Ca2[Ti(HPO4)2(PO4)]·H2O, Ca[Ti2(H2O)(HPO3)4]·H2O, and Ti(H2PO2)3: Solid-State Oxidation via Proton-Coupled Electron Transfer.

Titanium phosphorus oxides (TiPOs) are promising energy-conversion materials, but most are of tetravalent titanium (TiIV), with the trivalent TiIIIPOs less explored because of instability and obstacles in synthesis. In this study, we used a simple synthetic strategy and prepared three new TiIIIPOs with different phosphorus oxoanions: the phosphate Ca2Ti(HPO4)2(PO4)·H2O (1), the phosphite CaTi2(H2O)(HPO3)4·H2O (2), and the hypophosphite Ti(H2PO2)3 (3). Each possesses different structures in one, two, and three dimensions, yet they are related to one another because of their infinite chains. Compound 1 exhibits proton-coupled electron transfer (PCET) reactivity in a solid state, losing one proton from its own HPO4 in oxidation to yield Ca2Ti(HPO4)(PO4)2·H2O (designated as 1O), while compound 2 also exhibits PCET reactivity in which the octahedral core [TiIII(H2O)]3+ gives off two protons to become a titanyl unit [TiIV═O]2+ under oxidation, yielding CaTi2O(HPO3)4·H2O (2O). Both 1O and 2O retain their original frameworks from before oxidation, but there are some changes in the hydrogen and Ti-O bonds that affect the IR absorption and powder X-ray diffraction patterns. Compound 3 represents the first titanium hypophosphite, and two polymorphs were discovered that show structures related to 1 and 2. This work demonstrates a simple strategy that is effective for preparing titanium(III) compounds in a pure phase; further, new findings in the pathways of solid-state PCET reactions promote a greater understanding of the self-sustaining oxidation behavior for TiIIIPO solid materials.

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 TiIII can produce H2 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 CO2 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. Furthermore, In-dpe demonstrates a facile and unprecedented route to the superhydrophobicity of porous solids via a [2+2] photocycloaddition reaction between linker and foreign units. Our findings suggest that MPO may serve as a promising platform for hybrid frameworks to create many more functional porous materials.

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(PO4 )2 (H2 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. The neutral zincotitanophosphate layers, tightly stacked through hydrogen bonds, showed velcro-like behavior on intercalating 4,4'-trimethylenedipyridine (TMDP) reversibly. It rendered a remarkable luminescence property to 1, emitting blue-to-white light under UV excitation. Surprisingly, the replacement of TMDP for PCA in the hydrothermal synthesis still resulted in 1, plus another structure, Ti4 Zn2 (H2 TPB)(PO4 )4 (HPO4 )4 (H2 PO4 )2 (2) (TPB=1,2,4,5-tetra(4-pyridyl)benzene). Clearly, in situ C-C cracking and C-C coupling of TMDP simultaneously occurred to generate PCA and TPB and thereafter the oxidant, Zn(NO3 )2 , was quantitatively determined to isolate crystal 1 from 2. The structure of 2 also featured α-TiP layers with pedant Zn tetrahedra but formed a three-dimensional neutral framework through TPB. For the first time, α-TiP-derived structures and their properties have been elucidated, which help in understanding intriguing in situ ligand formation and intercalation-induced luminescence, to exploit potential photocatalysis in polymerization.

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 1.5G (100 mW cm(-2))) when we use solvent annealing process.

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. The reaction temperature controlled the shape in the second stage by regulation of the growth kinetics. These well-defined nanocrystals were loaded into MCF-17 mesoporous silica for examination of catalytic properties. Pt loadings and dispersions of the supported catalysts were determined by elemental analysis (ICP-MS) and H(2) chemisorption isotherms, respectively. Ethylene hydrogenation rates over the Pt nanocrystals were independent of both size and shape and comparable to Pt single crystals. For pyrrole hydrogenation, the nanocubes enhanced ring-opening ability and thus showed a higher selectivity to n-butylamine as compared to nanopolyhedra.

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. InO5 square pyramids are located within the 14-ring channels sharing corners with the silicate framework. The solid-state 29Si MAS NMR spectrum of compound 1 was recorded; it shows the influence of the indium atoms in the second coordination sphere of the silicon on the chemical shift. Crystal data: 1, orthorhombic, Pna21 (No. 33), a = 12.4914(3) A, b = 16.8849(3) A, c = 10.2275(2) A, V = 2157.1(1) A3 and Z = 4; 2, monoclinic, P21/n (No. 14), a = 8.4041(3) A, b = 11.4919(4) A, c = 10.4841(3) A, beta = 90.478(2) degrees , V = 1012.5(1) A3 and Z = 2.

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 = 20.779(1) A, b = 12.0944(6) A, c = 10.7761(5) A, V =2708.1(2) A(3), and Z = 4. The structure consists of 20-membered-ring silicate single layers of corner-sharing SiO4 tetrahedra interconnected by dimers of edge-sharing CoO4 tetrahedra and InO6 octahedra into a 3D framework. The Si:O ratio for the title compound is the lowest among the known single-layer silicates. Magnetic susceptibility confirms the divalent state of the cobalt ion. The powder sample has a second-harmonic-generation signal, confirming the absence of a center of symmetry in the structure.

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. The sixth corner of InO6 is coordinated H2O. The structure is related to that of the titanium silicate ETS-10, and these are the only two metal silicates that have the CdSO4-topological-type structure. In addition, the crystal of Rb3In(H2O)Si5O13 shows an intense second harmonic generation signal. Crystal data: H2Rb3InSi5O14, monoclinic, space group Cc (No. 9), a = 9.0697(5) A, b = 11.5456(6) A, c = 13.9266(8) A, beta = 102.300(1) degrees, V = 1424.8(1) A3, and Z = 4.

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 = 11.410(1) A, b = 8.373(1) A, c = 11.611(1) A, beta = 112.201(2) degrees, and Z = 4. The structure, which is analogous to that of K(2)CuSi(4)O(10), consists of unbranched vierer 4-fold chains of corner-sharing SiO(4) tetrahedra running along the b axis linked together via corner sharing by chains of trans-corner-sharing InO(4)(OH)(2) octahedra to form a 3-D framework which delimits 8-ring and 6-ring channels to accommodate K(+) cations. The presence of hydroxyl groups is confirmed by IR spectroscopy. The (29)Si MAS NMR exhibits four resonances at -88.6, -90.1, -97.4, and -98.2 ppm corresponding to four distinct crystallographic Si sites. A (1)H --> (29)Si CP/MAS NMR experiment was performed to assign the four resonances.

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. It crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.6354(8) A, b = 9.9786(6) A, c = 23.369(1) A, beta = 92.713(1) degrees, and Z = 4 with R(1) = 0.0389. The structure consists of dimers of edge-sharing vanadium(IV,V) octahedra that are connected by corner-sharing phosphate tetrahedra to form layers in the ab-plane, which are further linked through 4,4'-bipyridine pillars to generate a 3-D framework. Magnetic susceptibility confirms the valence of the vanadium atoms. The (31)P MAS NMR spectrum shows a resonance centered at 80 ppm with a shoulder at ca. 83 ppm in an intensity ratio close to 1:2, which correspond to two distinct P sites. The observed large downfield (31)P NMR shifts can be ascribed to magnetic exchange coupling involving phosphorus atoms. The unpaired electron spin density at the phosphorus nucleus was determined from variable-temperature (31)P NMR spectra. The (1)H MAS NMR spectrum was fitted to six components in accordance with the structure as determined from X-ray diffraction.