Shape and Phase-Controlled One-Pot Synthesis of Air Stable Cationic AgCdS Nanocrystals, Optoelectronic and Electrochemical Hydrogen Evolution Studies.

CdS-based materials are extensively studied for photocatalytic water splitting. By incorporating Ag+ into CdS nanomaterials, the catalyst's charge carrier dynamic can be tuned for photo-electrochemical devices. However, photo-corrosion and air-stability of the heterostructures limit the photocatalytic device's performance. Here, a one-pot, single molecular source synthesis of the air-stable AgCdS ternary semiconductor alloy nanostructures by heat-up method is reported. Monoclinic and hexagonal phases of the alloy are tuned by judicious choice of dodecane thiol (DDT), octadecyl amine (ODA), and oleyl amine (OLA) as capping agents. Transmission electron microscope (TEM) and powder X-ray diffraction characterization of the AgCdS alloy confirm the monoclinic and hexagonal phase (wurtzite) formation. The high-resolution TEM studies confirm the formation of AgCdS@DDT alloy nanorods and their shape transformation into nano-triangles. The nanoparticle coalescence is observed for ODA-capped alloys in the wurtzite phase. Moreover, OLA directs mixed crystal phases and anisotropic growth of alloy. Optical processes in AgCdS@DDT nano-triangles show mono-exponential decay (3.97 ± 0.01 ns). The monoclinic phase of the AgCdS@DDT nanorods exhibits higher electrochemical hydrogen evolution activity in neutral media as compared to the AgCdS@ODA/OLA alloy nanocrystals. DDT and OLA-capped alloys display current densities of 14.1 and 14.7 mA cm-2 , respectively, at 0.8 V (vs RHE).

Geometrically unprecedented 3-, 5- and 7-membered Hg(II)-Cu(I) and Hg(II)-Ag(I) thiolate clusters: precursors to intermetallics.

The syntheses of three polynuclear heterobimetallic complexes through the use of a homoleptic mercuric thiolate anion as a template for the assembly of coinage metal are presented. The complexes, [(PPh3)3Ag3(µ-SPh)7Hg2] (1), [Hg(µ-SPh)4{Cu(PPh3)2}2] (2) and [(dppe)2Cu5(µ-SPh)7Hg2(SPh)2] (3) were utilized as precursors for the fabrication of Hg-Ag and Hg-Cu intermetallics.

Studies of synthesis, structural features of Cu(I) thiophene-2-thiocarboxylates and unprecedented desulfurization of Cu(II) thiocarboxylate complexes.

Thiophene-2-thiocarboxylate complexes of Cu(I), [(Ph(3)P)(2)Cu(SCOth)] (1) and H[(Ph(3)P)(2)Cu(SCOth)(2)] (2) (where th = thiophene) were synthesized and characterized structurally by X-ray crystallography. Electronic absorption and emission spectral properties of the two compounds have been studied. Cu(II) complexes, [(TMEDA)Cu(SCOth)(2)] (3b) and [(Phen)Cu(SCOth)(2)] (4a) (where TMEDA = tetramethylethylenediamine; Phen = 1,10-phenanthroline) were prepared and characterized by spectroscopic measurements. 3b and 4a underwent desulfurization under ambient conditions readily yielding the corresponding carboxylate complexes [(TMEDA)Cu(O(2)Cth)(2)] (3a) and [(Phen)Cu(O(2)Cth)(2)·H(2)O] (4b). 3a and 4b have been characterized crystallographically.

The chemistry of cadmium-thiocarboxylate derivatives: synthesis, structural features, and application as single source precursors for ternary sulfides.

Novel heterobimetallic complexes [(PPh(3))(2)Cu(µ-SCOPh)(2)Cd(SCOPh)] (2a), [(PPh(3))(2)Cu(µ-SCOth)(2)Cd(SCOth)] (2b), [(PPh(3))(2)Ag(µ-SCOth)(2)Cd(SCOth)] (3a), [(PPh(3))(2)Ag(µ-SCOth)(2)Cd(H(2)O)(SCOth)] (3b), [(PPh(3))(2)Ag(µ-SCOPh)(2)Cd(SCOPh)] (3c), and a bimetallic complex [PPh(3)Cd(µ-SCOth)SCOth](2)·CH(2)Cl(2) (5) (th = thiophene) were prepared and characterized by single crystal X-ray diffraction analysis. A coordination polymer [Cd(SCOPh)(2)](n) (4) has also been characterized structurally that exhibited metal-like electrical conductivity. The heterobimetallic complexes on pyrolyzing under controlled conditions yielded ternary sulfides of composition CuCd(7)S(8), CuCd(10)S(11), Ag(2)Cd(8)S(9), and Ag(2)Cd(5)S(6), which have been characterized by SEM-EDX and X-ray diffractometry. Photophysical properties and electrical conductivities of the sulfides have also been studied.

Novel heterobimetallic thiocarboxylato complexes: synthesis, characterization and application as single source precursor for ternary chalcogenides.

Heterobimetallic complexes, (PPh(3))(2)M(mu-SCOPh)(2)Pb(SCOPh) [where, M = Cu(I) (1) or Ag(I) (2)] have been synthesized and characterized by FTIR, (1)H, (13)C and (31)P NMR spectroscopy. Molecular structures in solid state have been determined by single crystal X-ray diffraction. Electronic spectra of the compounds have been recorded and explained on the basis of TDDFT calculations. Luminescence and redox properties of the complexes have also been studied. Following the thermogravimetric analysis data the compounds were pyrolysed and one of the decomposition products has been characterized as Pb(4)Cu(5)O(22.6) (3) by SEM-EDX and X-ray diffraction studies.

Synthesis of a one-dimensional coordination polymer containing pendant hydrosulfide groups.

In view of the recent interest in compounds containing M-SH units, an organotin hydrosulfide compound, Me2Sn(SH)(O2CMe) (1) was prepared by controlled hydrolysis of the diorganotin thioacetate. Under similar mild hydrolytic conditions the corresponding benzoate could not be isolated. Instead, the thiobenzoate complex, Me2Sn(SOCPh)2 (3) was obtained in excellent yields indicating that there was no hydrolysis. Both 1 and 3 were characterized by X-ray crystallography. Some properties of the polymeric compound 1, such as spectral, electrical conductivity and NLO response were also studied. The reactivity and properties were explained using density functional calculations.