Ferrocenyl Dithiocarbamate Based d¹⁰ Transition‐Metal Complexes as Potential Co‐Sensitizers in Dye‐Sensitized Solar Cells

Abstract

Three new d 10 transition-metal dithiocarbamates containing ferrocene, namely [M(FcCH 2 EtOHdtc) 2 ] (M = Zn, Cd and Hg; dtc = dithiocarbamate) have been synthesized and characterized by elemental analyses, IR, 1 H, and 13 C NMR spectroscopy, and X-ray crystallography. The coordination geometries around the zinc and mercury ions in the complexes are distorted tetrahedral and distorted linear, respectively. The distorted linear geometry around the mercury complex can be attributed to the presence of the bulky methylferrocenyl [a]

Role of co-sensitization in dye-sensitized and quantum dot-sensitized solar cells

“…Other than ruthenium based dyes, organic and metalfree dyes, natural dyes oriented co-sensitization through successive absorption of two different natural dyes also attempted. Yadav et al [261,262] analyzed the sensitization effect of various transition metal complexes (in DCM/DMSO solution) with N719 dye (in ethanol) on the mesoporous TiO 2 layer. The authors found that zinc (Zn) based complexes resulted highest efficiency (7.10%) over other complexes.…”

Exploring the Topological Landscape Exhibited by Binary Zinc-triad 1,1-dithiolates

“…The dithiocarbamate ligands generally coordinate with disparate Hg-S bond lengths, with the differences between the short and long bonds usually being 0.3-0.4 Å . Supramolecular molecular association between centrosymmetrically-related molecules is always found in 146-155, with intermolecular Hg … S separations ranging from a short 3.18 Å in Hg[S2CN(CH2CH2OH)CH2(ferrocenyl)]2 (155) [70] to a long 3.85 Å in Hg[S2CN(Benzyl)CH2(1-Me-1H-pyrrol-2-yl)] (152) [146], much in the same way as discussed above for the transition of zinc dithiocarbamates between motifs M and O, see Figure 8. For mercury and sulphur, the sum of the van der Waals radii is assumed to be 3.35 Å [20].…”

“…S interactions [138]. Key geometric data for the 44 Hg(S 2 CNRR') 2 structures, 142-185 [39,70,101,105,, described in this section are listed in Table 5. The exceptional series of structures, at least in terms of forming intermolecular Hg···S interactions, are strictly monomeric 142-145 [139][140][141][142], illustrated for Hg[S 2 CN(i-Pr) 2 ] 2 (142) [139] in Figure 14a, as there are no intermolecular Hg···S contacts less than 4.0 Å in their respective crystals.…”

“…Compounds 146-155 [39,70,101,105,[143][144][145][146][147]] also adopt motif M, but lack the symmetry exhibited by 142-145. The dithiocarbamate ligands generally coordinate with disparate Hg-S bond lengths, with the differences between the short and long bonds usually being 0.3-0.4 Å. Supramolecular molecular association between centrosymmetrically-related molecules is always found in 146-155, with intermolecular Hg .…”

Tailoring the Optical Properties of Organic D‐π‐A Photosensitizers: Effect of Sulfur Introduction in the Acceptor Group

“…A small number of papers described the synthesis and application in DSSCs of organic dyes with sulfur‐based anchoring groups. Chauhan and co‐workers reported the application of ferrocenyl‐containing compounds bearing a dithiocarbamate coordinating group and the corresponding complexes with various metals (including Zn, Cd, Hg, Cu, Pd, Pt, Co) as sensitizers or co‐sensitizers in DSSCs, recording efficiencies close to those obtained with reference dye N719 under the same conditions . A few groups independently explored the possibility to use thiobarbituric acid as an anchoring group and compared the performances of the corresponding dyes with those of their oxygenated analogues: monodentate dyes based on simple phenyl or carbazole backbones,, or dyes with two anchoring groups on the same molecular structure were investigated.…”