Single-Crystalline UiO-67-Type Porous Network Stable to Boiling Water, Solvent Loss, and Oxidation.

With methylthio groups flanking the carboxyl groups, the 3,3',5,5'-tetrakis(methylthio)biphenyl dicarboxylate (TMBPD) linker forms a zirconium(IV) carboxylate porous framework featuring the topology of the UiO-67 prototype, i.e., with a face-centered-cubic array of the ZrO(OH) clusters.

Made in Water: A Stable Microporous Cu(I)-carboxylate Framework (CityU-7) for CO, Water, and Iodine Uptake.

Using water as the sole solvent, the bifunctional molecule tetrakis(methylthio)-1,4-benzenedicarboxylic acid (TMBD) was reacted with Cu(CHCN)BF to form a robust microporous metal-organic framework (MOF, CityU-7) featuring Cu(I) ions being simultaneously bonded to the carboxyl and thioether donors. The MOF solid is stable in air and can be easily activated by heating, without the need for treatment with organic solvents. The subnanoscopic pores (ca.

Metalation Triggers Single Crystalline Order in a Porous Solid.

We report the dramatic triggering of structural order in a Zr(IV)-based metal-organic framework (MOF) through docking of HgCl guests. Although as-made crystals were unsuitable for single crystal X-ray diffraction (SCXRD), with diffraction limited to low angles well below atomic resolution due to intrinsic structural disorder, permeation of HgCl not only leaves the crystals intact but also resulted in fully resolved backbone as well as thioether side groups. The crystal structure revealed elaborate HgCl-thioether aggregates nested within the host octahedra to form a hierarchical, multifunctional net.

A Boiling-Water-Stable, Tunable White-Emitting Metal-Organic Framework from Soft-Imprint Synthesis.

A new avenue for making porous frameworks has been developed by borrowing an idea from molecularly imprinted polymers (MIPs). In lieu of the small molecules commonly used as templates in MIPs, soft metal components, such as CuI, are used to orient the molecular linker and to leverage the formation of the network. Specifically, a linear dicarboxylate linker with thioether side groups reacted simultaneously with Ln(3+) ions and CuI, leading to a bimetallic net featuring strong, chemically hard Eu(3+) -carboxylate links, as well as soft, thioether-bound Cu2 I2 clusters.

Cyclometalated (boroxinato)gold(III) complexes from arrested transmetalation.

Organic boroxines are ubiquitous, but metallaboroxine analogues remain rare. A new class of (boroxinato)gold species are demonstrated here, as are observations of phosphorescence from boroxinato complexes. Four new compounds are crystallographically characterized.

In situ production of silver nanoparticles on an aldehyde-equipped conjugated porous polymer and subsequent heterogeneous reduction of aromatic nitro groups at room temperature.

In a metal-free procedure, chelating thiol groups and an electrophile react to assemble a robust, conjugated porous polymer with pendant aldehyde functionalities. These groups are able to reduce Ag(i) ions to generate, in situ, Ag(0) nanoparticles evenly dispersed in the polymer matrix. The Ag(0)-polymer composite enables selective reduction of aromatic nitro compounds as a heterogeneous catalyst, and can be conveniently recycled multiple times.

Suzuki-Miyaura coupling of arylboronic acids to gold(iii).

Gold(iii) is prominent in catalysis, but its organometallic chemistry continues to be restricted by synthesis. Metal-carbon bond formation often relies on organometallic complexes of electropositive elements, including lithium and magnesium. The redox potential of gold(iii) interferes with reactions of these classic reagents.

Pd uptake and H2S sensing by an amphoteric metal-organic framework with a soft core and rigid side arms.

Molecular components of opposite character are often incorporated within a single system, with a rigid core and flexible side arms being a common design choice. Herein, molecule L has been designed and prepared featuring the reverse design, with rigid side arms (arylalkynyl) serving to calibrate the mobility of the flexible polyether links in the core. Crystallization of this molecule with Pb(II)  ions led to a dynamic metal-organic framework (MOF) system that not only exhibits dramatic, reversible single-crystal-to-single-crystal transformations, but combines distinct donor and acceptor characteristics, allowing for substantial uptake of PdCl2 and colorimetric sensing of H2 S in water.

Immobilization of volatile and corrosive iodine monochloride (ICl) and I(2) reagents in a stable metal-organic framework.

The major discovery here is a robust and water-stable metal-organic framework (MOF) material capable of reversible binding of the volatile and reactive molecules of ICl and I2. The immobilization of I2 and ICl, as well as their controllable release thus achieved, is to facilitate the wide-ranging applications of these volatile species as catalysts and reagents in chemical and industrial processes. The framework material TMBP·CuI (hereafter TCuI) can be conveniently prepared in quantitative yields by heating CuI and the organic linker TMBP (3,3',5,5'-tetramethyl-4,4'-bipyrazol) in acetonitrile.

Convenient detection of Pd(II) by a metal-organic framework with sulfur and olefin functions.

A highly specific, distinct color change in the crystals of a metal-organic framework with pendant allyl thioether units in response to Pd species was discovered. The color change (from light yellow to orange/brick red) can be triggered by Pd species at concentrations of a few parts per million and points to the potential use of these crystals in colorimetric detection and quantification of Pd(II) ions. The swift color change is likely due to the combined effects of the multiple functions built into the porous framework: the carboxyl groups for bonding with Zn(II) ions to assemble the host network and the thioether and alkene functions for effective uptake of the Pd(II) analytes (e.

The role of the bridging group in exchange coupling in dinuclear homo- and heterometallic Ni(II) and Co(II) complexes with oxalate, oxamidate and dithiooxamidate bridges.

Six homodinuclear and two heteronuclear complexes Tp(Np)Co-C(2)O(4)-CoTp(Np) (1), Tp(Np)Co-C(2)O(4)-NiTp(Cy) (2), Tp(Cy)Ni-C(2)O(4)-NiTp(Cy) (3), Tp(Np)Co-C(2)O(2)(NH)(2)-CoTp(Np) (4), Tp(Cy)Ni-C(2)O(2)(NH)(2)-NiTp(Cy) (5), Tp(Np)Co-C(2)S(2)(NH)(2)-CoTp(Np) (6), Tp(Np)Co-C(2)S(2)(NH)(2)-NiTp(Cy) (7), Tp(Cy)Ni-C(2)S(2)(NH)(2)-NiTp(Cy) (8) (Tp(Np) = tris(3-neopentylpyrazolyl)borate, Tp(Cy) = tris(3-cyclohexylpyrazolyl)borate), were synthesized and characterized by mass spectrometry, electronic spectroscopy and X-ray crystallography. These compounds possess similar molecular structures, with the metal ions linked by bridging oxalate (1-3), oxamidate (4 and 5) or dithiooxamidate (6-8) ions. The heteronuclear nature of compounds 2 and 7 was additionally confirmed by high-resolution mass spectrometry.

Arylgold(I) complexes from base-assisted transmetalation: structures, NMR properties, and density-functional theory calculations.

The synthesis of gold(I) complexes of the type LAuR (L = PCy(3), IPr; R = aryl; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) starting from LAuX (X = Br, OAc) and boronic acids in the presence of Cs(2)CO(3) has been investigated. The reactions proceed smoothly in good to excellent yields over the course of 24-48 h in isopropyl alcohol at 50-55 °C. The aryl groups include a variety of functionalities and steric bulk, and in two cases, are heterocyclic.

Gold(I) styrylbenzene, distyrylbenzene, and distyrylnaphthalene complexes: high emission quantum yields at room temperature.

One gold(I)-substituted styrylbenzene, six digold(I) distyrylbenzenes, one tetragold distyrylbenzene, and four digold distyrylnaphthalene complexes were synthesized using base-promoted auration, alkynylation, triazolate formation, and Horner-Wadsworth-Emmons reactions. The gold(I) fragments are either σ-bonded to the aromatic system, or they are attached through an alkynyl or triazolate spacer. Product formation was monitored using (31)P{(1)H} NMR spectroscopy.

Constrained digold(I) diaryls: syntheses, crystal structures, and photophysics.

A series of di(gold(I) aryls), L(AuR)(2) (L = DPEphos, DBFphos, or Xantphos; R = 1-naphthyl, 2-naphthyl, 9-phenanthryl, or 1-pyrenyl), have been prepared. The complexes were characterized by multinuclear NMR spectroscopy, static and time-dependent optical spectroscopy, mass spectrometry, microanalysis, and X-ray crystallography. In addition, DFT calculations on model dinuclear gold complexes have been used to examine the electronic structures.

White light emission and second harmonic generation from secondary group participation (SGP) in a coordination network.

We describe a white emitting coordination network solid that can be conveniently applied as a thin film onto a commercial UV-LED lamp for practical white lighting applications. The solid state material was discovered in an exercise of exploring molecular building blocks equipped with secondary groups for fine-tuning the structures and properties of coordination nets. Specifically, CH(3)SCH(2)CH(2)S- and (S)-CH(3)(OH)CHCH(2)S- (2-hydroxylpropyl) were each attached as secondary groups to the 2,5- positions of 1,4-benzenedicarboxylic acid (bdc), and the resultant molecules (L1 and L2, respectively) were crystallized with Pb(II) into the topologically similar 3D nets of PbL1 and PbL2, both consisting of interlinked Pb-carboxyl chains.

Synthesis, structure and magnetic properties of Nd3+ and Pr3+ 2D polymers with tetrafluoro-p-phthalate.

Two lanthanide tetrafluoro-p-phthalate (L(2-)) complexes, Ln(L)(1.5)·DMF·H(2)O (Ln = Pr(3+) (1), Nd(3+) (2)), were synthesized using pyridine as a base. The compounds were found to be isostructural, and the structure of 1 has been determined by single crystal X-ray diffraction (monoclinic, space group C2, a = 22.

Semirigid aromatic sulfone-carboxylate molecule for dynamic coordination networks: multiple substitutions of the ancillary ligands.

We report dynamic, multiple single-crystal to single-crystal transformations of a coordination network system based on a semirigid molecule, TCPSB = 1,3,5-tri(4'-carboxyphenylsulphonyl)benzene, which nicely balances shape persistence and flexibility to bring about the framework dynamics in the solid state. The networks here generally consist of (1) the persistent core component (denoted as CoTCPSB) of linear Co(II) aqua clusters (Co-O-Co-O-Co) integrated into 2D grids by 4,4'-bipyridine and TCPSB and (2) ancillary ligands (AL) on the two terminal Co(II) ions-these include DMF (N,N'-dimethylformamide), DMA (N,N'-dimethylacetamide), CH(3)CN, and water. Most notably, the ancillary ligand sites are highly variable and undergo multiple substitution sequences while maintaining the solid reactants/products as single-crystals amenable to X-ray structure determinations.

Zinc complexes of Ttz(R,Me) with O and S donors reveal differences between Tp and Ttz ligands: acid stability and binding to H or an additional metal (Ttz(R,Me) = tris(3-R-5-methyl-1,2,4-triazolyl)borate; R = Ph, tBu).

Alkylzinc complexes, (Ttz(R,Me))ZnR' (R = tBu, Ph; R' = Me, Et), show interesting reactivity with acids, bases and water. With acids (e.g.

2,2'-[4,10-Bis(carb-oxy-meth-yl)-4,10-diaza-1,7-diazo-niacyclo-dodecane-1,7-di-yl]diacetate dihydrate.

In the title compound, C(16)H(28)N(4)O(8)·2H(2)O, the 12-membered macrocycle has twofold crystallographic symmetry and the asymmetric unit comprises one half-mol-ecule. The four carbox-yl/carboxyl-ate groups reside on the same side of the macrocycle. The mol-ecule is a double zwitterion with two of the carb-oxy-lic acid H atoms transferred to the two N atoms on the opposite sides of the macrocycle, resulting in both N atoms having positive charges and leaving the two resulting carboxyl-ate groups with negative charges.

catena-Poly[[[tetra-kis-(4-methyl-pyridine-κN)copper(II)]-μ-sulfato-κO:O'] 4.393-hydrate].

The structure of the title compound, {[Cu(SO(4))(C(6)H(7)N)(4)]·4.393H(2)O}(n), consists of Cu(2+) ions surrounded in a square-planar fashion by 4-methyl-pyridine ligands, forming two crystallographically independent Cu{H(3)C(C(5)H(4)N)}(4) units that are both located on crystallographic inversion centers. The Cu(4-methyl-pyridine)(4) units are, in turn, connected with each other via bridging sulfate anions, leading to the formation of infinite [Cu{H(3)C(C(5)H(4)N)}(4)SO(4)](n) zigzag chains along [001].

Coordination networks from Cu cations and tetrakis(methylthio)benzenedicarboxylic acid: tunable bonding patterns and selective sensing for NH(3) gas.

This paper aims to illustrate the rich potential of the thioether-carboxyl combination in generating coordination networks with tunable and interesting structural features. By simply varying the ratio between Cu(NO(3))(2) and the bifunctional ligand tetrakis(methylthio)benzenedicarboxylic acid (TMBD) as the reactants, three coordination networks can be hydrothermally synthesized in substantial yields, which present a distinct evolution with regard to metal-ligand interactions. Specifically, Cu(TMBD)(0.