AgI Ions Research Articles

Synthesis, spectroscopy and crystal structure of a new heterodinuclear silver(I)—copper(I) cryptate

A new heterodinuclear cryptate [AgCuL](ClO4−)2 was synthesized by transmetallation via its precursor [Ag2L](ClO4−)2 (L = ligand). The electrospray mass spectrum (ES-MS) showed that the heterodinuclear entity exists in the solution. The X-Ray structure analysis shows that the AgI ion has tetrahedral geometry while CuI lies in a three-coordinate environment.

Formation of novel discrete silver(i) coordination architectures with quinoline-based monothioethers: adjusting the intramolecular Ag⋯Ag distances and complex structures by ligands modifications and variations of counter anions

In our efforts to design discrete polynuclear metal complexes with tailored structures, four structurally related quinoline-based new monothioether ligands, 8-(2-pyridylsulfanylmethyl)quinoline (L1), 8-(4-pyridyl- sulfanylmethyl)quinoline (L2), 8-(2-pyrimidylsulfanylmethyl)quinoline (L3), 5-methyl-2-(8-quinolylmethyl- sulfanyl)-1,3,4-thiadiazole (L4) have been designed, and six new AgI complexes with these ligands, {[AgL1](ClO4)(CHCl3)}21, [Ag2L1(NO3)2]22, {[AgL1(CH3CN)](PF6)}23, [AgL2(NO3)]24, {[AgL3(CH3OH)](ClO4)}25 and {[AgL4](ClO4)}26 have been synthesized and characterized by single-crystal X-ray diffraction analysis. All six complexes adopt discrete structures, with 1,3,4,5 and 6 being dinuclear and 2 being tetranuclear, and Ag–Ag interactions were found to exist in complexes 1,2,3 and 6, as well as π–π stacking in 1–4. Furthermore, the Ag⋯Ag distances in 1–6 were compared. In the six complexes, the sulfur atoms of the ligands adopt quite different coordination modes: bridging in 1,2 and 3, chelating in 5 and non-coordination in 4 and 6. In addition, the structural differences of 1,2 and 3 indicate that the change in the counter anion greatly influences the coordination modes of the ligands and the coordination geometries of AgI ion, which consequently affects the resulting frameworks of such complexes.

A remarkable 14-nuclear Re(8)(V) Ag(I)(6) coordination oligomer derived from a 2D (Re(2)(V) Ag(I)(2))n coordination polymer with D-penicillaminate.

ReV polymer/oligomer switching: The aggregation of ReV octahedra, [ReO(d-pen-N,O)(d-pen-N,O,S)]− (d-H2pen=d-penicillamine), assisted by AgI ions, leads to the formation of a 2D (ReAg)n coordination polymer 1, which is converted into a ReAg coordination oligomer 2 (see picture; Ag green, S yellow, Re purple, O red, N blue). While 1 results from the self-assembly of ReAg units through AgO coordination bonding, the self-assembly of ReAg molecules in 2 is through COOH⋅⋅⋅OOC hydrogen bonding.

A Single-Strand Helical Motif Induced by Self-Assembly of [Ag(TFP)]+ Moieties with Nitrate Anions −31P NMR Spectroscopic and X-ray Crystal Structure Characterization of the Complexes Involved in Equilibrium Reactions of Silver Salts and TFP Ligand

The ability of the ligand tris(2-furyl)phosphane (TFP) to coordinate AgI ions has been investigated. The molar ratio and the nature of the counterions used (NO3−; BF4−) affected the reaction. Moreover, equilibrium reactions were observed and the [Ag(TFP)n]+ (n = 1−4) species involved were identified by variable-temperature 31P NMR spectroscopy. The [Ag(TFP)3]BF4 complex turned out to be the more labile species in solution and it disproportionates by means of an SN2 mechanism to yield the complexes [Ag(TFP)2(H2O)]BF4 (3) and [Ag(TFP)4]BF4 (4). Most of the compounds detected in solution were isolated and characterized in the solid state. The molecular structures of the complexes [Ag(TFP)NO3] (1), [Ag(TFP)3NO3] (2), and [Ag(TFP)2(H2O)]BF4 (3) were determined by X-ray crystal structure diffraction confirming the solution characterization data. In these structures the TFP ligand was always only bonded to the metal centre by the phosphorous atom. It is noteworthy to underline that the molecular structure of complex 1 consists of an infinite single-strand helix arising from the ability of the bridging nitrate anions to connect the [Ag(TFP)]+ units. In the structure the nitrate anions are coordinated to the metal centres in unusual modes acting simultaneously as chelating and bridging ligands. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Catena-Poly[[[1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene]silver(I)] nitrate

The bipyridyl-base ligand 1,4-bis(4-pyridyl)-2,3-di­aza-1,3-buta­diene (L) has been used in the synthesis of a new organomet­allic polymer. The reaction between AgNO3 and L afforded a one-dimensional chain structure of the cation of the title compound, {[Ag(C12N4H10)]NO3}n. The AgI ion lies on a twofold axis and is in a linear environment with respect to the two terminal N atoms of pyridyl rings. Weak interactions between H and nitrate O atoms, and between the Ag and nitrate O atoms, generate a three-dimensional framework.

The reactivity of N -2-(4-amino-1,6-dihydro-1-methyl-5-nitroso-6-oxo-pyrimidinyl)-L-histidine towards silver(I) and zinc(II) ions

Reactions of N-2-(4-amino-1,6-dihydro-1-methyl-5-nitroso-6-oxopyrimidinyl)-L-histidine with AgI and ZnII ions in 1/1 and 4/1 ligand-to-metal molar ratios, in aqueous media at 25 °C and 0.1 M KNO3 and KCl ionic strength, respectively, were followed by potentiometric techniques in order to determine formation equilibria for the complex species. The spectral curves, as a function of ligand-to-metal molar ratio at established pH values, were studied and four solid phases of stoichiometry: AgL·4H2O, Ag(HL)NO3·1.5H2O, AgL(OH)2K2·H2O and Zn(HL)2Cl2·7H2O were isolated and characterised by analytical, spectroscopic and thermal measurements.

Coordination polymer complexes of 4,4′-dipyridyldisulfide and AgX (X = PF6–, ClO4–, OTs–, NO3–, BF4–) with twisted rhomboid networks, 2-D sheets, and 1-D chain structures

Several AgI coordination polymers linked by the –S–S– bridged ligand 4-PDS (= 4,4′-dipyridyldisulfide) were prepared and their crystal structures characterized. The isomorphous complexes [Ag(4-PDS)2·PF6] 1 and [Ag(4-PDS)2·ClO4] 2 have twisted rhomboidal frameworks that consist of four AgI ions and four 4-PDS N-donor ligands, and show inclusion of the counter anions in their chiral cavities. The AgI ion has a tetrahedral coordination, and the rhomboidal units are assembled in the form of a 2-D sheet structure. The complex [Ag(4-PDS)·OTs] 3 (where OTs− = p-toluenesulfonate) shows a 2-D sheet structure, constructed from 1-D zigzag chains bridged by interchain Ag–Ag interactions. The AgI ion has a T-shaped coordination environment, and the OTs− anions are located between the sheets. The complex [Ag(4-PDS)·NO3·(CH3CN)0.5] 4 is a 1-D zigzag coordination polymer with a chiral chain structure, incorporating acetonitrile as a guest molecule between the chains.

A bent two-coordinate silver(I) complex with 2,2′,3,3′-tetrahydro-4,4′-dithia-1,1′-binaphylidene

The AgI complex of 2,2′,3,3′-tetra­hydro-4,4′-di­thia-1,1′-binaphyl­idene (ttp) has been synthesized and its molecular structure determined as its PF6− salt, i.e. (2,2′,3,3′-tetra­hydro-4,4′-di­thia-1,1′-binaphyl­idene)silver(I) hexa­fluoro­phosphate, [Ag(C18H16S2)]PF6. The AgI ion has a distorted linear geometry comprised of the two S atoms of ttp, with an Ag—S distance of 2.4889 (8) A and an S—Ag—S angle of 157.48 (4)°; the cation has twofold symmetry. This coordination mode results in the formation of a nine-membered ring.

Tetranuclear Copper(I)-Biphenanthroline Gridwork: Violation of the Principle of Maximal Donor Coordination Caused by Intercalation and CH-to-N Forces

Design principles in polynuclear coordination complexes have been based on the idea that metal ions would acquire donor atoms up to the metal's ligand field preference, and donor ligands, such as 1,10-phenanthroline, would not leave donor atoms uncoordinated to a metal ion. The geometry of the simple molecular grid formed from a series of 3,3′-biphenanthrolines complexed with CuI or AgI ions sets up a cleft that binds uncoordinated ligands through a combination of intercalation, solvation, and CH-to-N interactions (see picture).

Tetranuclear Copper(I)-Biphenanthroline Gridwork: Violation of the Principle of Maximal Donor Coordination Caused by Intercalation and CH-to-N Forces

Design principles in polynuclear coordination complexes have been based on the idea that metal ions would acquire donor atoms up to the metal's ligand field preference, and donor ligands, such as 1,10-phenanthroline, would not leave donor atoms uncoordinated to a metal ion. The geometry of the simple molecular grid formed from a series of 3,3′-biphenanthrolines complexed with CuI or AgI ions sets up a cleft that binds uncoordinated ligands through a combination of intercalation, solvation, and CH-to-N interactions (see picture).

Syntheses and Structures of Silver and Copper Coordination Polymers with 4,4′-Azopyridine − Effect of Counter Anions and π−π Interactions on the Network Systems

The syntheses and structures of [Ag(azpy)](NO3)⋅(H2O)⋅(CH3OH) (1), [Cu(azpy)2](ClO4) (2), [Cu(azpy)2(H2O)2](NO3)2⋅(H2O)2 (3) and [Cu(azpy)2(H2O)2](ClO4)2⋅(C2H5OH)2 (4), where azpy = trans-4,4′-azopyridine, are reported to test the dependence of network topology on counter anions and π−π interactions. Complex 1 contains pairs of linear chains of alternating AgI ions and azpy ligands, resembling a ladder structure in which the ligands form π−π interactions (with a distance of 3.53 Å) and AgAg interactions (with a distance of 3.30 Å). Complex 2 exists as a 3D adamantoid polymer in which each CuI center is coordinated to four azpy ligands in a tetrahedral geometry, the ligands are in turn coordinated to four other CuI centers. The cavities are filled with four other adamantoid units forming five interpenetrating networks. Complexes 3 and 4 are composed of two-dimensional sheets in which the CuII atom is coordinated in an octahedral geometry to two water molecules and four ligands. The ligands are in turn coordinated to four other CuII centers. While the sheets in complex 3 display inclined 2D interpenetration, the sheets in complex 4 are all parallel and isolated, with an intersheet separation of ca. 4.7 Å.

Rational Construction of Chiral Octanuclear Metallacycles Consisting of Octahedral CoIII, Square-Planar PdII, and Linear AuI or AgI Ions

Rational Construction of Chiral Octanuclear Metallacycles Consisting of Octahedral CoIII, Square-Planar PdII, and Linear AuI or AgI Ions

Syntheses and Structures of Silver and Copper Coordination Polymers with 4,4′-Azopyridine − Effect of Counter Anions and π−π Interactions on the Network Systems

The syntheses and structures of [Ag(azpy)](NO3)⋅(H2O)⋅(CH3OH) (1), [Cu(azpy)2](ClO4) (2), [Cu(azpy)2(H2O)2](NO3)2⋅(H2O)2 (3) and [Cu(azpy)2(H2O)2](ClO4)2⋅(C2H5OH)2 (4), where azpy = trans-4,4′-azopyridine, are reported to test the dependence of network topology on counter anions and π−π interactions. Complex 1 contains pairs of linear chains of alternating AgI ions and azpy ligands, resembling a ladder structure in which the ligands form π−π interactions (with a distance of 3.53 A) and AgAg interactions (with a distance of 3.30 A). Complex 2 exists as a 3D adamantoid polymer in which each CuI center is coordinated to four azpy ligands in a tetrahedral geometry, the ligands are in turn coordinated to four other CuI centers. The cavities are filled with four other adamantoid units forming five interpenetrating networks. Complexes 3 and 4 are composed of two-dimensional sheets in which the CuII atom is coordinated in an octahedral geometry to two water molecules and four ligands. The ligands are in turn coordinated to four other CuII centers. While the sheets in complex 3 display inclined 2D interpenetration, the sheets in complex 4 are all parallel and isolated, with an intersheet separation of ca. 4.7 A.

Rational Construction of Chiral Octanuclear Metallacycles Consisting of Octahedral Co(III), Square-Planar Pd(II), and Linear Au(I) or Ag(I) Ions This work was supported by a Grant-in-Aid for Scientific Research on Priority Area (no. 11136206, "Metal-Assembled Complexes") from the Ministry of Education, Science, Sports, and Culture.

Octahedral fac(S)-[CoIII(aet)3] molecules (aet=NH2CH2CH2S−) react with square-planar PdII ions to form a sulfur-bridged CoPdII trinuclear complex [Pd{Co(aet)3}2]2+, accompanied by the geometrical isomerization from fac(S) to mer(S). This complex was found to act as a sulfur-donating trinuclear-metalloligand toward linear AuI and AgI ions to afford CoPdM metallacycles with 16 chiral centers, [M{PdII[CoIII(aet)3]2}2]6+ (M=Ag, Au (1)), which were successfully resolved into the (Δ)4(R)12 and (Λ)4(S)12 enantiomers.

Three-Dimensionally Arranged Windmill and Grid Porphyrin Arrays by AgI-Promoted meso–meso Block Oligomerization

The syntheses of soluble windmill and grid porphyrin arrays through the AgI-promoted coupling reaction of 1,4-phenylene-bridged linear porphyrin arrays, which are comprised of a central ZnII β-free porphyrin and flanking peripheral NiII β-octaalkylporphyrins, are described. The coupling reaction is advantageous in light of its high regioselectivity occurring only at the meso-position of the ZnII β-free porphyrin as well as its easy extension to large porphyrin arrays. The windmill porphyrin arrays in turn serve as an effective substrate for further coupling reactions, to give three-dimensionally arranged grid porphyrin arrays. Further the grid porphyrin 12-mer (a tetramer of the linear porphyrin trimer) was also coupled to afford grid porphyrins (24-mer, 36-mer, and 48-mer). These porphyrin arrays were isolated in a discrete form by repetitive GPC/HPLC (GPC=gel-permiation chromatography). Competitive experiments with three linear porphyrin trimers bearing different peripheral metalloporphyrins (ZnII, NiII, and CuII), and the trapping experiment of the radical cation at the peripheral porphyrin with AgNO2, suggested that an initial one-electron oxidation of the easily oxidizable peripheral ZnII β-octaalkylporphyrin with an AgI ion and a subsequent endothermic hole transfer assist the generation of the radical cation at the central ZnII β-free porphyrin. In all ZnII-metallated windmill porphyrin arrays, the energy level of the S1 state of the meso–meso-linked diporphyrin core is lower than that of the peripheral porphyrins, thereby allowing an energy flow from the peripheral porphyrins to the central diporphyrin core; this has been confirmed by measurements of fluorescence lifetimes and picosecond time-resolved fluorescence spectra. The excitation energy transfer in the arrays encourages their potential use as an light-harvesting antenna.

Three-dimensionally arranged windmill and grid porphyrin arrays by AgI-promoted meso-meso block oligomerization

The syntheses of soluble windmill and grid porphyrin arrays through the AgI-promoted coupling reaction of 1,4-phenylene-bridged linear porphyrin arrays, which are comprised of a central ZnII beta-free porphyrin and flanking peripheral NiII beta-octaalkylporphyrins, are described. The coupling reaction is advantageous in light of its high regioselectivity occurring only at the meso-position of the ZnII beta-free porphyrin as well as its easy extension to large porphyrin arrays. The windmill porphyrin arrays in turn serve as an effective substrate for further coupling reactions, to give three-dimensionally arranged grid porphyrin arrays. Further the grid porphyrin 12-mer (a tetramer of the linear porphyrin trimer) was also coupled to afford grid porphyrins (24-mer, 36-mer, and 48-mer). These porphyrin arrays were isolated in a discrete form by repetitive GPC/HPLC (GPC= gel-permiation chromatography). Competitive experiments with three linear porphyrin trimers bearing different peripheral metalloporphyrins (ZnII, NiII, and Cull), and the trapping experiment of the radical cation at the peripheral porphyrin with AgNO2, suggested that an initial one-electron oxidation of the easily oxidizable peripheral ZnII beta-octaalkylporphyrin with an AgI ion and a subsequent endothermic hole transfer assist the generation of the radical cation at the central ZnII beta-free porphyrin. In all ZnII-metallated windmill porphyrin arrays, the energy level of the S1 state of the meso-meso-linked diporphyrin core is lower than that of the peripheral porphyrins, thereby allowing an energy flow from the peripheral porphyrins to the central diporphyrin core; this has been confirmed by measurements of fluorescence lifetimes and picosecond time-resolved fluorescence spectra. The excitation energy transfer in the arrays encourages their potential use as an light-harvesting antenna.

S-Cylindrophanes: From Metal Tweezers to Metal Sandwiches.

Inclusion of AgI and CuI ions by the preorganized cylindrophane cage compound 1 provides the first examples of bis(η6) sandwich complexes of these metals. Locked in a trigonal-planar heteroatom ligand field, the guest ions are shown by NMR spectroscopy to withdraw electron density from the aromatic rings. A statistical study of η6 coordination in the solid state supports the description of arene-metal contacts between 2.5 and 3.5 Å as bonds.

Anion Control in Bipyridylsilver(I) Networks: A Helical Polymeric Array

A helical staircase structure is observed for the layers made from chains of alternating AgI centers and pytz ligands in [Ag(pytz)(NO3)]∞ (pytz = 3,6-di-(4-pyridyl)-1,2,4,5-tetrazine). Decisive for the formation of this array—a view of the structure along the helical axis is shown on the right—is the anionic ligand NO, as shown by the comparison with the analogous PF and BF compounds. These two show parallel chains of alternating AgI ions and pytz ligands held in pairs through weak AgAg contacts and π–π interactions between adjacent pytz ligands.

Silver(I) Sandwich Complexes of Oxa‐Crowned Derivatives of Dithiomaleonitrile

AbstractThe coordination chemistry of the four oxa‐crowned derivatives of dithiomaleonitrile mn‐12S2O2, mn‐15S2O3, mn‐18S2O4, and mn‐21S2O5 as well as of the acyclic bis(methylthio)maleonitrile mn‐S2 with AgI was investigated by X ray structural and spectroscopic methods. The 2:1 complexes (ligand/AgI) [Ag(mn‐12S2O2)2]PF6, [1]PF6, [Ag(mn‐15S2O3)2]PF6, [2]PF6, and [Ag(mn‐S2)2]PF6, [6]PF6, and the 1:1 complexes [Ag(mn‐15S2O3)]ClO4, [3]ClO4, [Ag(mn‐18S2O4)]PF6, [4]PF6, and [Ag(mn‐21S2O5)]PF6 [5]PF6, were obtained with AgPF6 or AgClO4 in MeOH. The stoichiometry of the macrocyclic AgI complexes and the coordination mode of mn‐S2On+1 coronands (n = 1–4) is determined by the length of the macrocyclic oligoethylene chain. – The mn‐crown dithioethers mn‐12S2O2 and mn‐15S2O3 form with AgPF6 the new sandwich complexes [Ag(mn‐12S2O2)2]PF6, [1]PF6, and [Ag(mn‐15S2O3)2]PF6, [2]PF6. [1]PF6 crystallises in the triclinic space group P1. In the centrosymmetric cation [1]+ each mn‐12S2O2 ligand is coordinated to the AgI centre in an endo manner via both S atoms and one O atom. The distance of the second O atom of mn‐12S2O2 to AgI is somewhat longer than a normal Ag–Oether bond. The overall environment around AgI in [1]+ is that of a distorted cubic S4O4 set of donors. [2]PF6 crystallises in the monoclinic space group C2/c. In the centrosymmetric cation [2]+ silver(I) is planar‐coordinated by the four S atoms of both mn‐15S2O3 molecules. The six O atoms of both mn‐15S2O3 ligands show only long‐range interactions to the AgI ion. They surround AgI almost vertically to the planar S4 set of donors in a crown‐like manner. – The crystal structures of the 1:1 complexes [Ag(mn‐18S2O4)]PF6, [4]PF6, and [Ag(mn‐21S2O5)]PF6, [5]PF6, consist of linear chain polymers. [5]PF6 forms an N‐bridged chain polymer of endocyclic [Ag(mn‐21S2O5)]+ units with S1O4NNitrile coordination at the AgI centre. In the 2:1 complex [Ag(mn‐S2)2]PF6, [6]PF6, each mn‐S2 acts as a monodentate NNitrile donor. – 13C‐NMR studies in nitromethane solution confirm that the AgI ions in the complexes of the mn‐crown dithioethers remain coordinated. However, the AgI ion in complex of mn‐S2 is decoordinated.

Polymeric Networks of Silver(I) and Copper(I) Ions Linked by an Anionic Acetonyl Derivative of Tetracyanoethylene

Unexpectedly, the reaction of tetracyanoethylene (TCNE) with acetone yields a tetracyanopentanonide that forms interesting coordination polymers with AgI and CuI ions. [Ag(AcTCNE)] is a layer structure consisting of twofold interpenetrated 2D nets of hexagonal meshes, while [Cu(AcTCNE)]·Me2CO consists of a zeolite-like 3D network, whose large channels contain guest acetone molecules (shown on the right).