The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg 19 (dtp) 12 ] (dtp = S 2 P(O i Pr) 2 À ) 1 and [PdHAg 20 (dtp) 12 ] + 2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55 % yield. Further modification of the shell results in the formation of [PdAg 21 (dtp) 12 ] + 3 via an internal redox reaction, with the system retaining an 8-electron superatomic configuration. The interstitial hydride in 1 and 2 contributes its 1s 1 electron to the superatomic electron count and occupies a PdAg 3 tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT NMR spectroscopy. The emissive state of 3 has a lifetime of 200 μs (λ ex = 448; λ em = 842), while 1 and 2 are non-emissive. The catalytic reduction of 4-nitrophenol is demonstrated with 1-3 at room temperature.

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A series of seven luminescent copper­(I) dithiophosphonate (dtp) clusters of the type Cu4L4 (L = S2PR­(OR′)−) were formed from CuCl2·2H2O precursor in aqueous medium under ambient conditions. The dtp ligand serves the dual function of acting as a sacrificial reducing agent and cluster core stabilizer. The new clusters were characterized by 1H and 31P NMR and ESI-MS, and the single-crystal X-ray structures for two representative clusters [Cu4{(S2P­(1,4-C6H4OMe)­(OR′)}4] (R′ = OCH­(CH3)2; CH2C6H5) were determined. The redox reaction yielded clusters in satisfactory yield, and all exhibited luminescence with λem max in the range 519–534 nm and half-lives in the range 10–14 μs.

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.

The preparation of dialysis-free bacterial nanocrystalline cellulose (BNCC) derived from Kombucha and combined with a suitable polymer to form a robust conducting material is described.