Silver Thiolate Nano-sized Molecular Clusters and Their Supramolecular Covalent Frameworks: An Approach Toward Pre-templated Synthesis.

A series of seven new complexes including silver-thiolate molecular clusters and their covalent supramolecular frameworks have been assembled from the silver carbide precursor Ag C using a C pre-templated approach. Herein, two prototype clusters Ag (SR) and CO @Ag (SR) (R=isopropyl, cyclohexyl or tert-butyl; m=18 or 20) are employed to construct cluster-based metal-organic frameworks of different dimensions. In particular, both new ellipsoidal tetradecanuclear molecular cluster compounds, namely, Ag (S-iPr) (CO CF ) ⋅(DMSO) (two polymorphic forms 1, 2) and [Ag (S-Cy) (CO CF ) (DMSO) ]⋅(DMSO) (3), and a cluster-based metal-organic framework {Ag [Ag (S-iPr) (CO CF ) (H O) CH OH]⋅(H O) } (4) have been isolated and structurally characterized.

Chloride assisted supramolecular assembly of a luminescent gigantic cluster: [AgSCl(C[triple bond, length as m-dash]CPh)(HO)] with pseudo-T skeleton and five-shell arrangement.

Using a chloride-assisted supramolecular building-block approach, we have employed the molecular Cl@Ag(C[triple bond, length as m-dash]CPh) entity in the construction of a gigantic cluster namely [AgSCl(C[triple bond, length as m-dash]CPh)(HO)][Ag(imidazole)(HO)](SbF) (1), which contains the largest discrete organometallic cluster investigated by X-ray crystallography. Based on an icosahedral Cl@Ag kernel, this spheroidal cluster features an unprecedented five-shell structure Cl@Ag@S@Ag@SCl@Ag with idealized T symmetry. The MALDI-MS, 1D, 2D H NMR, electronic absorption, emission spectra and HR-TEM of 1 were measured.

Ethynide-stabilized high-nuclearity silver(i) sulfido molecular clusters assembled using organic sulfide precursors.

Inexpensive 1,1'-thiocarbonyldiimidazole and di(2-pyridyl) thionocarbonate have been used as respective sulfide precursors to assemble unprecedented high-nuclearity ethynide-stabilized silver(i) sulfido molecular clusters [Ag9S6@Ag36(C[triple bond, length as m-dash]C(t)Bu)32(H2O)2] [Ag(imidazole)(CH3OH)(H2O)](BF4)2·8H2O·2CH3OH (1) and [Ag120S24(PhC[triple bond, length as m-dash]C)52Cl4(2-pyridone)10(H2O)8](H3O)4(SiF6)8(BF4)4·CH3OH·22H2O (2), the latter being the largest isolated silver(i) ethynide cluster reported to date.

Cobalt(II) amido complexes derived from a monodentate arylamido ligand featuring a highly electron-withdrawing C6F5 substituent.

A series of cobalt(ii) complexes of a highly electron-withdrawing amido ligand, [N(C6F5)(C6H3Pr(i)2-2,6)](-) (L), were synthesized and structurally characterized. Mononuclear [CoL(Cl)(TMEDA)] (3) and heterobimetallic [CoL2(μ-Cl)Li(THF)3] (4) were obtained by direct metathetical reactions of anhydrous CoCl2 with one molar equivalent of [LiL(TMEDA)] (1) (TMEDA = Me2NCH2CH2NMe2) and [LiL(THF)3] (2), respectively. Complex 3 underwent facile ligand substitution reactions with LiMe and NaN3, yielding the corresponding mixed-ligand complexes [CoL(X)(TMEDA)] (X = Me 5, N36).

Organosilver(I) framework assembly with trifluoroacetate and enediyne-functionalized alicycles.

Eight new silver(I) trifluoroacetate complexes based on a series of designed ligands, each featuring an alicyclic ring with enediyne functionality, have been synthesized and characterized by single-crystal X-ray diffraction. Each ethynide terminal is inserted into an Agn (n = 4-5) basket, leading to the generation of coordination chain or layer structures, but the well shielded ethenyl group does not take part in silver-olefin bonding. Variation in ring size of the alicycles is shown to influence the construction of the organosilver(I) coordination networks, which are consolidated by weak intermolecular interactions in the crystal structures.