Polymeric Silver Research Articles

Synthesis and X-ray characterization of helical polymer complexes [Ag(1,2,3-L)(PPh3)2]n and [Ag(1,2,4-L)(PPh3)2]n (HL = triazole) and their antimicrobial activities

Two novel polymeric silver(I)–triphenylphosphine complexes with nitrogen-containing heterocycles, [Ag(1,2,3-L)(PPh3)2]n 3 and [Ag(1,2,4-L)(PPh3)2]n 4 (HL = triazole) were synthesized from reactions of polymeric precursors [Ag(1,2,3-L)]n 1 and [Ag(1,2,4-L)]n 2 with 3 equivalents of PPh3 in CH2Cl2, respectively. The polymeric precursors 1 and 2 have been obtained as non-crystalline, colorless powder-solids: 2 showed a wide spectrum of excellent antibacterial activities, but 1 did not. The antimicrobial activities of the complexes 1–4, evaluated by minimum inhibitory concentration, were compared and key factors affecting them discussed. The crystal structures of the complexes 3 and 4 were determined by single-crystal X-ray diffraction. The complexes 3 and 4 in the solid state were helical polymers consisting of AgN2P2 cores formed by bridging triazolate anions and two PPh3 ligands. The complexes 3 and 4 were also fully characterized by elemental analyses, TG/DTA and FT-IR in the solid state and by various solution NMR (31P, 109Ag, 1H and 13C) spectroscopies and molecular weight measurements in solution.

A double sandwich silver(I) polymer with 1,1′-bis(diethyldithiocarbamate)-ferrocene

The polymeric complex [Ag{Fc(S2CNEt2)2}]n[ClO4]n, in which the silver centres are bonded to two sulfur atoms of different ferrocene moieties and also to the cyclopentadienyl rings in an η2 fashion, is reported.

Platinum(II)-Silver(I) Polymers Bearing Platinum(II) Clusters Containing Chelated P,P- and Bridged P, N-2-Pyridylphosphine Ligands

Reactions PtI2L (L = P,P-bonded 1,2-bis ((2-pyridyl)phosphino(ethane, d(py)pe, or 1,2-bis ((2-pyridyl)phosphino)cyclopentane, d(py)pcp) with excess AgNO3 in acetic acid/ethanol afford the polymers [Pt2(d(py)pe)2Ag4(NO3)8(H2O)2]n(1 ) and [Pt2(d(py)pcp)2Ag6(NO3)10] n (2), respectively, which contain Pt2L 2 4+ cores with each L ligand nowP,N-bridging two Pt-atoms; these Pt2 cores are connected via bridging AgNO3 clusters, the Ag being bound to the pyridyl-N or nitrate-O atoms. X-ray crystallographic data reveal Pt–Pt contacts of ∼2.76 A indicative of bonding.

Polymeric Based Conducting Nanocomposites: Controlling The Distribution of the Conducting Phase

AbstractThe optimization of bulk properties of polymeric based nano– and mesoscale composites require the ability to spatially control phase distribution. In this study, electrical conductivity is introduced by incorporation of a metal precursor via infiltration into the polymer host and subsequent conversion in–situ by a reducing agent, templating the morphology of the polymer matrix. Distribution of nano– and mesoscale metal particles in isotropic and anisotropic swollen polymer hosts is discussed relative to metal precursor and reducing reagent diffusion and their in–situ bimolecular reduction reaction. The swelling and infiltration procedure employed to form the composites is generally applicable to rigid–rod, semi–flexible and flexible polymer matrices and not restricted to special synthesis of metal containing or complexing polymers. As an example, high–performance rigid–rod polymer fibers containing an interpenetrating network of polymer microfibrils and silver are produced with d.c. conductivities in excess of 104 S/cm and tensile

Ag(I)N bond-containing compound showing wide spectra in effective antimicrobial activities: Polymeric silver(I) imidazolate

A neutral, Ag(I)N bonding compound, polymeric silver(I)-imidazolate [Ag(imd)] n (1) consisting of Ag +: imd = 1:1 (Himd = imidazole, C 3H 4N 2), whowed wide spectra in effective antimicrobial activities against bacteria, yeast and mold. Of particular note are the activities against a wide range of mold. This polymeric solid does not crystallize and is sparingly soluble in all solvents. The monomeric, cationic, water-soluble Ag(I)N bonding complex, [Ag(Himd) 2](NO 3) (2), has also shown wide spectra of effective antimicrobial activities. These activities observed here were significantly different from those of the recently prepared oligomeric (Ag(I)S bonding complexes; the latter have shown narrow spectra. It is proposed that the Ag(I)N bonding is one of the key factors showing the wide spectra of antimicrobial activities and the potential targets for inhibition of bacteria and yeast by these Ag(I) complexes are proteins, but not nucleic acids. The physico-chemical properties of (1), in comparison with those of (2), with various measurements (FT-IR, Laser Raman scattering spectroscopy, ESCA and solid 13C CP-MAS NMR spectroscopies) are described.

Construction and Conductivity of W-Type Sandwich Silver(I) Polymers with Pyrene and Perylene.

Two organosilver(I) compounds of pylene and perylene presented here exhibit an unusual tetra-η2-coordination, bridging four metal centers and leading to W-type sandwich polymeric chains and sheets. Both compounds, show typical radical cation ESR signals upon irradiation with light or iodination.

Silver(I) Ion Induced Monolayer Formation of 2-Substituted Benzimidazoles at the Air/Water Interface

The monolayer formation of a series of 2-substituted benzimidazoles at the air/water interface was studied by the measurements of surface pressure-area isotherms. Concentrated silver(I) ion in the subphase can induce the monolayer formation of 2-alkylbenzimidazole derivatives (BzCn) with the alkyl chain equal to or greater than C5 although the derivatives cannot form monolayers on pure water surface except BzC17. Similar behavior of monolayer formation of 2-phenylbenzimidazole was also observed. The measurements of UV spectra and X-ray photoelectron spectroscopy analysis of the transferred films suggested that such monolayer formation was fulfilled through an in situ formation of a polymeric silver(I)−benzimidazole complex at the air/water interface.

Synthese und Koordinationsverhalten Me2NCH2CH2-funktionalisierter Metallocene von Titan, Vanadium und Chrom

Abstract The reaction of TiCl4 (1a) with two equivalents of Li(C5H4CH2CH2NMe2) (2a) in toluene yields (η5-C5H4CH2CH2NMe2)2TiCl2 (3). In a similar way the vanadocene and chromocene compounds (η5-C5H4CH2CH2NMe2)2M (4a: M = V, 4b: M = Cr) could be obtained. On treatment of the titanocene dichloride 3 with two molar equivalents LiC≡CSiMe3 (5) the bis(alkynyl) titanocene (η5-C5H4CH2CH2NMe2)2Ti(C≡CSiMe3)2 (6) is produced in 82% yield. The reaction of 6 with oligomeric or polymeric copper(I) or silver(I) compounds [M′X]n [7c: M′X = Cu(SC6H4CH2NMe2-2), 8a: M′X = AgCl, 8b: M′X = AgNO2] affords the heterobimetallic titanium—copper or titanium—silver complexes [(η5-C5H4CH2CH2NMe2)2Ti(C≡CSiMe3)2]M′X [9: M′X = Cu(SC6H4CH2NMe2-2), 10a: M′X = AgCl, 10b: M′X = AgNO2], respectively. The bis(η2-alkyne)M′X building block in compounds 9 and 10 represents a 16-valence electron organometallic fragment in which the Group 11 metal atom possesses a trigonal-planar environment. The solid state structures of compounds 6 and 9 are reported. Both complexes crystallize in the monoclinic space group C2/c with the following cell constants: 6, a = 2386(2), b = 651.3(4), c = 2084(1)pm, β = 100.92(5)°, V = 3180(4) × 106 pm3 and Z = 4; 9, a = 3864(2), b = 1261.2(6), c = 1842(1)pm, β = 113.85(4)°, V = 8211(7) × 106 pm3 and Z = 8.

Preparation and crystal structures of two polymeric silver(I) complexes of betaine derivatives

Polymeric silver(I) complexes of two betaine derivatives, namely [{Ag 2(L 1) 2(NO 3)(H 2O)} n ](NO 3) n ( 1) and [{ Ag 4( L 2) 3} n]( ClO 4) 4 4 · 3n H 2O ( 2) [L 1 = 4-dimethylaminopyridinio-acetate, p-Me 2NC 5H 4N +CH 2CO 2 −; L 2 = 1,4-diazoniabicyclo[2.2.2]octane-1,4-dipropionate; −O 2C(CH 2) 2N + (CH 2CH 2) 3N + (CH 2) 2CO 2 −], have been prepared and characterized by X-ray crystallography. Complex 1 exhibits a zigzag chain structure via comparatively weak metal-carboxylate linkages between adjacent bis(carboxylato- O, O′)-bridge dimers, in which the coordination spheres of two independent Ag I atoms are each completed by an unidentate nitrate or aqua ligand at a much longer contact. Complex 2 consists of three independent infinite zigzag chains running parallel to the b direction, in which the Ag I atoms are cross-linked by double betaine ligands in the end-to-end mode. The Ag ··· Ag separation [2.750(2)_Å] in one infinite chain based on bis(carboxylato- O, O′)-bridged centrosymmetric dimeric units is the shortest one hitherto found among silver(I) complexes and hence indicative of a significantly stronger metal-metal interaction.

Polymeric silver(I) complexes of the multinucleating ligand 4,7-dihydro-5-methyl-7-oxo[1,2,4]triazolo[1,5-a]pyrimidine. Analogous hydrogen-bonded structures in the crystal and vapour phases of the ligand

X-Ray crystallography showed that the crystal structure of Hmtpo (4,7-dihydro-5-methyl-7-oxo[1,2,4]triazolo[1,5-a]pyrimidine) is built up of hydrogen-bonded polymeric chains, whereas mass spectroscopy and solution 15 N NMR spectroscopy suggested the existence of a dimeric structure comprising eight-membered · · · H–N –C–N · · · H–N –C–N rings in less condensed phases. On the other hand, the reaction between the silver(I) salts AgX (X = NO 3 , ClO 4 or ½SO 4 ) and Hmtpo yielded polymeric complexes. The compounds have been structurally characterised by IR spectroscopy and X-ray crystallography. The X-ray results show that the compounds containing the Hmtpo derivative in its neutral form comprise infinite one-dimensional chains, in which the ligand bridges the metal centres through N(1) and N(3) donor atoms. The presence of an additional soft and bulky ligand such as triphenylphosphine in [{AgX(µ-Hmtpo-κ 2 N 1 ,N 3 )(PPh 3 )} n ] (X = NO 3 or ClO 4 ) partially changes the tendency to form polymeric complexes, lengthening the Ag–N(1) bond distance by 0.35 A. Finally, deprotonation of Hmtpo results in an additional available coordination position at N(4), the ligand bridging three metal centres in [{Ag 3 (µ 3 -mtpo-κ 4 N 1 ,N 3 ,N 4 ,O 7 ) 2 (HSO 4 )(H 2 O) 2 ]·H 2 O} n ]. The new co-ordination mode results in the formation of eight-membered Ag–N–C–N–Ag–N–C–N rings, which give rise to short intermetallic contacts of 3.078(1) A. The structures of free Hmtpo in the solid state and the postulated vapour-phase structure are compared to those of linear co-ordinated silver(I) complexes.

Coordination modes of the cyanoacetate ion; silver(I) and bis(η-cyclopentadineyl)tatinium(IV) cyanoacetates. X-ray crystal structures of [Ag(NCCH 2CO 2)] and [TiCp 2(NCCH 2CO 2) 2

Polymeric silver(I) cyanoacetate contains the classical bis(carboxylato- O, O′) bridged metal dimer arrays in which each pair of adjacent metal atoms is doubly bridged by co-planar carboxylate groups in the syn-syn conformation. These dimeric units are extended into a polymeric chain by terminal linkage of all cyano-nitrogen atoms to silver atoms of adjacent dimer units. In this manner, an individual cyanoacetate anion is O, O′, N-bonded to three different silver centres. EHMO calculations suggest weak direct metal-metal interactions can result from the mixing of metal s and p orbitals into the d 10 shells. Reactions of silver(I) or sodium cyanoacetates with [(η-C 5H 5) 2TiCl 2] afford the bis(cyanoacetato) complex [(η-C 5H 5) 2Ti(O 2CCH 2CN) 2] which has a solid state structure involving O-unidentate carboxylate groups, the cyano-nitrogen atoms not being bonded to a metal. This compound can also be prepared from [(η-C 5H 5) 2Ti(CH 3) 2] and cyanoacetic acid.

Synthesis and NMR studies of silver complexes with octaaza Schiff-base cryptands and the structure of a polymeric silver cryptate

Four binuclear and one polymeric silver of octaaza Schiff-base cryptands were synthesized by [2+3] condensation of tris(3-aminopropyl)amine (trpn) or tris(2-aminoethyl)amine (tren) with 5-R-2-methoxyl-1,3-benzenedicarboxaldehyde (R = OCH 3, CH 3, Br or Ph) in the presence of excess of Ag I ion. The polynucleating and extended coordination nature of the trpn-derived cryptand L 1 (R = OCH 3) was established by X-ray structure of [{Ag(Ag 2L 1)} n][(ClO 4) 3·2CH 3CN·CH 3OH·2 H 2O n . The polymeric cation [{Ag(Ag 2L 1)} n ] can be described as the bridge-twisted binuclear (Ag 2L 1) units linked together by silver atoms via a linear NAgN bridging bonding mode in alternate (inward, outward) conformations relative to the benzene rings, resulting in an infinite single helical chain. The benzene rings in the helix chain are almost parallel to each other, with a π-π stacking distance of 3.84 Å. The coordination behaviour of cryptands have also been studied by NMR spectroscopy in solution.

The FT-Raman Study of Reaction of 4-Aminophenyl Disulfide and Epoxy on Silver Surface

Abstract 4-Aminophenyl disulfide (APDS) can cleave and be chemisorbed on etched silver foil to form an assembled film. The film can serve as coupling agent to form an inter phase between silver and epoxy bulk. The coupling action and mechanism of APDS between silver and epoxy polymer were characterized by Fourier transform surface-enhanced Raman scattering spectroscopy.

Synthesis and Structure of Polymeric Silver(I) Complex of Tetrakis(methylthio)-tetrathiafulvalene: The First Example of the Silver(I) Ion Coordinated Directly to TTF-Derivatives

Abstract Reaction of silver(I) trifluoromethanesulfonate with tetrakis(methylthio)tetrathiafulvalene (TMT-TTF) yielded polynuclear silver(I) complex [Ag(TMT-TTF)(O3SCF3)]. The compound crystallizes in the orthorhombic system, space group Pbam with cell constants a = 14.855(5), b = 22.510(3), c = 13.310(8) A, Z = 8. It is a neutral 1: 1 metal/ligand complex in which each Ag(I) ion is six-coordinated by four sulfur atoms from the bridging TMT-TTF and two oxygen atoms from the bidentate O3SCF3 anion, which results in a two interwoven polymeric chain structure. It represents the first example of the silver(I) ion coordinated directly to TTF-derivatives. The compound is an insulator at room temperature but behaves as a semiconductor when doped with iodine.

Two Types of New Polymeric Silver(I) Complexes from 1,4-Thioxane and Silver Triflate.

Two Types of New Polymeric Silver(I) Complexes from 1,4-Thioxane and Silver Triflate.

Crystal Structures of Polymeric Complexes of Silver(I) Nitrate and Silver(I) Perchlorate With 1,4-Diazoniabicyclo[2.2.2]octane-1,4-diacetate

Two novel polymeric silver(I) complexes of a double betaine with a rigid tris (ethylene) bridge between the pair of nitrogen atoms, viz. [{Ag4(L)3(NO3)2}n] (NO,3)2n.nH,2O (1) and [{Ag4(L)3(ClO4)2}n] (ClO4)2n.-nEtOH (2) [L = -O2CCH2N+ (CH2CH2)3N+CH2CO2-], have been prepared and characterized by X-ray crystallography. Complexes (1) and (2) are both based on a two-dimensional framework constructed by the interlinkage of adjacent infinite belt-like zigzag chains, in which the uncoordinated NO3- groups and lattice water molecules in (1), and uncoordinated ClO4- groups and ethanol molecules in (2), are packed into the resulting pockets. Most atoms of the chains in (1) are centred about the (200) family of planes, whereas those in (2) are non-coplanar, and adjacent chains are cross-linked by strong Ag-O coordinate bonds in (2) but only weak Ag...Ag interactions in (1).

2D Polymeric Silver(I) Complexes Consisting of Markedly Undulated Sheets of Squares. X-ray Crystal Structures of [Ag(ppz)2](BF4) and [Ag(pyz)2](PF6) (ppz = Piperazine, pyz = Pyrazine)

ADVERTISEMENT RETURN TO ISSUEPREVArticle2D Polymeric Silver(I) Complexes Consisting of Markedly Undulated Sheets of Squares. X-ray Crystal Structures of [Ag(ppz)2](BF4) and [Ag(pyz)2](PF6) (ppz = Piperazine, pyz = Pyrazine)Lucia Carlucci, Gianfranco Ciani, Davide M. Proserpio, and Angelo SironiCite this: Inorg. Chem. 1995, 34, 22, 5698–5700Publication Date (Print):October 1, 1995Publication History Published online1 May 2002Published inissue 1 October 1995https://doi.org/10.1021/ic00126a048RIGHTS & PERMISSIONSArticle Views204Altmetric-Citations73LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (348 KB) Get e-AlertsSupporting Info (2)»Supporting Information Supporting Information Get e-Alerts

Electron beam induced coalescence in plasma polymer silver composite films

Plasma polymer thin films with embedded silver particles (5-50 nm) were irradiated by a small focussed electron beam of 10 kV. Before and after irradiation the films were investigated by transmission electron microscopy (TEM) to characterize the microstructure given by size and shape of the embedded silver particles. The changes of the microstructure after the electron beam irradiation were limited to small lines (<2 μm). Most changes were coalescence of the silver particles. Furthermore, after increased irradiation time and higher energy input areas nearly free of silver particles but without destruction of the plasma polymer matrix were found.

Powder route to crystal structures: X-ray powder diffraction determination of polymeric silver imidazolate

Silver imidazolate has been synthesized and its solid-state structure determined, ab initio, from conventional X-ray powder diffraction data only. The crystals are orthorhombic, space group P212121, with a= 5.5759(4), b= 6.7452(4), c= 22.174(1)A, U= 834.0(1)A3, Z= 8, Dc= 2.786 g cm–3. The structure was solved by a real-space scavenger technique and refined by the Rietveld method down to RP and RF values of 0.062 and 0.027, respectively, for 4401 data points (1262 reflections) measured at room temperature in the 17–105°(2θ) range. The crystal structure of [{Ag(im)}n](Him = imidazole) consists of a complex packing of polymeric chains folding about the crystallographic c axis, containing linearly co-ordinated silver atoms joined by imidazolate fragments. Short interchain Ag ⋯ Ag contacts [3.161(4)A] were observed.

Studies on the preparation and properties of conductive polymers. VII. Use of two‐stage method to prepare Ag–Hg alloy on polymer films

AbstractPolymer metal chelate films were prepared by silver nitrate mixed with polymers containing functional groups such as poly(vinyl alcohol) (PVA) by using two‐stage method to prepare Ag–Hg alloy on polymer films. In the first stage, polymer silver chelate was treated with doping agents. In the second stage, these treated films were further treated with Hg metal. After the two stage treatment, films with good electrical conductivity can be obtained. © 1994 John Wiley & Sons, Inc.