Herein we report the one-pot electrodeposition of copper indium gallium diselenide, CuIn(1-x)Ga(x)Se(2) (CIGS), thin films as the p-type semiconductor in an ionic liquid medium consisting of choline chloride/urea eutectic mixture known as Reline. The thin films were characterized by scanning electron microscopy with energy dispersive X-ray analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, Raman microspectroscopy, and UV-visible spectroscopy. Based on the results of the characterizations, the electrochemical bath recipe was optimized to obtain stoichiometric CIGS films with x between 0.2 and 0.4. The chemical activity and photoreactivity of the optimized CIGS films were found to be uniform using scanning electrochemical microscopy and scanning photoelectrochemical microscopy. Low-cost stoichiometric CIGS thin films in one-pot were successfully fabricated.

The complexes [PtMe2(NN)] (NN = 2,2′-bipyridine = bipy, 1a; NN = di-2-pyridylamine = dpa, 1b; NN = di-2-pyridyl ketone = dpk, 1c) react with dimethyldioxirane in moist acetone to give the hydroxoplatinum(IV) complexes [Pt(OH)2Me2(NN)] (NN = bipy, 2a; NN = dpa, 2b, or [Pt(OH)Me2(dpkOH)], 3). Complex 2a crystallizes as the hydrate 2a·7H2O, which has a complex supramolecular network structure formed through hydrogen bonding between PtOH groups and water molecules. Attempts to trap a potential oxoplatinum(IV) intermediate in these reactions were unsuccessful, and computational studies suggest that oxoplatinum(IV) intermediates are improbable. It is suggested that oxygen atom transfer from the dioxirane to platinum is coupled to proton addition to give the hydroxoplatinum group directly.

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The complex [PtMe2(bipy)] (1; bipy = 2,2′-bipyridine) fails to react with the oxaziridine derivatives RCHON-t-Bu (R = H, Ph, 2-pyridyl) in acetone at room temperature, but an easy reaction occurs in methanol solution to give the platinum(IV) complex [Pt(OH)(OMe)Me2(bipy)] and the corresponding imine RCHN-t-Bu. In the case with R = Ph, the hemiaminal intermediate [Pt(OMe)(OCHPhNH-t-Bu)Me2(bipy)] was formed and then reacted only slowly to form [Pt(OH)(OMe)Me2(bipy)] and PhCHN-t-Bu. Computational studies indicate that the reaction of 1 with oxaziridines occurs to give a charge transfer complex but that further reaction requires assistance from hydrogen bonding and coordination with specific methanol molecules. The work provides strong support for the theory that oxygen atom transfer to 1 from either dioxiranes or oxaziridines must be coupled to proton transfer and does not involve oxoplatinum(IV) intermediates.

Complexes [PtMe 2 (NN)], with NN = 2,2′-bipyridine (bipy), 4,4′-ditert-butyl-2,2′-bipyridine (bu 2 bipy), di-2-pyridylamine (dpa), or di-2-pyridyl ketone (dpk), react easily with phthaloyl peroxide to give a mixture of the chelate complex [PtMe 2 {κ 2 -O,O′-1,2-(O 2 C) 2 C 6 H 4 }(NN)], which was structurally characterized when NN = bu 2 bipy, and an oligomer or polymer [PtMe 2 {μ-κ 2 -O,O′-1,2-(O 2 C) 2 C 6 H 4 }-(NN)] n . In the case with NN = dpa, no phthalate chelate complex is formed. These complexes are easily hydrolyzed, and the complexes cis-[PtMe 2 (OH){κ 1 -O-O 2 CC 6 H 4 -2-CO 2 H}(bipy)] and trans-[PtMe 2 {κ 1 -O-O 2 CC 6 H 4 -2-CO 2 H}(dpkOH)]have been structurally characterized. It is argued that the oxidative addition of phthaloyl peroxide occurs by a polar mechanism and that the hydrolysis is easy because there is no special stability associated with the seven-membered platinumphthalate chelate ring.