As an important optoelectronic and energy-storage material, porous silicon (PSi) has attracted great interest in various fields. The preparation of PSi, however, usually suffers from low yields and/or complicated syntheses. Herein, we report a facile solution method to prepare PSi with controllable high specific surface area. Commercial Zintl compound Mg2Si readily reacts with HSiCl3 in the presence of amines at room temperature to produce amorphous PSi in high yields, where in situ formed salt byproducts serve as templates to generate uniform mesopores of ca. 3.8 nm in diameter. After crystallization treatment at 700 °C in flow Ar gas for 40 min, the obtained crystalline PSi coated with carbon layers shows excellent electrochemical performance when served as lithium ion battery anodes. The reversible specific capacity is about 2250 mA h g–1 at 0.1 A g–1 and the capacity retention is maintained at 90% after cycling at high current density of 2 A g–1 for 320 times. This simple, facile preparation method is very promising and paves the way for massive production of porous Si as high-performance anodes in Li-ion battery industry or for other applications, such as drug delivery systems and catalysis.Keywords: anode material; lithium ion battery; mesoporous structure; porous silicon; solution method; synthesis design;

The preparation of highly active, sustainable, nonprecious metal materials as hydrogen evolution and oxygen evolution reaction (HER and OER) catalysts that can relieve the environmental pollution and energy shortage problems present a great challenge to chemists. We herein report the fabrication of a highly active metal phosphide–carbon composite catalyst for HER and OER in acid and basic solution, respectively. The catalyst is derived through carbonization and subsequent phosphorization of two-dimensional (2D) cobalt porphyrinic metal-organic framework nanosheets. It consists of cobalt phosphide nanoparticles embedded in mesoporous N-doped graphitic carbon materials. The catalyst shows good electrocatalytic activities for HER in 0.5 M H2SO4 and OER in 1 M KOH with overpotentials of 98 and 370 mV at a current density of 10 mA cm–2 and the Tafel slopes of 74 and 79 mV dec–1, respectively. In addition, the catalyst also shows good durability. The method used in this study could be applied to prepare new, highly efficient water-splitting catalysts by using diverse 2D metal-organic frameworks as templates.Keywords: cobalt phosphide; hydrogen evolution reaction; nanoparticles; oxygen evolution reaction; two-dimensional metal-organic frameworks;

AbstractAn operationally green, electron-catalyzed, photochemical tandem carbodifluoroalkylation/radical cyclization of enol ethers is disclosed. The reactions occur via addition of difluoroacyl radicals to methylene-2-oxazolines and subsequent intramolecular base-promoted homolytic alkyl substitution (BHAS) of the intermediate oxyl-alkyl radicals. Initiation of the radical chain reaction is best achieved with a commercially available and cheap organic base, and readily accessible visible light is used as the energy source.

Core–shell structured Si-mesoporous TiO2 (Si@mTiO2) composite nanospheres are designed and prepared via a step-by-step assembly method. Si@mTiO2 exhibit excellent lithium-storage properties when used as anode materials in lithium ion batteries. The reversible specific capacity is maintained at as high as 700 mA h g−1 with no capacity decay even after 200 cycles at 1 A g−1.

Ultra-thin SiOx (0 < x < 2) nanosheets were obtained via a convenient solvothermal route from a Zintl compound CaSi2. After carbon coating, the SiOx@C nanosheet anodes exhibit high capacity, good rate and superior cycling performance for high-capacity lithium ion battery applications. The specific capacity can be maintained as high as 760 mA h g−1 with almost no capacity decay after 400 cycles at a current density of 0.5 A g−1.

Nanostructured silicon has attracted a great deal of attention as an excellent anode material for Li ion batteries (LIBs). However, the use of Si nanomaterials in LIBs is severely hindered by their preparative methods owing to the high cost, low yield, and harsh synthetic conditions. Herein, we report a new method for the synthesis of uniform Si nanocrystals based on the magnesiothermic reduction of natural attapulgite clay. The obtained Si nanocrystals with a uniform size of ca. 10 nm are coated with polypyrrole (denoted ppy@Si) and show excellent electrochemical performance as anode materials for LIBs. After charging–discharging for 200 cycles at a current density of 0.6 A g−1, the specific capacity value of the ppy@Si anode is ∼954 mA h g−1. Because of the abundance of attapulgite, the obtained silicon nanoparticles can be exploited as a practical anode material for high-performance Li-ion batteries.

A new UiO-67-type zirconium metal organic framework (MOF) material UiO-67-bpy-Me (bpy = 2,2-bipyridine-4,4′-dicarboxylic acid, Me = methyl) was prepared by N-quaternization of the pyridine sites in UiO-67-bpy. After N-quaternization, the pristine neutral framework turned cationic while its high thermal and chemical stabilities were primarily preserved. Fast and enhanced anionic dye adsorption was observed in UiO-67-bpy-Me. In addition, despite the decrease in surface area and pore volume, UiO-67-bpy-Me exhibited an evident increase in CO2 uptake compared to UiO-67-bpy. The enhancement was ascribed to the strong interactions between CO2 and the N-quaternized framework. More importantly, as the N-quaternization has changed the electronic structure of the organic linker. UiO-67-bpy-Me showed optical absorption up to ca. 800 nm with a large red shift of 450 nm compared to the pristine UiO-67-bpy (ca. 350 nm). The extended optical absorption may lead to more efficiency in light utilization. A proof-of-concept demonstration showed that UiO-67-bpy-Me could more efficiently catalyze methyl-orange degradation under UV-Vis light irradiation than the pristine UiO-67-bpy. These findings demonstrate that N-quaternization could serve as a facile post-synthetic modification method to tune the chemical/physical properties of free pyridyl-containing MOFs.

Hollow-structured Si/SiC@C nanospheres were prepared through a magnesiothermic reduction of resin-coated SiO2 spheres. These nanostructured materials with high surface area not only show high adsorption capacities of industrial dyes from wastewater, but also exhibit excellent catalytic activities for chemical fixation of CO2 under mild, solvent-free conditions.

The chiral germanosilicate zeolite ITQ-37 was prepared using a readily-obtained, semi-rigid achiral organic structure-directing agent (SDA) 1,1′,1′′-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)tris-(3-methyl-1H-imidazol-3-ium) (denoted tmbi). The synthetic factors, including crystallization temperature, water content, germanium and tmbi concentrations for the crystallization of ITQ-37, were studied by means of single crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, liquid and 13C/19F/29Si solid NMR and photoluminescence spectroscopy. The results showed that high Ge content, high tmbi concentration and low temperature (150 °C) conditions favor the formation of extra-large pore ITQ-37 when supramolecular interactions between tmbi molecules occur. On the other hand, a much diluted tmbi solution and a higher reaction temperature favor the crystallization of an unknown lamellar phase, wherein tmbi is present as monomers. These studies revealed that supramolecular assemblies of tmbi were formed during the zeolite synthesis and acted as SDAs for crystallization of ITQ-37, providing a general and applicable strategy for synthesizing large and extra-large pore zeolites.

The yolk–shell structured Si/SiC@C (YSSC) nanospheres were prepared by a facile magnesiothermic reduction process. After coating with TiO2 nanoparticles, the YSSC@TiO2 composites possess a Brunauer–Emmett–Teller (BET) and Langmuir surface area of 423 and 584 m2 g−1, respectively, and show high adsorption capability for methyl blue (MB) and Congo red in water. Moreover, the nanocomposites show a strong photon absorbance throughout the visible light region, and exhibit excellent photocatalytic performance for degrading MB in water. The MB degradation follows the pseudo 1st order kinetics and the calculated rate constant for YSSC@TiO2 under UV (visible) light irradiation is approximately 4.5 (7.9), 8 (17), and 7.6 (22.7) times larger than that of the synthesized TiO2, commercial P25 and YSSC spheres, respectively. Stability tests show that the YSSC@TiO2 nanospheres possess high stability and maintain good photocatalytic activity over four runs of cycle experiments. The excellent photocatalytic activity of YSSC@TiO2 can be ascribed to the synergism of high adsorption of dye molecules on the surface, extended light adsorption range and the formation of semiconductor heterostructures that allow for efficient separation of photogenerated electrons and holes through a Z-scheme system within the catalyst.

•A new UiO-66-type metal–organic framework UiO-66(AN) with anthracene-9,10-dicarboxylic acid as linker•UiO-66(AN) has good thermal and chemical stability.•UiO-66(AN) shows an intense absorption band in the visible light region.•UiO-66(AN) is an efficient photocatalyst for degradation of methyl orange.A new UiO-66-type zirconium metal organic framework material UiO-66(AN) was prepared by using chromophoric anthracene-9,10-dicarboxylic acid as linker. The large-sized conjugate π-system in the ligand results in the bathochromic shift of the absorption peaks into the visible light region in the absorption spectrum of UiO-66(AN), compared to those of UiO-66 and analogs UiO-66(NA) made of terephthalate and naphthalene-1,4-dicarboxylic acid, respectively. UiO-66(AN) was shown to be an efficient photocatalyst for degradation of methyl orange. Our finding shows promises for the development of more efficient MOFs as photocatalysts by using chromophoric conjugate ligands.A new UiO-66-type metal–organic framework UiO-66(AN) was synthesized by using anthracene-9,10-dicarboxylic acid as linker, which showed enhanced photocatalytic activity for degradation of methyl orange in comparison with the UiO-66 and analogs UiO-66(NA) made of terephthalate and naphthalene-1,4-dicarboxylic acid, respectively.

By using the octadentate ligand tetrakis[(3,5-dicarboxyphenoxy)methyl] methane (H8L), a rare (4,8)-scu type microporous coordination polymer, [In2L][NH2(CH3)2]2·(DMF)4(H2O)16, was synthesized and structurally characterized. The compound possesses an anionic three-dimensional open framework and exhibits permanent porosity with selective gas adsorption of CO2 over CH4. It exhibited strong fluorescence emission upon excitation at RT, and a selective, efficient emission quenching response towards nitroaromatic explosives.

By using a semi-rigid multidentate carboxylate linker 4,4′,4′′-(((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(oxy))tribenzoic acid (H3L), four coordination polymers, namely, [Cd3(L)2(H2O)4]·(guest) (1), [Mn3(L)2(DMF)2(H2O)2]·(guest) (2), [Co7(L)4(DMF)6(COOH)2]·(guest) (3), and [Zn3(L)2(DMF)2(H2O)3]·(guest) (4), were obtained and characterized by single-crystal X-ray diffraction, thermogravimetric and photoluminescent studies. Compound 1 is a two-dimensional (2-D) hcb-type layered structure made of rare, interlocked double-layered honeycomb sheets. Compound 2 is a doubly-interpenetrating (3,6)-connected 3-D network, in which L and Mn3 act as triangle and trigonal prismatic nodes, respectively. Compound 3 has a (4,12)-connecting 3-D polycatenated network made of a rare four-ladder 2-D sheet, in which the Co7 cluster is considered as a 12-connecting node and the ligand L3− is a 3-connecting node. Similar to 1, compound 4 also possesses a 2-D hcb-type layered structure, but it is built from two interpenetrating single sheets. Compounds 1 and 4 exhibited strong blue photoluminescent emissions at room temperature upon excitation, owing to a ligand-centered excited state. The emission intensities of the two compounds varied upon contact with different solvents or analytes, exhibiting selective emission quenching responses towards nitroaromatics.

Two new metal–organic open frameworks (MOFs) [Zn3L2(btc)2(H2O)]·(guests) (1), [CdL(bdc)]·(guests) (2), were successfully prepared by using a photoluminescent BODIPY-based bipyridine linker, L, and auxiliary ligands 1,4-benzenedicarboxylate (H2bdc) and 1,3,5-benzenetricarboxylate (H3btc), respectively. MOF 1 has a 2-fold interpenetrating three-dimensional (3D) framework with an 8-connecting body centered cubic (bcu) net, built upon a paddlewheel cluster [Zn2(O2CR)4], a tetrahedrally connecting Zn and a 3-connected btc3− ligand. MOF 2 has a highly open framework with a kagome-type net. It is a pillared layered structure made of 2D [Cd(bdc)] kagome sheets and L as pillars. MOF 1 was shown to exhibit permanent porosity and adsorption of N2, H2, CO2 and CH4. Both MOFs exhibited strong photoluminescent emissions at room temperature with peaks at 540 nm upon excitation, owing to a ligand L-based excited state.

Three microporous coordination polymers, namely, [Co2L(DPE)]·2DMF·5H2O (1), [Zn2L(DPE)]·2.5DMF·2H2O (2) and [Cd(H2L)]·3DMF·3.5H2O (3), were solvothermally prepared in the presence of the flexible tetrahedral carboxylate ligand tetrakis[(4-carboxyphenyl)oxamethyl]methane acid (H4L) and a secondary bidentate linker (E)-1,2-di(pyridin-4-yl)ethane (DPE). Compounds 1 and 2 are isostructural and possess a 2-fold interpenetrating (4,4)-pts network. Compound 3 has a 3D structure with a uninodal 4-connected {4.85} topology. All the three compounds consist of large solvent-accessible voids, but only compounds 1 and 2 possess permanent porosity as confirmed by N2, CO2 and CH4 gas adsorption measurements. In addition, compounds 2 and 3 exhibited strong photoluminescent emissions at room temperature with a peak at 495 and 440 nm, respectively, owing to a ligand-centered excited state. The emission intensities of 2 varied upon contact with different solvents or analytes.

Two manganese sulfates, [C2H6O2][MnSO4] (1) and [C4N2H12][Mn(SO4)2(H2O)] (2), were solvothermally synthesized in the presence of ethylene glycol and piperazine. Both compounds are constructed from 4-membered ring ladder chains made of MnO6 and SO4 units, with 1 displaying a 3D zeolite gismondine (GIS) framework and 2 possessing a 1D chain structure, respectively.

By using a rigid tetrapodal linker 4,4′,4′′,4′′′-silanetetrayltetrabenzoic acid (H4L) and lanthanide metal ions, three new coordination polymers, namely, [NdL(H2O)][NH2(CH3)2]·(DMF)x·(H2O)y (x ≈ 2, y ≈ 4) (1), [Eu4L3(H2O)6]·(DMF)y·(H2O)x (x ≈ 2, y ≈ 4) (2) and [Er4L3(H2O)6]·(DMF)x·(H2O)z (x ≈ 2, z ≈ 5) (3), were solvothermally synthesized and structurally characterized. Compound 1 is a 3D framework with a (4,8)-connected flu structure, built from distorted cuboid dinuclear neodymium–carboxylate building block and a 4-connected tetrahedral L ligand. Compounds 2 and 3 are isostructural, possessing a non-interpenetrated three-dimensional network with rare (4,4,12) highly-connected topology. In compounds 2 and 3, the fully deprotonated L4− ligands act as pseudotetrahedral 4-connecting nodes and S-shaped tetranuclear lanthanide metal–carboxylate building blocks act as 12-connecting nodes. Compound 1 possesses permanent porosity as confirmed by N2, H2, O2, CO2 and CH4 gas adsorption measurements.

•Two pyridine-substituted BODIPY dyes were prepared via Suzuki coupling reactions;•Two dyes are fluorescent with high quantum yields and little solvent dependence;•Two dyes show highly selective Cu+ sensing properties.Two new pyridine-substituted boron-dipyrromethene (BODIPY) dyes have been synthesized via the Suzuki coupling reactions of 2,6-diiodo-1,3,5,7-tetramethyl-8-methyl-4,4-difluoroboradiazaindacene and respective pyridinylboronic acid. The molecular structures of the two title compounds have been determined by single-crystal X-ray diffraction analyses. The absorption and steady-state fluorescent properties in different solvents were investigated, which showed that the two compounds are highly fluorescent with a relatively small Stokes shift, high fluorescent quantum yields and little solvent dependence, similar to other BODIPY chromophores. The fluorescence of two compounds were highly sensitive towards Cu+, owing to significant interactions between Cu+ and the nitrogen atoms on the pyridine rings.Two fluorescent pyridine-substituted boron-dipyrromethene (BODIPY) dyes were prepared and shown to be highly selective towards Cu+.

By using an octadentate ligand tetrakis[(3,5-dicarboxyphenoxy)methyl] methane (H8L), a new microporous metal–organic framework [Cu4L(H2O)4](H2O)31 (1) was solvothermally synthesized and structurally characterized. MOF 1 is built from the 4-connected square planar [Cu2(O2CR)4] cluster and 8-connected cube ligand L to have a highly open framework with scu topology. It possesses permanent porosity as confirmed by N2, H2, C2H2, CO2 and CH4 gas adsorption measurements and exhibits high acetylene storage of 193 and 154 cm3 g−1 at 273 and 296 K under 1 atm, respectively.

Nanostructured silicon hollow spheres with a thin shell have been synthesized by magnesium reduction of silica spheres, which possess a high BET surface area and are electrochemically active in capacitive energy storage with a maximum specific capacitance of 193 F g−1 in the neutral Na2SO4 aqueous solution.

By using a rigid octadentenate carboxylate linker 5,5′,5″,5″′-silanetetrayltetraisophthalic acid (H8L), three new microporous coordination polymers, namely, [Cu4L(H2O)4]·2DMF·10H2O (1), [Zn5L2(H2O)4][NH2(CH3)2]6·2DMF·4H2O (2), and [Cd3(H2L)2][NH2(CH3)2]6·4DMF·14H2O (3), were solvothermally synthesized and structurally characterized. Compound 1 is a 3D framework built from a square paddlewheel [Cu2(O2CR)4] and a 8-connected cube L ligand to give a (4,8)-connected scu structure. Compound 2 is a 3D 4-nodal (4,4,4,8)-connected network with small 1D channels built on three tetrahedral Zn units and a 8-connecting ligand L. Compound 3 possesses a 3D structure with a (4,4,6)-connected net built on two tetrahedral Cd units and a 6-connecting ligand H2L6–. All the three compounds consist of large solvent accessible voids, but only compound 1 possesses permanent porosity as confirmed by N2, H2, O2, CO2 and CH4 gas adsorption measurements. Compounds 2 and 3 exhibited strong blue fluorescent emissions with a peak at 414 and 412 nm, respectively, at RT upon excitation owing to a ligand-centered excited state.

By using a flexible multidentate carboxylate linker 4,4′,4′′-(((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(oxy))tribenzoic acid (H3L), four novel coordination polymers [Mn7L4(DMF)4(H2O)4Cl2]·10(H2O) (1), [Cd7L4(DMF)4(H2O)4Cl2]·10(H2O) (2), [Co7L4(DMF)4(H2O)4(OH)2]·11(H2O) (3), and [Co4L2(DMF)2(H2O)4Cl2]·4(DMF)·3(H2O) (4) were obtained and characterized by single-crystal X-ray diffraction, thermogravimetric and magnetic studies. Compounds 1–3 are isomorphous, built upon a 12-connecting linear M7 cluster and a 3-connecting L3− ligand to form a polycatenated 3D network. 4 comprises of 3-connecting trigonal M2 clusters and L3− linkers to form a 2D layered structure with hcb topology. The magnetic studies of the M7-cluster compounds 1 and 3 show the presence of antiferromagnetic interactions between the M2+ ions in 1 and 3.

By using a semi-rigid tetracarboxylate ligand 5,5′-(1,4-phenylenebis(methylene))bis(oxy)diisophthalic acid (H4L), three novel coordination polymers were synthesized solvothermally and characterized by single-crystal X-ray diffraction, thermogravimetric, photoluminescent and gas adsorption studies. Compound [Zn(H2L)(H2O)2] (1) is a two-dimensional (2D) network with sql/Shubnikov topology built from the 4-connecting Zn2(OOC)2 cluster and bridging ligand H2L2−. Compound [Co2(H3L)2(H2L)(H2O)2]·5H2O (2) is a one-dimensional (1D) zigzag chain-like polymer made of 2-connecting ligand H2L2− and Co2O6(H2O)4 clusters, which form a 3D network through hydrogen bonding interactions. [Cd3(L)2]·(H3O)2(H2O)(DMF)4 (3) possesses a rare (4,8)-connected flu (CaF2) net built from 8-connecting Cd3 clusters and 4-connecting L ligands. In three complexes, the ligand H4L exhibits diverse coordination configurations and modes owing to its flexibility. Upon excitation at room temperature, complexes 1 and 3 exhibit strong violet and blue emissions, respectively. N2 gas adsorption measurements at 77 K showed that compound 3 possesses permanent porosities.

By using flexible tricarboxylate 4,4′,4″-(((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(oxy))tribenzoic acid (H3L) and multiimidazole 1,3,5-tri(imidazo-1-ylmethyl)-2,4,6-trimethylbenzene (titb) ligands simultaneously, three novel coordination polymers [M3L2(titb)2]·2H2O·2.5DMF (M = Co,1; Zn, 2; Cd, 3) were synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, thermogravimetric and photoluminescent studies. The three compounds are isomorphous and possess a three-dimensional (3D) framework built from 2D sheets of L3− ligands and M ions, and 1D chains of titb ligands and M ions. Topological analyses showed that they exhibit a novel (3,3,4,4) four-nodal 3D net constructed from two 4-connecting metal, and two 3-connecting L3− and titb nodes. Compounds 2 and 3 are photoluminescent upon excitation at room temperature.Graphical abstractThree unprecedented coordination polymers [M3L2(titb)2]·(solvent)x (M = Co, 1; Zn, 2; Cd, 3) were synthesized under solvothermal conditions by using two flexible tripod multicarboxylate H3L and multiimidazole titb ligands.Highlights► Three unprecedented coordination polymers based on two flexible tripod ligands. ► They are isomorphous and possess a three-dimensional (3D) framework. ► They exhibit a novel (3,3,4,4) four-nodal 3D net. ► Compounds 2 and 3 are photoluminescent upon excitation at room temperature.

Three indium phosphates [In16(HPO4)28(H2O)12](NH4)8(H2O)12 (1), [In2(OH)(HPO4)2(PO4)](H2O)(C6H18N2) (2) and [In3(HPO4)6](C2N2H10)(H3O)(H2O)2 (3) were solvothermally synthesized from water/ethylene glycol (EG) mixed solvent systems by using 1,3-propyldiamine (1,3-PDA), 2-methyl-pentamethylenediamine (MPMD) and diethylenetriamine (DETA) as structure directing agents (SDAs), respectively. Compound 1 consists of anionic layers of [In7(HPO4)14(H2O)6]7−, which are connected by InO6 octahedra to form an anionic three-dimensional (3-D) open framework with intersecting 12-membered rings channels. The channels are filled with charge-balancing ammonium cations and guest water molecules. Compound 2 possesses a 2-D layered structure consisting of anionic layers of [In2(OH)(HPO4)2(PO4)]2– formed by InO6 octahedra and PO4 tetrahedra, in which the protonated MPMD and water molecules lie between the layers. Compound 3 is constructed from a [3.3.3] propellane-like building unit made of strict alternation of InO6 octahedra and PO4H tetradedra, forming a 3-D open framework with intersecting 8- and 12-membered ring channels. The protonated water and ethylenediamine derived from the decomposition of DETA during the synthesis are located within the channels. The three compounds were characterized by powder X-ray diffraction (PXRD), single crystal X-ray diffraction, Fourier-transformed infrared (FT-IR) spectra, thermogravimetric analysis (TGA), inductively coupled plasma-atomic emission spectroscope (ICP-AES) and elemental analyses.Graphical abstractThree new indium phosphates were solvothermally prepared from the mixed water–ethylene glycol solvent systems by using different amines as structure directing agents under otherwise same conditions, which possess a 3-D pillared layer, a 2-D sheet and a 3-D framework of pcu topology, respectively.Highlights► Three indium phosphates solvothermally obtained from the water/ethylene glycol mixed solvent systems. ► Compound 1 is a 3-D open framework with intersecting 12-membered rings channels. ► Compound 2 possesses a 2-D layered anionic structure. ► Compound 3 is a 3-D open framework of pcu topology with intersecting 8- and 12-membered ring channels.

By using a semirigid quadricarboxylate ligand 5,5′-(biphenyl-4,4′-diylbis(methylene))bis(oxy)diisophthalic acid (H4L), four novel coordination polymers were obtained solvothermally and characterized by single-crystal X-ray diffraction, thermogravimetric, photoluminescent and gas adsorption studies. Compound [Zn2(L)]·CH3CN, 1, is a three-dimensional (3D) framework built from one-dimensional (1D) rod-shaped Zn–O–C secondary building units (SBUs) that are linked together by the 4-connecting L ligands to give rod packing of pcu type and elliptical channels of 7.7 × 8.4 Å2. Compound [Zn4(L)2(H2O)4]·5H2O, 2, possesses a 3D open framework with a doubly interpenetrated sra net built from 4-connecting Zn2(OOC)4 unit and L ligand. Compound [Mn2(L)(H2O)2]·2H2O, 3, is built from trigonal–bipyramidal binuclear Mn2(OOC)3 units and octadentate L ligands, forming a binodal 5,5-connected 43.66.8 net. Compound [Mn(H2L)(DMA)(H2O)]·(DMA)(H2O), 4, is a two-dimensional (2D) layered structure made of 4-connecting mononuclear Mn atoms and half-deprotonated L ligands. N2 gas adsorption measurements at 77 K showed that compounds 1, 2, and 4 possess permanent porosities.

A new microporous coordination polymer [Cd4(L)2(BDC)4]·(DMF)3(H2O) (L = 1,1′,1′′-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)tripyridinium-4-olate, BDC = benzene-1,4-dicarboxylic acid) was synthesized, which possesses a (3,7)-connected framework with rectangular tubular open channels, and exhibits permanent porosity and strong photoluminescence with solvatochromic behavior upon excitation.

By using bidentate thioether linkers 1,4-bis(ethylthio)benzene (L1) and 4,4′-bis(ethylthiomethyl)biphenyl (L2), four novel coordination polymers (CuI)x(L)y·z(solvent), MSF–n (metal-sulfide-framework, MSF–6, x = y = 2, L = L1; MSF–7, x = 4, y = 2, L = L1; MSF–8, x = y = 2, L = L2; MSF–9, x = 4, y = 1.5, L = L2) were obtained and characterized by single-crystal X-ray diffraction, thermogravimetric, solid state diffuse reflectance UV-Vis and photoluminescent studies. MSF–n (n = 6–9) possess 2D layered structures built from (CuI)x clusters and linear thioether linkers, the formations of which are dependent on the cluster size and linker length. MSF–6 and MSF–8 possess the same structure topology, consisting of lozenge-shaped sql single sheets of 4-connecting Cu2I2 units and linear thioether linkers L1 and L2, respectively. MSF–7 and –9 are cubane cluster Cu4I4-based layered compounds, composed of 2-fold interpenetrating sql and 3-fold interpenetrating hcb sheets, respectively. The solid state diffuse reflectance UV-Vis spectra show that MSF–6 to –9 are wide-gap semiconductors with band gaps of 3.11, 3.25, 3.52 and 3.07 eV, respectively. MSF–7 and –9 are photoluminescent at room temperature owing to the existence of the Cu⋯Cu interactions within the Cu4I4 cluster, while MSF–6 and –8 do not emit upon excitation because of luminescence quenching.

An unprecedented three-dimensional (3D) coordination polymer [Cu4(CN)4(tpom)]n (tpom = tetrakis(4-pyridyloxymethylene)methane) (1) was solvothermally prepared and characterized by single-crystal X-ray diffraction, IR, TGA, adsorption and photoluminescent studies. Compound 1 is constructed from a 1D CuCN chain and a tetrahedral ligand tpom, in which the CN ligand was in situ generated by the C―C bond cleavage of acetonitrile molecule under solvothermal conditions. Compound 1 possesses a three-fold interpenetrating framework with ths-z type of rod packing topology. It exhibits relatively high thermal stability up to 330 °C and weak photoluminescent emissions at room temperature. The gas absorption studies revealed that 1 can selectively adsorb 0.8 wt% H2 at 77 K and 1 atmospheric pressure.A triply-interpenetrating microporous coordination polymer was prepared by in situ generation of CN from acetonitrile, which is built on a CuCN chain and tetrahedral tpom ligand, and exhibits weak photoluminescent emissions at RT.Highlights► An unprecedented triply-interpenetrating 3D coordination polymer [Cu4(CN)4(tpom)]n with ths-z topology. ► It was formed by in situ generation of CN from acetonitrile. ► It exhibits relatively high thermal stability and weak photoluminescent emissions at RT. ► It selectively adsorbs 0.8 wt% H2 at 77 K and 1 atm.

A triply-interpenetrating diamondoid coordination polymer [Cu4(SCN)4(tpom)]·2H2O (1, tpom = tetrakis(4-pyridyloxymethylene)methane) was prepared, which is built from an unprecedented pseudohalide cubane cluster Cu4(SCN)4 and tetrahedral tpom ligand. 1 exhibits high thermal stability and temperature-dependent photoluminescence behaviors resembling those of Cu4Cl4 complexes.A triply-interpenetrating diamondoid coordination polymer was prepared, which is built on an unprecedented pseudohalide cubane cluster Cu4(SCN)4 and exhibits temperature-dependent photoluminescence behaviors resembling those of Cu4Cl4 complexes.Research Highlights► The first structurally characterized compound with a pseudohalide cluster Cu4(SCN)4. ► A coordination polymer with a three-fold interpenetrated diamond net. ► A rigid open framework that just allows H2 to pass through. ► Its temperature-dependent photoluminescence resembles those of Cu4Cl4 complexes.

Four novel porous metal sulfide coordination polymers, [M(tpom)Sx(SH)y]·z(H2O) (metal-sulfide frameworks, denoted MSF-n, n = 1, Cd; 2, Mn; 3, Fe; 4, Co; x = 0, y = 2 for 1, 2, and 4 and x = 0.54, y = 1.46 for 3), were solvothermally prepared by using a quadridentate linker, tetrakis(4-pyridyloxymethylene)methane (tpom), in the presence of organic sulfur compound under an acidic conditions. MSF-n (n = 1−4) is isostructural and built upon the tetrahedral tpom linker and square planar MSx(SH)y unit, which form a binodal 4,4-connected porous framework with a 2-fold interpenetrated 4284-pts net. With rectangular pore channels of about 5 × 6 Å2 (interatomic distances between the nearest protruding H atoms across) running along both the crystallographic a and b directions, MSF-n possesses permanent porosity with a BET surface area of 575, 622, 617, and 767 m2/g for MSF-1, -2, -3, and -4, respectively, as estimated from N2 adsorption measurements. MSF-n (n = 1−4) has hydrogen storage capacities of 1.03, 1.37, 1.29, and 1.58 wt % at 77 K and 1 atm, respectively, each corresponding to 2.0 H2 molecules per unit cell. In addition, MSF-n (n = 1−4) can adsorb 24.1, 25.0, 21.6, and 24.1 wt % of carbon dioxide and 6.0, 6.1, 5.6, and 6.4 wt % of methane, respectively, at room temperature and 20 atm.

Two new homochiral metal−organic coordination polymers, M2(TPOM)(d-Cam)2(H2O)2 (M = Zn for 1, Cd for 2, d-H2cam = d-camphoric acid, TPOM = tetrakis(4-pyridyloxymethylene)methane) have been prepared under solvothermal conditions and characterized by single crystal X-ray structure analyses, thermogravimetric analyses, circular dichroism, second-order nonlinear optical (NLO), and photoluminescent measurements. Compounds 1 and 2 are isostructural and crystallize in the chiral space group P21212 (No. 18). In 1, Zn(II) is tetrahedrally coordinated, while Cd(II) in 2 is six-coordinated. Both possess a three-dimensional (3D) framework with a 4-connected node. Tetrahedral quadridentate linker TPOM connects four M(II) ions through its four peripheral pyridyl groups to form a wavelike two-dimensional (2D) sheet [M2(TPOM)]n. The chiral bidentate d-H2cam ligand connects two M(II) ions to form a homochiral left-handed one-dimensional helical chain [M(d-cam)]n. The homochiral helical chains interweave the 2D wavelike sheets via sharing the metal sites to form a 3D homochiral framework with 2-fold interpenetrating quartz (6482) topology. Both 1 and 2 are NLO-active materials and exhibit relatively high thermal stabilities.

The assemblies of tetrahedral linker tetrakis[4-(carboxyphenyl)oxamethyl]methane acid (H4L) with ZnCl2 and CdBr2 yield two noncentrosymmetric, NLO-active coordination polymers [Zn4(L2)(H2O)3(DMA)]·2H2O (1) and [Cd2L(DMA)2(H2O)2] (2), respectively. 1 has an unprecedented 2-fold interpenetrating sxa topology with ferroelectric properties, while 2 has a 7-fold interpenetrating dia network.

The assembly of a semi-rigid tetrahedral linker tetrakis[4-(carboxyphenyl)oxamethyl]methane acid (H4X) with CuII yields a binodal 4,4-connected coordination framework of distorted PtS topology, which exhibits permanent porosity confirmed by gas adsorption experiments of N2, H2, CO2, and CH4.

An unprecedented 4-connected metal–organic framework [Zn2(tpom)(bdc)2]·2H2O (tpom = tetrakis(4-pyridyloxymethylene)methane, bdc = benzene-1,4-dicarboxylic acid) with a binodal 6284 net has been solvothermally synthesized from the assembly of a semirigid tetrahedral ligand (tpom) and a rigid linear bidentate ligand (bdc). The network of 1 is constructed by tetrahedrally connected tpom ligands and metal sites, in which 1D chains [Zn(bdc)]n interweave 2D diamondlike sheets [Zn2(tpom)]n into a 3D porous framework with a binodal 6284 net. 1 has a relatively high thermal stability and exhibits permanent porosity.

Using Zn(SPhMe-4)2 as precursor, a new thermostable zinc sulfide superlattice [Zn10(μ3-S)4(SPhMe-4)12(DMF)4] (1), was synthesized through diffusion method at room temperature. Compound 1 is built upon a neutral T3 supertetrahedral [Zn10(μ3-S)4(SPhMe-4)12(DMF)4] cluster, which is assembled through weak interactions into a 3-dimensional body-centered cubic superlattice that is chemically stable and free of strong covalent coupling. The four DMF group were located at the tetrahedron corners of the T3 cluster in such a manner that both the local charge balance and global charge compensation could be satisfied. The UV–Vis diffuse reflectance spectrum shows that 1 is a wide-gap semiconductor with the band gap of 2.99 eV.A thermostable semiconducting zinc sulfide superlattice was synthesized through diffusion method at room temperature, which is built upon a neutral T3 supertetrahedral [Zn10(μ3-S)4(SPhMe-4)12(DMF)4] cluster and possesses a three-dimensional body-centered cubic superlattice.

A new two-dimensional layered cadmium sulfide framework MSF-5 based on a capped-supertetrahedral C1 cluster [Cd17S4(SPhMe-4)27(SH)]2− has been synthesized. MSF-5 possesses a 3-connected 63–hcb net, in which each C1 cluster connects through Cd–S(PhMe-4)–Cd covalent bonds with three neighboring clusters to form a 2D superlattice with 6-membered rings. The 2D sheets stack over each other to form a 3D network. MSF-5 has high thermal stability and is a wide-gap semiconductor.A new two-dimensional layered cadmium sulfide framework MSF-5 based on a capped-supertetrahedral C1 cluster [Cd17S4(SPhMe-4)27(SH)]2− has been synthesized, which has high thermal stability and is a wide-gap semiconductor.

A new, triply-interpenetrating diamondoid metal–organic framework, which exhibits strong photoluminescence at room temperature and high thermal stability, was prepared by the self-assembly of tetrahedral quadridentate linker tetrakis(4-pyridyloxymethylene)methane and tetrahedral Cu4I4clusters under solvothermal conditions.

A novel, single-walled coordination nanotube [CuSCN(L)]·(DMF)0.5 (L = 1,3-di(pyridin-4-yl)propane, DMF = N,N-dimethylformamide) was easily prepared using two bidentate ligands and characterized by single crystal X-ray diffraction, which shows guest exchange properties and strong photoluminescence at room temperature.

A novel single-stranded helix coordination polymer [Cu(L)(SO4)(H2O)] (L = dihydroglyoxaline sulfide) was synthesized and characterized by single-crystal X-ray diffraction, IR, and TGA analysis. The polymer is an unprecedented 1D helical polymer based on a sulfate bridge and a dihydroglyoxaline sulfide chelating ligand. Both ligands were formed in situ through copper-mediated oxidation of 1,3-imidazolidine-2-thione. The helical chain is interlocked with each other through strong hydrogen bonding interactions to form a 2D sheet, which then stacks together to generate a 3D hydrogen bonding network.

A novel open-framework material [Cu(H2O)2(OH)]2Ge(PO4)2, which was synthesized by a hydrothermal method, is built of GeO6, CuO6 octahedra and PO4 tetrahedra, and possesses a network of interconnecting six- and eight-membered ring channels.

Novel 3d–3d heterometallic metal-organic frameworks, [M(ox)(bipy)] (1, M = Co and Zn; 2, M = Co and Cd; ox = oxalate, bipy = 4,4-bipyridine), have been synthesized by using two bidentate ligands under hydrothermal conditions. The Co(II) and Zn(II) ions in 1, and Co(II) and Cd(II) in 2 are location disordered, with a molar ratio of 0.72:0.28, and 0.96:0.04, respectively. The co-existence of the two metal ions in the structures makes them more thermally stable than previously reported homometallic polymers of Co(II) or Zn(II) ions. Compound 1 exhibits weaker antiferromagnetism than the pure Co(II) complex owing to the incorporation of Zn(II).By using two bidentate ligands, 3d–3d mixed heterometallic coordination polymer [M(ox)(bipy)] (1, M = Co0.72Zn0.28; 2, M = Co0.96Cd0.04; ox = oxalate, bipy = 4,4-bipyridine) have been obtained under hydrothermal conditions. Both process a rare two-dimensional rectangular grid framework with undistinguished heterometallic sites. The co-existence of two metal ions makes them exhibit interesting thermal and magnetic properties in comparison with monometallic organic framework of same structural topology.

A new three-dimensional (3D) framework cadmium germanium phosphate, CdGe(OH)3PO4 was synthesized by solvothermal methods. The crystal structure of CdGe(OH)3PO4 was established by single-crystal X-ray diffraction: CdGeH3O7P, Orthorhombic, Cmca, a=7.1415(7) Å, b=10.9034(1) Å, c=13.1098(1) Å, Z=8, R1=0.0365 (F2>2σ(F2) and wR2=0.0985 (all data). The framework of CdGe(OH)3PO4 is built by a mixed network of GeO6, CdO6 octahedra and PO4 tetrahedra, which are linked to form a 3-membered ring (3-MR). The GeO6 and CdO6 octahedra share common vertexes and edges, respectively, to form one-dimensional (1D) Ge–O–Ge and Cd–O–Cd chains, which are further connected forming corrugated Ge–O–Cd layers. The layers are linked by PO4 tetrahedra, leading to a 3D open-framework structure with 3- and 6-MR channels.A new three-dimensional framework cadmium germanium phosphate, CdGe(OH)3PO4 was synthesized by solvothermal methods. The framework of CdGe(OH)3PO4 is built by a mixed network of GeO6 octahedra, CdO6 octahedra and PO4 tetrahedra and contains a network of one-dimensional 3 and 6-membered ring channels. It belongs to a class of metal germanium phosphates with an open framework.

Nanostructured silicon hollow spheres with a thin shell have been synthesized by magnesium reduction of silica spheres, which possess a high BET surface area and are electrochemically active in capacitive energy storage with a maximum specific capacitance of 193 F g−1 in the neutral Na2SO4 aqueous solution.

Nanostructured silicon has attracted a great deal of attention as an excellent anode material for Li ion batteries (LIBs). However, the use of Si nanomaterials in LIBs is severely hindered by their preparative methods owing to the high cost, low yield, and harsh synthetic conditions. Herein, we report a new method for the synthesis of uniform Si nanocrystals based on the magnesiothermic reduction of natural attapulgite clay. The obtained Si nanocrystals with a uniform size of ca. 10 nm are coated with polypyrrole (denoted ppy@Si) and show excellent electrochemical performance as anode materials for LIBs. After charging–discharging for 200 cycles at a current density of 0.6 A g−1, the specific capacity value of the ppy@Si anode is ∼954 mA h g−1. Because of the abundance of attapulgite, the obtained silicon nanoparticles can be exploited as a practical anode material for high-performance Li-ion batteries.

By using an octadentate ligand tetrakis[(3,5-dicarboxyphenoxy)methyl] methane (H8L), a new microporous metal–organic framework [Cu4L(H2O)4](H2O)31 (1) was solvothermally synthesized and structurally characterized. MOF 1 is built from the 4-connected square planar [Cu2(O2CR)4] cluster and 8-connected cube ligand L to have a highly open framework with scu topology. It possesses permanent porosity as confirmed by N2, H2, C2H2, CO2 and CH4 gas adsorption measurements and exhibits high acetylene storage of 193 and 154 cm3 g−1 at 273 and 296 K under 1 atm, respectively.

By using the octadentate ligand tetrakis[(3,5-dicarboxyphenoxy)methyl] methane (H8L), a rare (4,8)-scu type microporous coordination polymer, [In2L][NH2(CH3)2]2·(DMF)4(H2O)16, was synthesized and structurally characterized. The compound possesses an anionic three-dimensional open framework and exhibits permanent porosity with selective gas adsorption of CO2 over CH4. It exhibited strong fluorescence emission upon excitation at RT, and a selective, efficient emission quenching response towards nitroaromatic explosives.

The assemblies of tetrahedral linker tetrakis[4-(carboxyphenyl)oxamethyl]methane acid (H4L) with ZnCl2 and CdBr2 yield two noncentrosymmetric, NLO-active coordination polymers [Zn4(L2)(H2O)3(DMA)]·2H2O (1) and [Cd2L(DMA)2(H2O)2] (2), respectively. 1 has an unprecedented 2-fold interpenetrating sxa topology with ferroelectric properties, while 2 has a 7-fold interpenetrating dia network.

A new UiO-67-type zirconium metal organic framework (MOF) material UiO-67-bpy-Me (bpy = 2,2-bipyridine-4,4′-dicarboxylic acid, Me = methyl) was prepared by N-quaternization of the pyridine sites in UiO-67-bpy. After N-quaternization, the pristine neutral framework turned cationic while its high thermal and chemical stabilities were primarily preserved. Fast and enhanced anionic dye adsorption was observed in UiO-67-bpy-Me. In addition, despite the decrease in surface area and pore volume, UiO-67-bpy-Me exhibited an evident increase in CO2 uptake compared to UiO-67-bpy. The enhancement was ascribed to the strong interactions between CO2 and the N-quaternized framework. More importantly, as the N-quaternization has changed the electronic structure of the organic linker. UiO-67-bpy-Me showed optical absorption up to ca. 800 nm with a large red shift of 450 nm compared to the pristine UiO-67-bpy (ca. 350 nm). The extended optical absorption may lead to more efficiency in light utilization. A proof-of-concept demonstration showed that UiO-67-bpy-Me could more efficiently catalyze methyl-orange degradation under UV-Vis light irradiation than the pristine UiO-67-bpy. These findings demonstrate that N-quaternization could serve as a facile post-synthetic modification method to tune the chemical/physical properties of free pyridyl-containing MOFs.

Hollow-structured Si/SiC@C nanospheres were prepared through a magnesiothermic reduction of resin-coated SiO2 spheres. These nanostructured materials with high surface area not only show high adsorption capacities of industrial dyes from wastewater, but also exhibit excellent catalytic activities for chemical fixation of CO2 under mild, solvent-free conditions.

A novel open-framework material [Cu(H2O)2(OH)]2Ge(PO4)2, which was synthesized by a hydrothermal method, is built of GeO6, CuO6 octahedra and PO4 tetrahedra, and possesses a network of interconnecting six- and eight-membered ring channels.

Ultra-thin SiOx (0 < x < 2) nanosheets were obtained via a convenient solvothermal route from a Zintl compound CaSi2. After carbon coating, the SiOx@C nanosheet anodes exhibit high capacity, good rate and superior cycling performance for high-capacity lithium ion battery applications. The specific capacity can be maintained as high as 760 mA h g−1 with almost no capacity decay after 400 cycles at a current density of 0.5 A g−1.

An indium based metal–porphyrinic framework, denoted NUPF-3, was prepared based on a new amido-decorated porphyrin ligand. NUPF-3 possesses a rarely seen 4-fold interpenetrated pts framework with segmented pores and dense metalloporphyrin central sites. The structure can retain its crystallinity in commonly used solvents, as well as acidic/alkaline solutions with pH ranging from 1 to 12 for 48 h, exhibiting high chemical stability. Meanwhile, thermal analysis reveals that NUPF-3 possesses relatively high thermal stability. Owing to the presence of amido groups, structural interpenetration and a charged framework, NUPF-3 exhibits relatively high CO2 uptake. Moreover, NUPF-3 could be used as a good heterogeneous catalyst for cycloaddition of CO2 and epoxides, under relatively mild conditions, with good recyclability.

We herein report a series of microporous metal–porphyrinic frameworks (MPFs), denoted as NUPF-2M, based on rare earth (RE) clusters. NUPF-2M represent the first examples of RE cluster-based MPFs, possessing a rarely seen shp-a topology and exhibiting high thermal and thermal stabilities. After a post-metallization process with FeCl3, NUPF-2M is catalytically active as an efficient heterogeneous catalyst for intermolecular N–H carbene insertion.