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.

High-temperature, high-pressure hydrothermal synthesis, crystal structure, and infrared and NMR spectroscopy of a barium lead borate with a 2D layer structure: [Ba3Pb(H2O)][B11O19(OH)3].

With a high-temperature, high-pressure hydrothermal technique, a new barium lead borate, [Ba3Pb(H2O)][B11O19(OH)3] (1), has been synthesized and characterized by single-crystal X-ray diffraction, and infrared and solid-state NMR spectroscopy. The structure of 1 contains planar thick layers of borates with the Ba2+ cations at sites in the inter- and intralayer space. Each layer consists of three single sheets. The central sheet is very corrugated and is built up from the fundamental building block (FBB) 2Δ3□:Δ2□-Δ2□. On both sides of the central sheet there are borate single chains formed of the very rare FBB 2Δ4□:Δ2□-3â–¡Δ via corner-sharing. This FBB was first observed in a high-pressure polymorph of CaB2O4. These chains are linked into a sheet by PbO5(H2O) polyhedra, which are further linked to the central sheet by sharing vertices between triangles and tetrahedra to form a thick layer. The IR spectrum shows the presence of hydroxyl groups of HBO4, water molecules, BO3 triangles, and BO4 tetrahedra. The presence of BO3 and BO4 polyhedra was also confirmed by 11B MAS NMR spectroscopy.

Publisher Correction: Rapid desolvation-triggered domino lattice rearrangement in a metal-organic framework.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Rapid desolvation-triggered domino lattice rearrangement in a metal-organic framework.

Topological transitions between considerably different phases typically require harsh conditions to collectively break chemical bonds and overcome the stress caused to the original structure by altering its correlated bond environment. In this work we present a case system that can achieve rapid rearrangement of the whole lattice of a metal-organic framework through a domino alteration of the bond connectivity under mild conditions. The system transforms from a disordered metal-organic framework with low porosity to a highly porous and crystalline isomer within 40 s following activation (solvent exchange and desolvation), resulting in a substantial increase in surface area from 725 to 2,749 m2 g-1. Spectroscopic measurements show that this counter-intuitive lattice rearrangement involves a metastable intermediate that results from solvent removal on coordinatively unsaturated metal sites. This disordered-crystalline switch between two topological distinct metal-organic frameworks is shown to be reversible over four cycles through activation and reimmersion in polar solvents.

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.

Microporous 2D indium metal-organic frameworks for selective CO2 capture and their application in the catalytic CO2-cycloaddition of epoxides.

Four new 2D indium metal-organic frameworks (MOFs) (Me2NH2)[In(SBA)2] (1), (Me2NH2)[In(SBA)(BDC)] (2), (Me2NH2)[In(SBA)(BDC-NH2)] (3), and (NH4)3[In3Cl2(BPDC)5] (4), (H2SBA = 4,4'-sulfonyldibenzoic acid; H2BDC = 1,4-benzenedicarboxylic acid; H2BDC-NH2 = 2-amino-1,4-benzenedicarboxylic acid; H2BPDC = 4,4'-biphenyldicarboxylic acid) have been synthesized under solvothermal reaction conditions for compounds 1 to 3 and the DES (deep eutectic solvent) reaction has been attempted for compound 4. The structure of these MOFs has been determined by using single crystal X-ray diffraction study and all of theses four 2D monolayer framework with porous properties. The N2 gas sorption measurements indicated that Brunauer-Emmer-Teller (BET) and Langmuir surface areas of compound 1 are 207 and 301 m2 g-1, respectively, which is probably the first one having substantial gas uptake properties in the entire 2D In-MOF family to date. Furthermore, these new indium MOFs on the addition of n-Bu4NBr were active for the cycloaddition of CO2 and propylene oxide, generating propylene carbonates in high conversions under mild conditions. Particularly, the most active MOF 4 was found to efficiently couple CO2 with a series of terminal epoxides to give the corresponding cyclic organic carbonates with high selectivities.

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.

Tuning the Color Temperature of White-Light-Emitting Electrochemical Cells by Laser-Scanning Perovskite-Nanocrystal Color Conversion Layers.

The development of white-light-emitting electrochemical cells (LECs) has attracted great attention owing to their numerous advantages. Recently, perovskite materials have also shown many outstanding optoelectronic properties in light absorption and emission, and hence they are suitable for serving as the color conversion layers (CCLs) in solid-state white-light-emitting diodes (LEDs). Here, white LECs were fabricated by integrating non-doped blue-green LECs with CCLs made of a single composition of perovskite nanocrystal (NCs). Moreover, the correlated color temperatures (CCTs) of the white LECs can be tuned by modifying the optical properties of the perovskite NCs, in the same way as so as the color conversion properties of CCLs are tuned, through laser scan. By controlling the laser power, scanning number, and duty cycle of the scanned grating patterns on perovskite-NC CCLs, the CCTs of the white LECs can be tuned from 2502 K to nearly 4300 K. Since this method is much different from that used with conventional CCLs, which use multiple compositions of perovskite NCs to produce white light, the inherent anion-exchange issue of perovskite NCs can be avoided.

Achiral polyamine-induced chiral zinc gallophosphates with fused double helix-like strands exhibiting blue to green photoluminescence.

This study found non-chiral polyamines to be effective in inducing chiral frameworks. Four zinc gallophosphates with a chiral UCSB-7 topology were generated from the use of four different linear-chain polyamines as templates. In the structure, helical inorganic strands and templates appeared to fuse into a double helix-like arrangement. Notably, they are the first chiral frameworks to display optical analogues and intriguing photoluminescence properties.

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.

Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization.

The in situ and systematic high-throughput investigation of the system Al3+/4,4'-benzophenonedicarboxylic acid (H2BPDC)/DMF/H2O in the presence of various additives was carried out, and a new Al-MOF of composition [Al(OH)(BPDC)], denoted as CAU-21-BPDC, was obtained. Its crystal structure was determined from single-crystal X-ray diffraction data (space group I422, a = b = 17.2528(7) Å, c = 23.864(1) Å). The structure is built up by octanuclear rings of cis corner-sharing AlO6 polyhedra forming the inorganic building unit (IBU). These {Al8O8} IBUs are arranged in a bcu packing and connected via BPDC2- ions in a way that each IBU is linked via two linker molecules to each of the eight adjacent IBUs. Thus, accessible, one-dimensional modulated pores with a diameter between 3.6 and 6.5 Å are formed. In addition, tetrahedral cavities are formed by the BPDC2- linker molecules. The framework of CAU-21-BPDC is polymorphous with that of CAU-8-BPDC, which contains one-dimensional chains of trans corner-sharing AlO6 polyhedra connected by BPDC2- ions. Replacing H2BPDC by 4,4'-oxydibenzoic acid (H2ODB), which contains an oxygen atom between the phenyl rings instead of a keto group, leads to the synthesis of Al-MOFs isoreticular with CAU-8-BPDC and CAU-21-BPDC. In addition, a coordination polymer, [Al(HODB)2(OH)], was discovered and structurally characterized. The structure of CAU-8-ODB was refined from powder X-ray diffraction data, while a Pawley refinement was carried out for CAU-21-ODB to determine the lattice parameters and confirm phase purity. The structure of CAU-21-ODB was confirmed using density functional theory (DFT) calculations. A thorough characterization shows that the CAU-8 and CAU-21-type structures are stable up to 350 and 300 °C in air, respectively, almost independent of the linker molecules incorporated. The former MOFs are porous toward N2 and CO2, while the latter only adsorb CO2.

From Bola-Surfactant Templated Bimetal Phosphites to the Design of Crystalline Inorganic Mesoporous Frameworks.

Reproducing inorganic modules in situ for pore augmentation of pure inorganic frameworks is challenging but can be a key to rational synthesis. After the first success of using monoamines of varied lengths as a template in producing a set of building blocks that led to a series of growing channels up to a 72-membered ring (72R), research continued into those building blocks to seek any new topologies from them. In this study, another type of template is reported that can control the same building blocks to repeatedly form in situ. By using long linear-chain bola-type surfactants, two new bimetal phosphites, a monoclinic phase exhibiting remarkable quasi-channels of 1.15 nm and an orthorhombic phase with 28R channels of 1.06 nm have been created. By taking them as the first members, two series of novel topologies can be devised, each having a general formula to predict the size and channel wall compositions.

Correction: A highly flexible inorganic framework with amphiphilic amine assemblies as templates.

Correction for 'A highly flexible inorganic framework with amphiphilic amine assemblies as templates' by Hui-Lin Huang et al., Dalton Trans., 2017, DOI: 10.1039/c6dt04165e.

A highly flexible inorganic framework with amphiphilic amine assemblies as templates.

A zinc phosphite-phosphate framework, (HA)2[Zn3(HPO3)4-x(HPO4)x] (1; A = cha, coa, iba, pa, and ha; x = 0.3-1) with nanometer-scale channels was prepared. The framework exhibited an extraordinarily high flexibility, 13% expansion at ambient pressure and 27% contraction under a high pressure of over 2.3 GPa without undergoing any phase transformation. The volume changes in the compression-decompression process are reversible. Such unusual adaptability is rare in pure inorganic networks. The molecular volumes of templates range from 165 Å3 to 228 Å3, which allows to vary channel aperture increasingly from 13.02 to 15.34 Å. Remarkably, three types of organic amine template assemblies, captured in inorganic frameworks, were identified in this study. Presented herein is the first example that demonstrates a successfully controlled template assembly that helps to obtain a flexible inorganic framework with nanosized pores in a systematic manner.

A Crystalline Mesolamellar Gallium Phosphate with Zwitterionic-type Templates Exhibiting Green Afterglow Property.

We synthesized a unique layer structure of gallium phosphates containing zwitterionic-type templates under mild hydrothermal reactions. The zwitterionic-type templates, formed of long-alkyl-chain diamine cations and biphenyldicarboxylate anions, resided upright between adjacent layers, propping the interlayer distance up to 2.2 nm. For the first time, the mesoscale interlayer templates were sufficiently well-ordered to afford elucidation to the atomic-level. The mesolamellar (HDADD)2(BPDC)0.5[Ga3(OH)2(HPO4)4] (1; DADD = 1,12-diaminododecane, BPDC = 4,4'-biphenyldicarboxylate) was composed of inorganic layers built up exclusively with a unique type of heptameric unit which featured an unprecedented trimeric cluster of [Ga3(OH)2O12]. Unexpectedly, compound 1 possessed an unusual green afterglow. To interpret the interesting photoluminescence (PL) property, three other low-dimensional structures related to 1 were prepared as well. The data from PL and electron paramagnetic resonance indicated that the afterglow was mainly attributed to lattice defects and the orientations of BPDC.

High color-rendering warm-white lamps using quantum-dot color conversion films.

Colloidal quantum dots are promising next-generation phosphors to enhance the color rendition of light-emitting diodes (LEDs) while minimizing the brightness droop. In order to exploit the beneficial tunability of quantum dots for highly efficient devices, optimization and determination of the performance limit are of crucial importance. In this work, a facile preparation process of red-emission quantum dot films and simulation algorithm for fitting this film with two commercial LED flat lamps to the optimized performance are developed. Based on the algorithm, one lamp improves from cold-white light (8669 K) with poor color rendition (Ra = 72) and luminous efficacy (85 lm/W) to warm-white light (2867 K) with Ra = 90.8 and R9 = 74.9, and the other reaches Ra = 93 ∼ 95. Impressively, the brightness droop is only about 15 ∼ 20% and the luminous efficacy of 68 lm/W is achieved. Furthermore, our device shows reliability over 1000 hours with only PET (polyethylene-terephthalate) films as the barrier, indicating that this auxiliary red-emission film can be easily applied to improve the color rendition of most commercial LED flat lamps.

Polyamine-Cladded 18-Ring-Channel Gallium Phosphites with High-Capacity Hydrogen Adsorption and Carbon Dioxide Capture.

In this study, we synthesized a unique inorganic framework bearing the largest 18-membered-ring channels in gallium phosphites, denoted as NTHU-15, which displayed genuine porosity even though large organic templates were present. The idea of using the "template-cladded" strategy succeeded in releasing channel space of up to ∼24% of the unit-cell volume as highly positive-charged organic templates were manipulated to cling to the anionic inorganic walls. NTHU-15 showed both high H2 uptake of 3.8 mmol/g at 77 K and effective CO2 adsorption of ∼2.4 mmol/g at 298 K, which surpassed those of all other known extra-large-channel inorganic framework structures. NTHU-15 has been successful at overcoming the long-standing problem of organic-templated extra-large-channel structures as opposed to a "true open" framework. Moreover, it realized practical gas sorption functionality in innovated metal phosphites. In view of its high stability in hot water and high selectivity for CO2 adsorption, NTHU-15 may be the first novel inorganic framework material to be applied to the field of flue gas cleaning.

Synthesis and controllable oxidation of monodisperse cobalt-doped wüstite nanoparticles and their core-shell stability and exchange-bias stabilization.

Cobalt-doped wüstite (CWT), Co0.33Fe0.67O, nanoparticles were prepared via the thermal decomposition of CoFe2-oleate complexes in organic solvents. A controllable oxidation process was then performed to obtain Co0.33Fe0.67O/CoFe2O4 core-shell structures with different core-to-shell volume ratios and exchange bias properties. The oxidized core-shell samples with a ∼4 nm CoFe2O4 shell showed good resistance to oxygen transmission. Thus, it is inferred that the cobalt ferrite shell provides a better oxidation barrier performance than magnetite in the un-doped case. The hysteresis loops of the oxidized 19 nm samples exhibited a high exchange bias field (H(E)), an enhanced coercivity field (H(C)), and a pronounced vertical shift, thus indicating the presence of a strong exchange bias coupling effect. More importantly, the onset temperature of H(E) was found to be higher than 200 K, which suggests that cobalt doping increases the Néel temperature (T(N)) of the CWT core. In general, the results show that the homogeneous dispersion of Co in iron precursors improves the stability of the final CWT nanoparticles. Moreover, the CoFe2O4 shells formed following oxidation increase the oxidation resistance of the CWT cores and enhance their anisotropy energy.

Nanoribbon-structured organo zinc phosphite polymorphs with white-light photoluminescence.

The first neutral organo zinc phosphites composed of 2.8 nm-wide ribbons were obtained in pure phases and exhibit near-white-light photoluminescence (PL). By using the "mesitylene strategy", interesting polymorphism in the system of NTHU-14 was discovered. The S-shaped ribbons are arranged into R and L arrays, resulting in RLR and RRR stacking for two polymorphs. π-π interactions exist within each array and hydrogen bonding between adjacent arrays. Besides a common ligand-based emission band at 410 nm, the PL curves of polymorphs 14-α and 14-ß are distinctly different: 14-α gave a defect-based emission at 565 nm, whereas 14-ß primarily shows a π-excimer-based emission at 535 nm. Electron paramagnetic resonance (EPR) data disclosed that radical species exist in the reaction and that the two phases were growing from different environments. Based on these results, the origin of the 565 nm band can be ascribed to lattice defects, and one possible cause of 14-ß not showing noticeable yellow emission is identified.