Structural Regulations of Layered Borates: From Centric Layers to Chiral Porous Layers.

Three pentaborates were made by precise structural regulations under hydrothermal conditions, namely, KCs[BO(OH)]·0.5CO (), KNaCs[BO(OH)]·2OH (), and NaBa[BO(OH)] (). Compound features the typical 2D layers constructed from the four-connected BO(OH) clusters.

A sandwiched Co-added polyoxometalate for efficient visible light-driven hydrogen evolution.

A new Co-added polyoxometalate (CoAP) Cs[(Co(HO)){(μ-Co(HO))Co(HO)(B-α-GeWO)}]·6HO (1) has been made using a lacunary directing strategy under hydrothermal conditions. Single-crystal X-ray diffraction analysis demonstrated that 1 is a one-dimensional (1D) chain, in which CoAP is linked by cobalt-oxygen octahedra to form a 1D structure with excellent chemical stability. The visible light-driven H evolution test demonstrated that 1 has high activity, with an H evolution rate of 1485.

Three new aluminoborates: from 1D tube to 3D framework.

Three new aluminoborates (ABOs) KCs[Al{BO(OH)}{BO(OH)} (1), KCs[Al{BO}{BO(OH)}] (2), and Cs[Al{BO}{BO(OH)}] (3) have been made under solvothermal conditions. 1 features a 1D tube constructed by the alternation of [BO(OH)] clusters and AlO units, onto which the [BO(OH)] triangles are grafted. To further construct higher dimensional structures based on the structure 1, solvents were adjusted for high basicity, resulting in the formations of the 3D ABO frameworks 2 and 3.

NaCs[Al{BO}{BO(OH)}]: An Acentric Layered Aluminoborate with Nonlinear-Optical Properties.

An acentric aluminoborate (ABO), NaCs[Al{BO}{BO(OH)}] (), has been made under solvothermal conditions. The alternations of AlO tetrahedra and BO triangles first build up the 2D ABO layer with 6-MR (membered-ring) windows. The fanlike BO(OH) cluster adorns the layer through Al-O-B linkages, producing a pair of unclosed channels with 7-MR aperture on the lateral side of the layers.

Two New Aluminoborates with 3D Porous-Layered Frameworks.

Two new aluminoborates, NaKCs[AlBO(OH)]·HO () and KNa[AlBO(OH)]·5HO (), have been hydro(solvo)thermally made with mixed alkali metal cationic templates. Both and crystallize in the monoclinic space group 2/ and contain similar units of [BO(OH)] cluster and AlO tetrahedra. The [BO(OH)] cluster is composed of three classical BO rings by vertex sharing, of which two of them connect with AlO tetrahedra to constitute monolayers, and one provides an O atom as a bridging unit to link two oppositely orientated monolayers by Al-O bonds to form 3D porous-layered frameworks with 8-MR channels.

Two New Nonaborates with {B} Cluster Open-Frameworks and Short Cutoff Edges.

Two new nonaborates, NaBa[BO]·HO () and NaCa[BO(OH)] (), have been solvothermally made with mixed alkali and alkaline-earth metal cationic templates. and are constructed by two different types of nonaborate clusters. In , the [BO] cluster is composed of three corner-sharing [BO] clusters, of which two of them interconnect to the 1D BO-based chains and are further bridged to the 3D framework with 7 types of 10-MR channels by another [BO] bridging cluster.

Two layered galloborates from centric to acentric structures: syntheses and NLO properties.

Two layered galloborates (GBOs), NaGaBO (1) and NaGa[BO(OH)]·2B(OH) (2), have been solvothermally made. 1 exhibits an unprecedented layer built by GaO tetrahedra and BO clusters. 2 was made by raising the ratio of B/Ga and the reaction temperature of 1, featuring a 2D acentric layer built by GaO groups and BO(OH) clusters.

Designed Syntheses of Three {NiPW}-Based Polyoxometalates, from Isolated Cluster to Cluster-Organic Helical Chain.

Three new hexa-Ni-substituted Keggin-type polyoxometalates (POMs), [Ni(OH)- (DACH)(HO)(PWO)]·31HO (), [Ni(DACH)][Ni(OH)(DACH)(HMIP)(HO)(PWO)]·56 HO (), and [Ni(DACH)][Ni(OH)(DACH)(AP)(HO)(PWO)]·2HO () (DACH = 1,2-Diami- nocyclohexane, MIP = 5-Methylisophthalate, AP = Adipate) were successfully made in the presence of DACH under hydrothermal conditions. is an isolated hexa-Ni-substituted Keggin unit decorated by DACH. In order to further construct POM cluster-organic frameworks (POMCOFs) on the basis of , by analyzing the steric hindrances and orientations of the POM units, the rigid HMIP and flexible AP ligands were successively incorporated, and another anionic monomeric POM and the new 1D POM cluster organic chain (POMCOC) were obtained.

Chiral {NiPW} Cluster-Organic Framework: Synthesis, Structure, and Properties.

A chiral three-dimensional polyoxometalate cluster-organic framework (POMCOF) H[(btc)Ni(μ-OH)(HO)(B-α-PWO)]·17HO (, btc = 1,2,4-benzenetricarboxylate) has been made under hydrothermal conditions in the absence of amine or chiral starting reagents. shows high stability in CHCN/DMF (1:3), acidic, and basic solutions with the pH ranging from 2 to 12 for 5 days. The UV-vis reflectance spectra and Mott-Schottky measurements reveal that could be a suitable catalyst for photocatalysis.

K Na [{B O (OH)}{B O (OH) }] ⋅ H O: A Layered Borate Built by Mixed Oxoboron Clusters with Nonlinear-Optical Property.

A new acentric borate, K Na [{B O (OH)}-{B O (OH) }] ⋅ H O (1) has been made under solvothermal condition. 1 has layered structure made by B O (OH)-based chains and B O (OH) -bridging clusters. Second-harmonic generation (SHG) measurements reveal that 1 is a phase-matchable nonlinear optical (NLO) material, showing the SHG signal intensity of 1.

Three Inorganic-Organic Hybrid Gallo-/Alumino-Borates with Porous-Layered Structures Containing [MBO(OH)] (M = Al/Ga) Cluster Units.

Three inorganic-organic hybrid gallo-/alumino-borates [GaBO(OH)]·Hdah (, dah = 1,6-diaminohexane), K[GaBO(OH)(en)] (, en = ethylenediamine), and K[AlBO(OH)(en)]·HO () were synthesized under solvothermal conditions. Compound features a 3D porous-layered structure built by the alternation of [GaBO(OH)], [BO] clusters and GaO tetrahedra, in which the novel [GaBO(OH)] cluster is first observed. Compounds and are isostructural and made by [MBO(OH)], [BO(en)] clusters and MO tetrahedra (M = Ga/Al); their 3D porous layers are similar to those of and further bridged by en linkers through the rare B-N-C covalent bonds, resulting in the 3D inorganic-organic hybrid framework.

Syntheses and structures of a new 2D layered borate and a novel 3D porous-layered aluminoborate.

Two new layered and porous-layered borates ([Hdap][BO(OH)] (1, dap = 1,2-propanediamine) and [HO]KNa{Al[BO(OH)][BO][BO]}[CO] (2)) have been solvothermally made. 1 features a 2D layer made of the [BO(OH)] cluster, in which Hdap is located in the windows of the layers. The fundamental building block (FBB) [BO(OH)] cluster in 1 represents a new type of FBB of the hepta-borate family.