Melt-quenched glass formation of a family of metal-carboxylate frameworks.

Metal-organic framework (MOF) glasses are an emerging class of glasses which complement traditional inorganic, organic and metallic counterparts due to their hybrid nature. Although a few zeolitic imidazolate frameworks have been made into glasses, how to melt and quench the largest subclass of MOFs, metal carboxylate frameworks, into glasses remains challenging. Here, we develop a strategy by grafting the zwitterions on the carboxylate ligands and incorporating organic acids in the framework channels to enable the glass formation.

MOF-supported crystalline ionic liquid: new type of solid electrolyte for enhanced and high ionic conductivity.

Solid-state electrolyte (SSE) is crucial for a high-performance all-solid-state battery. Here, a new solid sodium electrolyte based on the ionic liquid EIMS-NaTFSI and one metal-organic framework (MOF) UiO-67-MIMS functionalized with zwitterion groups MIMS was obtained (UiO-67 and was assembled with 4,4'-biphenyldicarboxylate linker and cluster ZrO(OH)) (EIMS = 1-(1-ethyl-3-imidazolio)propane-3-sulfonate, NaTFSI = sodium bis(trifluoromethanesulfonyl)imide, MIMS = 1-(1-mthyl-3-imidazolio)propane-3-sulfonate). By contacting and pairing EIMS-NaTFSI (abbreviated as EN-1) to the MIMS group on the framework, EN-1 was directed and arranged along the channels within UiO-67-MIMS, forming a solid composite EN-1@UiO-67-MIMS with Bragg scatter, , a crystalline ionic liquid containing Na salts (NaTFSI).

Facile Strategy for Efficient Charge Separation and High Photoactivity of Mixed-Linker MOFs.

Two new sets of UiO-Zr metal-organic framework (MOF) bearing mixed linkers and that have different band gaps and edges were prepared through post oxidation and direct methods, namely, ( = 4, 9, 12 oxidation hours) and ( = 0, 0.4, 0.6, 2), respectively.

Atomically precise nanoclusters with reversible isomeric transformation for rotary nanomotors.

Thermal-stimuli responsive nanomaterials hold great promise in designing multifunctional intelligent devices for a wide range of applications. In this work, a reversible isomeric transformation in an atomically precise nanocluster is reported. We show that biicosahedral [AuAg(PPh)Cl]SbF nanoclusters composed of two icosahedral AuAg units by sharing one common Au vertex can produce two temperature-responsive conformational isomers with complete reversibility, which forms the basis of a rotary nanomotor driven by temperature.

MOF-Directed Synthesis of Crystalline Ionic Liquids with Enhanced Proton Conduction.

Arranging ionic liquids (ILs) with long-range order can not only enhance their performance in a desired application, but can also help elucidate the vital between structure and properties. However, this is still a challenge and no example has been reported to date. Herein, we report a feasible strategy to achieve a crystalline IL via coordination self-assembly based reticular chemistry.

A Homoleptic Alkynyl-Ligated [Au Ag L ] Cluster as a Catalytically Active Eight-Electron Superatom.

A new alkynylated cluster [Au Ag (C H NO) ] is prepared by a NaBH mediated reduction method. The AuAg clusters are confirmed by sophisticated characterization techniques. It has a unique "Au @Ag @Au Ag " metal framework which is protected by 24 atypical alkyne ligands L (L=C H NO).

Tailoring the stability, photocatalysis and photoluminescence properties of Au nanoclusters doping engineering.

Dopants in gold nanoclusters have been proved to mediate the intrinsic electronic properties of homo-clusters. In this work, we report the precise synthesis of atomically precise AuAg(PPh)Cl alloy nanoclusters with multiple Ag dopants for the first time. Their structure was resolved by single-crystal X-ray crystallography.

Supramolecular topology design of silver(i) and copper(ii) coordination polymers through a new semi-rigid sulfonyl ligand with different anion templates.

A series of metal organic coordination polymers (MOCPs) of silver(i) and copper(ii) coordinated with a novel multifunctional semi-rigid sulfonyl ligand with different anion templates and oxidation states were designed for the first time. In addition, their atomically precise molecular structure was determined by single crystal X-ray diffraction analysis. In comparison, the topology of silver(i)-based MOCPs is affected significantly by different anion templates.

A Methylthio-Functionalized-MOF Photocatalyst with High Performance for Visible-Light-Driven H Evolution.

Recently, the emergence of photoactive metal-organic frameworks (MOFs) has given great prospects for their applications as photocatalytic materials in visible-light-driven hydrogen evolution. Herein, a highly photoactive visible-light-driven material for H evolution was prepared by introducing methylthio terephthalate into a MOF lattice via solvent-assisted ligand-exchange method. Accordingly, a first methylthio-functionalized porous MOF decorated with Pt co-catalyst for efficient photocatalytic H evolution was achieved, which exhibited a high quantum yield (8.

A route to robust thioether-functionalized MOF solid materials displaying heavy metal uptake and the ability to be further oxidized.

Here we developed a facile solvent-assisted ligand exchange method for synthesizing thioether-containing hybrid metal-organic frameworks (MOFs) that cannot be made using direct synthesis. Such a tailored approach provides an alternative method to achieve thioether-based MOFs and its oxidation-decorated materials. These materials showed the ability to take up heavy metals from solution and the ability to capture CO.

Synthesis, crystal structures and antitumor activity of two platinum(II) complexes with methyl hydrazinecarbodithioate derivatives of indolin-2-one.

Two new platinum(II) complexes 7a and 7b with methyl hydrazinecarbodithioate derivatives of indolin-2-one have been prepared and characterized by single-crystal X-ray diffraction, NMR spectroscopy and mass spectrometry. Antiproliferative activity of the two complexes and their ligands 6a and 6b against HCT-116, MCF-7 and MDA-MB-231 cell lines was determined by the MTS assay. Complexes 7a and 7b exhibited stronger antiproliferative activity against three cell lines than compounds 6a and 6b (IC, 1.

A Metal-Organic Framework Impregnated with a Binary Ionic Liquid for Safe Proton Conduction above 100 °C.

To develop proton-conducting materials under low-humidity conditions and at moderate working temperature still remains challenging for fuel-cell technology. Here, a new type of proton-conducting material, EIMS-HTFSA@MIL, which was prepared by impregnating the binary ionic liquid, EIMS-HTFSA (EIMS=1-(1-ethyl-3-imidazolium)propane-3-sulfonate; HTFSA=N,N-bis(trifluoromethanesulfonyl)amide), into a mesoporous metal-organic framework, MIL-101 ([Cr F(H O) O(BDC) ⋅n H O] (n≈0.25, BDC=1,4-benzenedicarboxylate)) is reported.

A stepwise bulk-to-cluster-to-particle transformation toward the efficient synthesis of alkynyl-protected silver nanoclusters.

We report herein the efficient synthesis of alkynyl-protected silver nanoclusters in terms of macrocycle-assisted bulk-to-cluster-to-nanoparticle transformation. Different substituted phenylacetylide ligands are applied to stabilize the silver nanoclusters by metal-carbon bonds and meanwhile determine the size of silver nanoclusters.

Aptasensor for electrochemical sensing of angiogenin based on electrode modified by cationic polyelectrolyte-functionalized graphene/gold nanoparticles composites.

Herein, a label-free and highly sensitive electrochemical aptasensor for the detection of angiogenin was proposed based on a conformational change of aptamer and amplification by poly(diallyldimethyl ammonium chloride) (PDDA)-functionalized graphene/gold nanoparticles (AuNPs) composites-modified electrode. PDDA-functionalized graphene (P-GR) nanosheets as the building block in the self-assembly of GR nanosheets/AuNPs heterostructure enhanced the electrochemical detection performance. The electrochemical aptasensor has an extraordinarily sensitive response to angiogenin in a linear range from 0.

High-nuclearity silver(I) cluster-based coordination polymers assembled with multidentate oligo-α-heteroarylsulfanyl ligands.

Two novel coordination polymers [Ag16(SO4)8][Ag4(SO4)2]3(L1)12·nH2O (n = 72) (1) and [Ag10(SO4)5(L2)4(H2O)2]·8H2O (2) based on conformationally variable oligo-α-heteroarylsulfanyl ligands 2-(pyrazin-2-ylthio)-6-(pyridin-2-ylthio)pyrazine (L1) or 2,6-bis(pyrazin-2-ylthio)pyrazine (L2) and sulfate-templated high-nuclearity Ag(I) clusters as structure-building units (SBUs) have been synthesized under mild conditions. Single-crystal X-ray analysis showed that complex 1 exhibits a porous three-dimensional framework containing Ag16(SO4)8 and Ag4(SO4)2 SBUs that are interconnected by L1 ligands, whereas 2 has a much denser network constructed from Ag10(SO4)5 SBUs and L2 linkers. To our knowledge, the Ag16(SO4)8 cluster core found in 1 is the largest sulfate-based polynuclear SBU in coordination polymers, and the 14-connected Ag10(SO4)5 in 2 is the highest-connectivity Ag(I) cluster SBU reported to date.

2,2'-Sulfonyl-dipyrazine 4-oxide.

In the title compound, C(8)H(6)N(4)O(3)S, the dihedral angle between the pyrazine rings is 85.04 (1)°. In the crystal, mol-ecules are arranged along the a axis and are linked by C-H⋯N hydrogen bonds and pyrazine-pyrazine π-π inter-actions [centroid-centroid distance = 3.

3,3'-Carbonyl-dipyridinium bis-(perchlorate).

In the title molecular salt, C(11)H(10)N(2)O(2+)·2ClO(4) (-), the complete cation is generated by crystallographic twofold symmetry. The dihedral angle between the pyridyl rings is 67.07 (7)°.

Supramolecular framework in catena-poly[[(nitrato-κO)silver(I)]-μ-(R,S)-2-(pyridin-4-ylsulfinyl)pyrimidine-κ3N,O:N'].

In the title complex, [Ag(NO(3))(C(9)H(7)N(3)OS)](n), η(1):η(1):η(1):μ(2)-bridging 2-(pyridin-4-ylsulfinyl)pyrimidine (pypmSO) ligands with opposite chiralities are alternately arranged to link the Ag(I) cations through two N atoms and one sulfinyl O atom of each ligand, leading to an extended zigzag coordination chain structure along the [ ̅201] direction. An FT-IR spectroscopic study shows a decreased stretching frequency for the η(1)-O-bonded S=O group compared with that of the free ligand. The parallel chains are arranged and interconnected via O(S=O)···π(pyridine/pyrimidine) and C-H(pyridine)···O(NO(3)(-)) interactions to furnish a layer almost parallel to the ac plane.

5-Fluoro-1-(4-meth-oxy-benz-yl)indoline-2,3-dione.

In the title compound, C(16)H(12)FNO(3), the dihedral angle between the benzene ring and the plane of the indole ring system is 71.60 (6)°. In the crystal, mol-ecules stack along the b axis through π-π inter-actions between the adjacent indole-2,3-dione units with a centroid-centroid distance of 3.

3,3-Dichloro-1-(chloro-meth-yl)indolin-2-one.

In the title compound, C(9)H(6)Cl(3)NO, the pyrrole ring is almost coplanar with the benzene ring [dihedral angle = 1.90 (9)°], while the Cl-C-N-C torsion angle is 98.78 (17)°.

Poly[hexa-μ-acetato-bis-(dimethyl sulfoxide)-trimanganese(II)].

In the title complex, [Mn(3)(CH(3)CO(2))(6)(C(2)H(6)SO)(2)](n), the Mn(II) ions exhibit similar MnO(6) octa-hedral coordination geometries but with different coordination environments. One type of Mn(II) ion is surrounded by five acetate groups and a terminal dimethyl sulfoxide group, while the other lies on a twofold axis and is coordinated by six O atoms from three symmetry-related acetate ions. The acetate anions exhibit three independent bridging modes, which flexibly bridge the Mn(II) ions along the c-axis direction, forming an infinite chain structure; the chains are further inter-connected through weak C-H⋯O and C-H⋯S hydrogen-bonding inter-actions.

2-(2,3-Dioxoindolin-1-yl)ethyl 4-(4-nitro-phen-yl)piperazine-1-carbodithio-ate.

In the title compound, C(21)H(20)N(4)O(4)S(2, )the piperazine ring adopts a chair conformation. The 1-ethyl-indoline-2,3-dione system links to one N atom of the piperazine ring via a carbodithio-ate group. The indoline-2,3-dione ring and the nitro-benzene ring subtend adihedral angle of 37.

1,1'-(Ethane-1,2-di-yl)bis-(indoline-2,3-dione).

The mol-ecule of the title compound, C(18)H(12)N(2)O(4), is situated on a crystallographic centre of symmetry. The mol-ecule has a zigzag structure, with two parallel symmetry-related indoline-2,3-dione fragments linked by an ethyl-ene group at each N atom. In the crystal, the mol-ecules stack in columns along the b axis.

Chlorido{N,N-dibenzyl-N,N-bis-[(diphenyl-phosphan-yl)meth-yl]pyridine-2,6-diamine}-methyl-platinum(II).

In the title mononuclear complex, [Pt(CH(3))Cl(C(45)H(41)N(3)P(2))], the pyridine-2,6-diamine ligand can be viewed as a centrosymmetric motif having two pendant N-benzyl-N-[(diphenyl-phosphan-yl)meth-yl] arms, the two P atoms of which chelate to the Pt(II) ion, forming a ten-membered metallocycle. A distorted square-planar coordination geometry around the Pt(II) atom is completed by a methyl ligand and a chloride ion. The packing between the mononuclear units is achieved through C-H⋯π inter-actions, which link the mol-ecules into chains along the c axis.

Bis[5-(2-pyrid-yl)pyrazine-2-carbonitrile]-silver(I) tetra-fluorido-borate.

In the title mononuclear complex, [Ag(C(10)H(6)N(4))(2)]BF(4), the Ag(I) atom adopts a square-planar N(4 )coordination geometry and is surrounded by two 5-(2-pyrid-yl)pyrazine-2-carbonitrile ligands. The tetra-fluorido-borate anions link the mononuclear cations through inter-molecular C-H⋯F hydrogen-bonding inter-actions, forming an infinite tape structure along [110]. Other weak inter-actions occur: π-π stacking with centroid-centroid distances of 3.