一种由[Ag(CN)2]-和Mn(Ⅱ)建筑块组装的三个三维网穿插的超分子配合物的结构和荧光性质

0 Introduction Recently, a considerable effort on crystal engi- neering has been devoted to the research of supramolecular assemblies because they show abun- dant topologic structures and offer possibilities for po- tential applications of functional mate…     

Assembly of infinite silver(I) columns, chains, and bridged aggregates with supramolecular synthon bearing substituted phenylethynides

Structural correlation in a series of eight silver(I) complexes bearing substituted phenylethynide ligands was systematically investigated through variation of the position or steric bulk of substituents on the aromatic ring. All coordination frameworks are constructed with the supramolecular synthon Ar--C triple bond C superset Ag(n) (Ar=4-MeC6H4, 3-MeC6H4, 2-MeC6H4, 4-tBuC6H4, 3,5-(CF3)2C6H3; n=4, 5), and the presence of coexisting ligands was found to influence the supramolecular assembly. The role of pi-pi stacking, C--Hpi and Ag-C(aromatic) interactions in stabilizing the coordination networks is also discussed.     

Structural,Photoluminescent and Theoretical Evidence for Ligand-unsupported Argentophilic Interactions in a Supramolecular Aggregate of [Ag2（Hida）（NH3）2]

A new neutral [Ag2（Hida）（NH3）2] molecule （1, H3ida = 1H-imidazole-4,5-dicarboxylic acid） has been synthesized and structurally characterized by single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 18.3928（8）, b = 8.3299（5）, c = 13.682（7） A, β = 113.179（2）°, V = 1926.9（10）A^3, Z = 8 and Dc = 2.784 g·cm^-3. In the solid state, this disilver（I） compound can aggregate to furnish the energetically stable ligand-unsupported Ag^I-Ag^I interaction concomitant with significant photoluminescence changes in different aggregate states, and such argentophilicity interaction is also supported by molecular orbital calculations.     

Novel mu5-coordination modes of aryl and alkyl ethynides and classification of metal-ligand interactions in silver(I) complexes

Novel mu(5)-eta(1),eta(1),eta(1),eta(1),eta(2) and mu(5)-eta(1),eta(1),eta(1),eta(2),eta(2) coordination modes of alkyl and aryl ethynide moieties are found in silver(I) complexes 1-5, and the metal-ligand distances can be classified into sigma, pi and mixed (sigma,pi) types. With the consistent square-pyramidal capping Ag(5) baskets of the ethynide moiety as supramolecular synthons, a series of two- and three-dimensional coordination networks are obtained.     

Metallophilicity versus pi-pi interactions: ligand-unsupported argentophilicity/cuprophilicity in oligomers-of-dimers [M2L2]n (M=CuI or AgI, L=tridentate ligand)

To verify whether attractive metallophilic interactions exist in the dimer-of-dimers [Cu(2)(ophen)(2)](2) (Hophen=1H-[1,10]phenanthrolin-2-one) (1), we designed and synthesized a series of such [M(2)L(2)](2) structures by varying the d(10) metal and/or the ligand (M=Cu(I) or Ag(I), L=ophen or obpy; Hobpy=1H-[2,2']bipyridinyl-6-one), and have successfully obtained three dimers-of-dimers: [Ag(2)(ophen)(2)](2).6 H(2)O (2), [Cu(2)(obpy)(2)](2) (3), and [Ag(2)(obpy)(2)](2).4.5 H(2)O.0.5 DMF (4). X-ray analyses of these structures show that interdimer M-M separations in [Ag(2)-(ophen)(2)](2) (3.199 A) are remarkably shorter than those in [Cu(2)(ophen)(2)](2) (3.595 A). Shorter interdimer M-M separations are found in the structures of [M(2)(obpy)(2)](2) (2.986 and 2.993 A in [Cu(2)(obpy)(2)](2), 3.037 to 3.093 A in [Ag(2)(obpy)(2)](2)), in which the pi systems are smaller than in the complexes with the ophen ligand. Detailed structural comparison of these dimers-of-dimers indicates that the interdimer, face-to-face pi-pi interactions repulse rather than support the interdimer metal-metal attractive interactions. This study also yields qualitative comparison of the strengths between argentophilic, cuprophilic, and face-to-face pi-pi interactions. DFT calculations on the four dimers-of-dimers further support the above deduction. The structure of a trimer-of-dimers [Ag(2)(obpy)(2)](3) (Ag-Ag 3.171 to 3.274 A) is further evidence that the oligomerization of the [M(2)L(2)] molecules is favored by stronger metallophilic and weaker face-to-face pi-pi interactions.     

The Potential of the Diarsene Complex [(C5H5)2Mo2(CO)4(μ,η2-As2)] as a Connector Between Silver Ions

The reaction of the organometallic diarsene complex [Cp₂Mo₂(CO)₄(μ,η²-As₂)] ( B ) (Cp = C₅H₅) with Ag[FAl{OC₆F₁₀(C₆F₅)}₃] (Ag[FAl]) and Ag[Al{OC(CF₃)₃}₄] (Ag[TEF]), respectively, yields three unprecedented supramolecular assemblies [(η²- B )₄Ag₂][FAl]₂ ( 4 ), [(μ,η¹:η²- B )₃(η²- B )₂Ag₃][TEF]₃ ( 5 ) and [(μ,η¹:η²- B )₄Ag₃][TEF]₃ ( 6 ). These products are only composed of the complexes B and Ag^I. Moreover, compounds 5 and 6 are the only supramolecular assemblies featuring B as a linking unit, and the first examples of [Ag^I]₃ units stabilized by organometallic bichelating ligands. According to DFT calculations, complex B coordinates to metal centers through both the As lone pair and the As−As σ-bond thus showing this unique feature of this diarsene ligand.     

Enhanced Metallophilicity in Metal–Carbene Systems: Stronger Character of Aurophilic Interactions in Solution

Metallophilicity is an essential concept that builds upon the attraction between closed shell metal ions. We report on the [M₂(bisNHC)₂]²⁺ (M=Au^I, Ag^I; NHC=N-heterocyclic carbene) systems, which display almost identical features in the solid state. However, in solution the Au₂ cation exhibits a significantly higher degree of rigidity owed to the stronger character of the aurophilic interactions. Both Au₂ and Ag₂ cationic constructs are able to accommodate Ag⁺ ions via M–M interactions, despite their inherent Coulombic repulsion. When electrostatic repulsion between host and guest is partially diminished, M–M distances are substantially shortened. Quantum chemical calculations estimate intermetallic bond orders up to 0.2. Although at the limit of (or beyond) the van der Waals radii, metallophilic interactions are responsible for their behavior in solution.     

The nature of the AgI...AgI interaction in different Ag(NH3)2 dimers embedded in supramolecular solids

An isolated silver(I) ammonia monomer, a dimer, and a novel dimer containing an intercalated water molecule have been embedded as guests in supramolecular frameworks, [Ag(NH3)2][(H2thpe)(H3thpe)].MeCN (1), [{Ag(NH3)2}2][(H2thpe)2]4.25 H2O (2), and [{Ag(NH3)2}-H2O-{Ag(NH3)2}][(H2thpe)(2)]benzene (3) (H3THPE=tris(hydroxyphenyl)ethane). The [{Ag(NH3)2}2]2+ dimer is not stable as an isolated entity, but is stabilized by hydrogen bonding in the supramolecular framework. The water-intercalated silver(I) ammonia dimer, which constitutes a novel species, is also subject by hydrogen bonding in concentrated solutions. The destabilization energy of the dimer relative to isolated monomers is calculated to be approximately 300 kJ mol(-1) by both perturbation methods and DFT theory. For the water-intercalated dimer it is calculated to be approximately 200 kJ mol(-1) according to the BSSE-corrected MP2 calculation. The different aggregate states show a dramatic variation of absorption and emission properties, in accordance with the concentration dependent red-shift observed in solutions. Natural-bond-orbital analysis shows that the disilver-ammonium-aquo "sandwich" cation in 3 is stabilized by interaction between the pi lone pair orbital on the oxygen atom of the water molecule and Ag(I)--N sigma antibonding molecular orbital.     

Silver(I) Double and Multiple Salts Containing the 1,3‐Butadiynediide Dianion: Coordination Diversity and Assembly with the Supramolecular Synthon Ag4⊂CC?CC⊃Ag4

A series of 13 silver(I) double and multiple salts containing 1,3‐butadiynediide, C₄^2?, were synthesized by dissolving the silver carbide Ag₂C₄ in a concentrated aqueous solution of one or more of the silver salts AgNO₃, AgCF₃CO₂, AgC₂F₅CO₂, AgF, AgBF₄, and AgPF₆. The 1,3‐butadiynediide anion invariably adopts a μ₄,μ₄ coordination mode in these compounds, which indicates that the Ag₄?C?C? C?C?Ag₄ moiety can be used as a new type of metalloligand supramolecular synthon for the construction of coordination networks. Fine‐tuning with various ancillary anionic ligands caused the Ag₄ aggregate at each ethynide terminus to adopt a butterfly‐shaped, planar, or barblike configuration, within which the silver–ethynide interactions can be classified into three types: σ, π, and mixed (σ,π). The effect of coexisting nitrile ligands and quaternary ammonium salts on supramolecular assembly with the above synthon was also explored. The hydrolysis of PF₆^? and BF₄^? led to the formation of the quadruple salt Ag₂C₄?4 AgNO₃?AgPF₂O₂?Ag₃PO₄ and a novel (F)₂(H₂O)₁₈ hydrogen‐bonded tape in the triple salt Ag₂C₄?2 AgF? 10 AgC₂F₅CO₂?CH₃CN?12 H₂O, respectively. The largest silver–ethynide cluster aggregate described to date, (C₄)₃@Ag₁₈, occurs in 3 Ag₂C₄? 12 AgC₂F₅CO₂?5[(BnMe₃N)C₂F₅CO₂]? 4 H₂O (Bn=benzyl).