Ca[Ti(HPO)(PO)]·HO, Ca[Ti(HO)(HPO)]·HO, and Ti(HPO): Solid-State Oxidation via Proton-Coupled Electron Transfer.

Titanium phosphorus oxides (TiPOs) are promising energy-conversion materials, but most are of tetravalent titanium (Ti), with the trivalent TiPOs less explored because of instability and obstacles in synthesis. In this study, we used a simple synthetic strategy and prepared three new TiPOs with different phosphorus oxoanions: the phosphate CaTi(HPO)(PO)·HO (), the phosphite CaTi(HO)(HPO)·HO (), and the hypophosphite Ti(HPO) (). Each possesses different structures in one, two, and three dimensions, yet they are related to one another because of their infinite chains.

A titanium(iii) phosphite exhibits polymorph-distinct redox activity involving proton-coupled electron transfer.

A novel titanium(iii) phosphite with intriguing polymorphism and solid-state proton-coupled electron transfer (PCET) oxidation is presented. The polymorphs show structure-dependent PCET reactivity, interpretable by proton distribution in channels. Combined with subsequent photoreduction, the redox cycle initiated with Ti can produce H and transform organics.

Carboxylic acid-protruding zincophosphate sheets exhibiting surface mechanochemical reactivity and intriguing nano-morphological reversibility.

For the first time, functional carboxylic acid (-COOH) groups protruding on both sides of zincophosphate sheets are prepared, leading to a unique surface-active lamellar material characterized by modifiable wettability via a facile mechanochemical reaction. The interior -COOH groups lead to high thermal stability unusual to hybrid-layer structures and undergo the intriguingly reversible nano-morphological transformation never unveiled in metal oxysalts before.

Indium Phosphite-Based Porous Solids Exhibiting Organic Sensing and a Facile Route to Superhydrophobicity.

In searching for practical crystalline porous solids, two unique hybrid materials with featured functions, In-bpy and In-dpe, were prepared without deliberately designed organic linker units or complex post-modification procedures. Composed of oxalate-embedded metal phosphite (MPO) sheets and bipyridyl-type ligands of varied molecular lengths, they show a common pillar-layered topology but are the first well-characterized organo-MPOs to possess genuine porosity, substantiated by CO adsorption, and structural stability under harsh conditions. In-bpy exhibits a turn-on fluorescence signal when in contact with p-xylene, making it the first MPO-based sensing material with selectivity and recyclability.

Transition Metal Titanophosphates with Intercalated Molecular Photoluminescence and Catalytic Properties.

In this study, α-TiP layered structure incorporating a heterometal center for organic ligand binding to enhance structural complexity and functionality were prepared. The protons of the α-TiP layer were replaced with zinc ions coordinated by 4-pyridinecarboxylic acid (PCA) and water to form a layer structure, TiZn(PO ) (H O)(PCA) (1). The tetrahedral zinc center with coordinated water in 1 is unprecedented in zincophosphate or zinc-MOF systems and is usually only found in metalloenzyme systems.

Low-bandgap conjugated polymer for high efficient photovoltaic applications.

We investigate the morphological and performance of organic photovoltaics based on blended films of alternating poly(thiophene-phenylene-thiophene) and [6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM). The resulting fine-scale phase separation leads to enhanced performance and the highest power efficiency (6.4% under AM 1.

Sub-10 nm platinum nanocrystals with size and shape control: catalytic study for ethylene and pyrrole hydrogenation.

Platinum nanocubes and nanopolyhedra with tunable size from 5 to 9 nm were synthesized by controlling the reducing rate of metal precursor ions in a one-pot polyol synthesis. A two-stage process is proposed for the simultaneous control of size and shape. In the first stage, the oxidation state of the metal ion precursors determined the nucleation rate and consequently the number of nuclei.

Flux synthesis, crystal structures, and solid-state NMR spectroscopy of two indium silicates containing varied In-O coordination geometries.

Two novel indium silicates, K5In3Si7O21 (1) and K4In2Si8O21 (2), have been synthesized by a flux-growth method and characterized by single-crystal X-ray diffraction. The structure of 1 consists of siebener single chains of corner-sharing SiO4 tetrahedra running along the b axis linked via corner-sharing by In2O9 face-sharing octahedral dimers and InO5 trigonal bipyramids to form a 3D framework. The structure of 2 consists of a 3D silicate framework containing 6- and 14-ring channels.

Rb6(InCo)2(Si9O26): a mixed-metal silicate containing 20-membered-ring silicate single layers with a very low Si:O ratio.

A new cobalt-indium silicate, Rb6(InCo)2(Si9O26), has been synthesized via a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. It crystallizes in the noncentrosymmetric orthorhombic space group Aba2 (No. 41) with a = 20.

Rb3In(H2O)Si5O13: a novel indium silicate with a CdSO4-topological-type structure.

A novel indium silicate, Rb3In(H2O)Si5O13, has been synthesized using a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. The structure consists of five-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to four adjacent five-membered rings to form a 3D silicate framework that belongs to the CdSO4 topological type. The InO6 octahedron shares five of its corners with five different SiO4 tetrahedra to form a 3D frame-work that delimits two types of channels to accommodate the rubidium cations.

Hydrothermal synthesis, crystal structure, and solid-state NMR spectroscopy of a new indium silicate: K2In(OH)(Si4O10).

A new indium(III) silicate, K(2)In(OH)(Si(4)O(10)), has been synthesized by a high-temperature, high-pressure hydrothermal method. It crystallizes in the monoclinic space group P2(1)/m (No. 11) with a = 11.

Synthesis, crystal structure, and solid state NMR spectroscopy of NH(4)[(V(2)O(3))(2)(4,4'-bpy)(2)(H(2)PO(4))(PO(4))(2)].0.5H(2)O, a mixed-valence vanadium(IV,V) phosphate with a pillared layer structure.

A mixed-valence vanadium phosphate, NH(4)[(V(2)O(3))(2)(4,4'-bpy)(2)(H(2)PO(4))(PO(4))(2)].0.5H(2)O, has been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction.