New di-ferrocenyl-ethynylpyridinyl triphenylphosphine copper halide complexes and related di-ferricenyl electro-crystallized materials.

Three new neutral di-ferrocenyl-ethynylpyridinyl copper complexes, [L2(CuCl)2(PPh3)2] (), [L2(CuBr)2(PPh3)2] (), and [L2(CuI)2(PPh3)2] () were synthesized from the ferrocenyl-ethynylpyridine ligand (L) (), the appropriate copper halide CuX (with X = Cl(-), Br(-), I(-)) and triphenylphosphine. These neutral complexes were fully characterized by spectroscopic methods and by single crystal X-ray crystallography. Cyclic voltammetry in dichloroethane revealed chemically reversible ferrocenyl oxidation signals followed by characteristic "stripping reduction peaks" showing evidence for oxidation-product electro-crystallization. Scanning electron microscopy confirmed spontaneous formation of crystalline oxidation products with three distinct morphologies for X = Cl(-), Br(-), I(-). Energy dispersive X-ray elemental analysis data show Fe : P ratios of 1 : 2.0, 1 : 2.1 and 1 : 2.1 for electro-crystallization products of complexes , , and , respectively, indicating the presence of two [PF6](-) anions in the vicinity of the dioxidized complexes, and suggesting product formulae [](2+)[PF6](-)2, [](2+)[PF6](-)2 and [](2+)[PF6](-)2.

Solution-processed mesoscopic Bi2S3:polymer photoactive layers.

The fabrication of solution-processed nontoxic mesoporous Bi2S3 structures is demonstrated and the suitability of these structures for use in hybrid solar cells investigated. Mesoporous Bi2S3 electrodes are prepared via thermal decomposition of a thin film composed of a bismuth xanthate single source precursor. The resultant Bi2S3 films are made up of regular needles with approximate dimensions of 50×500 nm, as confirmed by scanning electron microscopy (SEM). The crystallinity of the Bi2S3 is found to be dependent on the annealing temperature, as determined by X-ray diffraction. The porous Bi2S3 films are infiltrated with the hole conductor P3HT to generate novel hybrid films, and laser-based transient absorption spectroscopy is used to interrogate the charge-separation reaction at the resulting Bi2S3/P3HT heterojunction. Specifically, optical excitation of the hybrid films results in efficient and long-lived charge separation (microsecond to millisecond timescale), thereby rendering such films suitable for the development of novel low-cost solar-energy conversion devices.

New multi-ferrocenyl- and multi-ferricenyl- materials via coordination-driven self-assembly and via charge-driven electro-crystallization.

Three new tetra-ferrocenylethynylpyridinyl copper complexes, L4(CuI)4 (3), L4(CuBr)2 (4), and L4(CuCl)2 (5) have been prepared from the reaction of ferrocenylethynylpyridine (L)(2) with copper halides CuX (with X = I(-), Br(-), Cl(-)).The ligand 2 and the complexes 3-5 have been fully characterized by spectroscopic methods. The structures of 2-4 have been confirmed by single-crystal X-ray crystallography. 2 forms a dimer in the crystalline-state through C-H··N hydrogen bonds. 4 and 5 are dimers and 3 a tetramer, in all cases linked through Cu-X··Cu bridging interactions. Cyclic voltammetry in dichloroethane showed chemically reversible multiferrocenyl oxidation signals with evidence for product electro-crystallization. The oxidation products were isolated by electrodeposition onto a Pt disc electrode and investigated by scanning electron microscopy which confirmed the spontaneous formation of crystalline oxidation products with distinctive morphologies. Energy dispersive X-ray elemental analysis shows the presence of hexafluorophosphate (counterion) with the P:Fe ratio of 1:1, 0.5:1, and 1:1 for the electrocrystallized products 3, 4, and 5, respectively, suggesting the formulas [3](4+)(PF6(-))4, [4](2+)(PF6(-))2, and [5](4+)(PF6(-))4 for the electro-crystallized products.

The Reaction and Materials Chemistry of [Sn6 (O)4 (OSiMe3 )4 ]: Chemical Vapour Deposition of Tin Oxide.

[Sn6 (O)4 (OSiMe3 )4 ] and [{Sn(OSiMe3 )2 }2 ] have been used to deposit SnO thin films by chemical vapour deposition. Films derived from [Sn6 (O)4 (OSiMe3 )4 ] comprise uniform cubes and are highly oriented, whereas those deposited from [{Sn(OSiMe3 )2 }2 ] are made up of a continuous non-oriented layer with oriented cubes on the surface. The structure of a co-crystal, 2 Sn6 (O)4 (OSiMe3 )4 ⋅[Sn(OSiMe3 )2 ]2 ⋅4 THF, shows that [{Sn(OSiMe3 )2 }2 ], a liquid at room temperature, adopts a µ-OSiMe3 -bridged dimeric structure. [Sn6 (O)4 (OSiMe3 )4 ] reacts with O2 in a controlled manner to afford the novel oxo-cluster [Sn4( O)(OSiMe3 )8 ], the structure of which is reported. In addition, a crystal of {[Sn4 (O)(OSiMe3 )5 ]+ 2 [Sn(O)(OSiMe3 )4 Cl]+ 2 }[Cl]- 4 has been fortuitously isolated from the presence of SnCl2 in the starting material for the preparation of [Sn6 (O)4 (OSiMe3 )4 ], and has been shown to incorporate two novel cationic oxo-tin clusters.

Thermal decomposition of solution processable metal xanthates on mesoporous titanium dioxide films: a new route to quantum-dot sensitised heterojunctions.

We introduce a straightforward route to the fabrication of metal sulfide semiconductor (e.g. CdS, Sb(2)S(3), Bi(2)S(3)) sensitised TiO(2) films. Our approach is based upon the controllable thermal decomposition of a single-source metal xanthate precursor on a mesoporous metal oxide film. The growth of the metal sulfide deposit is confirmed by Raman and UV-Vis steady-state absorption measurements. Transient absorption spectroscopy measurements provide evidence for charge separation across the metal sulfide/TiO(2) interface. Moreover, a high yield of long-lived photogenerated charges is observed in a three-component TiO(2)/metal sulfide/spiro-OMeTAD film, thus demonstrating the potential of such multicomponent films for solar energy conversion devices.

The synthesis and reaction chemistry of new amino-functionalised tin(II) alkoxides.

Sn(ii) derivatives of the aminoalcohols (t)Bu(H)NC(Me)(H)CH(2)OH (Htbap, ), (R(1)R(2)NCH(2))(2)C(H)OH (R(1) = R(2) = Me, , Hbdmap; R(1) = (t)Bu, R(2) = H, , Hbtbap), (R(1)R(2)NCH(2))(3)COH (R(1) = R(2) = Me, , Htdmap; R(1) = (t)Bu, R(2) = H, , Httbap) have been synthesised by reaction of the alcohol with Sn[N(SiMe(3))(2)](2). The structures of the ligands , .H(2)O, along with Sn(ttbap)(2) have been determined; the latter is pseudo-trigonal bipyramidal with nitrogen atoms in axial sites and oxygen atoms and a stereochemically-active lone pair in the equatorial positions. Sn(ttbap)(2) reacts with Fe(2)(CO)(9) in 2 : 1 ratio (Sn : Fe = 1 : 1) to afford the donor-acceptor complex (ttbap)(2)Sn:-->Fe(CO)(4), while in 1 : 1 ratio (Sn : Fe = 1 : 2) the Sn(0) complex (Httbap)Sn[Fe(CO)(4)](2) is formed, in which Httbap is a neutral zwitterionic form of the ligand. The structures of both bimetallic species are reported. Thermal decomposition of (Httbap)Sn[Fe(CO)(4)](2) under low-pressure CVD conditions gives a film containing a mixture of cubic-Sn, cubic-Fe and the hexagonal intermetallic phase Fe(3)Sn.

Nanostructured hybrid polymer-inorganic solar cell active layers formed by controllable in situ growth of semiconducting sulfide networks.

Nanostructured composites of inorganic and organic materials are attracting extensive interest for electronic and optoelectronic device applications. In this paper, we introduce a general method for the fabrication of metal sulfide nanoparticle/polymer films employing a low-cost and low temperature route compatible with large-scale device manufacturing. Our approach is based upon the controlled in situ thermal decomposition of a solution processable metal xanthate precursor complex in a semiconducting polymer film. To demonstrate the versatility of our method, we fabricate a CdS/P3HT nanocomposite film and show that the metal sulfide network inside the polymer film assists in the absorption of visible light and enables the achievement of high yields of charge photogeneration at the CdS/P3HT heterojunction. Photovoltaic devices based upon such nanocomposite films show solar light to electrical energy conversion efficiencies of 0.7% under full AM1.5 illumination and 1.2% under 10% incident power, demonstrating the potential of such nanocomposite films for low-cost photovoltaic devices.