell application of nickel(II), zinc(II) and cadmium(II) ferrocenyl dithiophosphonate complexes were investigated. The multidentate monoanionic ligand [S 2 PFc(OH)] À (L1) was synthesized. The reaction between metal salt precursors and L1 produced Ni(II) complexes of the type [Ni{S 2 P(Fc)(OH)} 2 ] (1) (molar ratio 1:2), and a tetranickel(II) complex of the type [Ni 2 {S 2 OP(Fc)} 2 ] 2 (2) (molar ratio (1:1). It also produced a Zn(II) complex [Zn{S 2 P (Fc)(OH)} 2 ] 2 (3), and a Cd(II) complex [Cd{S 2 P(Fc)(OH)} 2 ] 2 (4). Complexes 1-4 were characterized by 1 H and 31 P NMR, FTIR and elemental analysis, and complexes 1 and 2 were additionally analyzed by X-ray crystallography. The first examples of dyesensitized solar cells (DSSCs) co-sensitized with ferrocenyl dithiophosphonate complexes 1-4 are reported. Co-sensitization with the ruthenium dye N719, produced the dye materials (3)-N719 (η = 8.30%) and (4)-N719 (η = 7.78%), and they were found to have a better overall conversion efficiency than the pure Ru N719 dye standard (η = 7.14%) under the same experimental conditions. The DSSCs were characterized using UV/vis, cyclic voltammetry, electrochemical impedance spectroscopy (EIS), photovoltaic-(IÀ V curves), and performing incident photon-to-current efficiency (IPCE) measurements.

Solar energy conversion using first row d-block metal coordination compound sensitizers and redox mediators

“…Co-sensitization with N719 led to slightly enhanced performances with respect to N719 alone for the Zn(II) and Cd(II)-based dyes. 254 Several examples of derivatives of 1,1 0 -bis(diphenyl)phosphanoferrocene (dppf) have been trialled as sensitizers in DSCs. 255,256 The dimetallic complexes [Ni(dppf)(S 2 C]C(H)NO 2 )] and [Ni(dppf)(S 2 C]C(COMe) 2 )] absorb in the visible with maxima ca.…”

“…A number of dithiolate and dithiocarbamate complexes of nickel and bearing peripheral ferrocenyl units were described earlier in this review. [254][255][256] Zhang et al reported the formation and structure of the 1Dcoordination polymer [Ni(en) 2 (azobc)] n (H 2 azobc ¼ azobenzene-4,4 0 -dicarboxylic acid) (Fig. 14).…”

Electrochemical Properties and Structure of Multi-Ferrocenyl Phosphorus Thioesters

“…An alternative way to multi-ferrocenyl compound is using phosphorus acids derivatives, containing ferrocene fragments. These ferrocene derivatives can be easily accessed via low cost syntheses with good yields [14,15]. It was demonstrated that ferrocene containing phosphate molecules can be successfully used for the construction of multi-step multi-electron redox systems [16][17][18][19].…”

Diversity of Lawesson's Reagent: Advances and Scope

“…Proposed mechanism for the formation of macrocycles 46, 47, and 50. sensitizers for TiO 2 -based DSSC (Dye-Sensitized Solar Cells). [21] Unlike their previous report [20] they proceeded with water instead of alcohol to compose ferrocenyl dithiophosphonate ligand 69. Hydrated Ni(II), Cd(II), and anhydrous Zn(II) salts reacted with 69 in different molar ratios in THF to furnish four unique architectures (70-73) (Scheme 24).…”

“…Another interesting report was provided by the same group where they invented new nickel(II), zinc(II), and cadmium(II) complexes bearing the FcLR ligand capable of acting as sensitizers for TiO 2 ‐based DSSC (Dye‐Sensitized Solar Cells) . Unlike their previous report they proceeded with water instead of alcohol to compose ferrocenyl dithiophosphonate ligand 69 .…”