AgI Ions Research Articles

A novel polyoxometalate-based metal-organic compound constructed from an unprecedented [Ag8(Hpyttz)4(H2pyttz)2] cluster and an in-situ [VW12O40]3 − anion

A novel polyoxometalate (POM)-based metal-organic compound constructed from a multinuclear AgI cluster and Keggin-type [VW12O40]3− anion, [Ag4(Hpyttz)2(H2pyttz)][HVW12O40]·3H2O (1) (H2pyttz=5′-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole), was hydrothermally synthesized and characterized by IR spectroscopy, TG analysis, powder and single-crystal X-ray diffraction. In compound 1, [VW12O40]3− (VW12) was in-situ transformed from [SiW12O40]4− anion. Eight AgI ions were connected by six Hpyttz/H2pyttz ligands with three coordination modes forming an unprecedented [Ag8(Hpyttz)4(H2pyttz)2] cluster, which connected with six VW12 anions to construct a 2-D double-layer (3,6)-connected network with {43}2{46.66.83} topology. Moreover, the photocatalytic activity of 1 has been investigated.

Influence of N-donor sites in 5-(x-pyridyl)-1H-tetrazole ligands (x = 2, 4) on assembly of polyoxometalate-based compounds modified by multinuclear metal clusters and infinite chains

Through tuning the N-donor site of the pyridyl group in 5-(x-pyridyl)-1H-tetrazole ligands (x = 2, 4), four new Keggin-based compounds, [Cu7(2-ptz)8(OH)2(H2O)2(HPMoVI10MoV2O40)]·4H2O (1), [Cu5(2-ptz)6(HPMoVI10MoV2O40)(H2O)4]·4H2O (2), [Ag6(4-ptz)4(H2SiMo12O40)] (3) and [Ag5(4-ptz)4(H2PMo12O40)]·5H2O (4) (2-ptzH = 5-(2-pyridyl)-1H-tetrazole, 4-ptzH = 5-(4-pyridyl)-1H-tetrazole), were successfully synthesized under hydrothermal conditions and structurally characterized. Compound 1 possesses two kinds of CuII subunits: penta-nuclear clusters and mono-nuclear subunits, which connect with each other to form a one dimensional (1D) stair-like metal–organic chain. The adjacent 1D stair-like chains are further linked by tetradentate Keggin anions to construct a 2D layer. In compound 2, the tetra-nuclear CuII clusters and mono-nuclear CuII subunits construct a 2D metal–organic layer, which is further linked by bidentate Keggin anions to build a 3D framework. In compound 3, the 4-ptz ligand links AgI ions with tetrazole groups to form 1D infinite Ag–ptz chains, which are extended by the pyridyl group of 4-ptz and the tetrazole groups of other 4-ptz molecules to construct a 2D layer. The adjacent 2D layers are further linked by 6-connected Keggin anions to build a 3D framework. In compound 4, the 4-ptz ligands are linked by AgI ions to form 1D infinite Ag–ptz belts. The Keggin anions are linked by AgI ions to construct another infinite inorganic chain, in which each Keggin anion provides six oxygen atoms to coordinate with the AgI ions from adjacent Ag–ptz belts to construct a 2D layer. The roles of the ptz ligands with different N-donor sites in the construction of multinuclear clusters and 1D chains are discussed. The electrochemical and photocatalytic properties of the title compounds were investigated as well.

G-quadruplex-based logic gates for HgII and AgI ions employing a luminescent iridium(iii) complex and extension of metal-mediated base pairs by polymerase.

We report herein the synthesis of a series of cyclometallated iridium(iii) complexes as luminescent G-quadruplex-selective probes, which were used to construct AND, OR and INHIBIT logic gates for the detection of HgII and AgI ions. To our knowledge, this is the first time that the C-AgI-T mismatched base pair has been used for the construction of luminescent assays or logic gates.

Synthesis of Nanometer-Sized Cylinder-Like Structures from a 1,3,5-Triphenylbenzene-Bridged Tris-NHC Ligand and AgI, AuI, and CuI

The metal-controlled self-assembly of nanometer-sized trinuclear cylinder-like assemblies is described. The 1,3,5-triphenylbenzene-derived trisimidazolium salt [1](PF6)3 reacts with 1.5 equiv of Ag2O to yield the trinuclear AgI hexacarbene complex [2](PF6)3, where three AgI ions are sandwiched in between two C3-symmetric tris-NHC ligands. Transmetalation of [2](PF6)3 with 3 equiv of [AuCl(SMe2)] or CuI yields the trinuclear AuI hexacarbene complex [3](PF6)3 or the trinuclear CuI hexacarbene complex [4](PF6)3, respectively, with retention of the metallosupramolecular structure. The 1,3,5-triphenylbenzene ligand in the gold complex adopts a nonplanar geometry to allow π interactions between the central phenyl rings.

Nanomolar Detection of AgI Ions in Aqueous Medium by Using Naphthalimide‐Based Imine‐Linked Fluorescent Organic Nanoparticles – Application in Environmental Samples

AbstractThe synthesis of fluorescent organic nanoparticles (FONPs) with an imine‐linked 1,8‐naphthalimide‐based dipodal chemosensor for AgI is described. The FONPs were prepared by using a re‐precipitation method, and they were successfully applied for the nanomolar detection of AgI ions in aqueous media. More specifically, the chemosensor was utilized for the selective and ratiometric sensing of AgI in a concentration range 15–65 nM with a 15.5 nM detection limit. The work was extended to monitor the AgI concentration in samples of environmental importance.

Crystal structure of (1,3-di-methyl-thio-urea-κS)tris-(tri-phenyl-phosphane-κP)silver(I) acetate.

In the mononuclear title salt, [Ag(C3H8N2S)(C18H15P)3](CH3COO), the AgI ion exhibits a distorted tetra­hedral coordination sphere defined by three P atoms from three tri­phenyl­phosphane ligands and one S atom from a 1,3-di­­methyl­thio­urea ligand. In the crystal, the acetate anion is linked with the complex cation via duplex N—H⋯O hydrogen bonds [graph-set motif R 2 2(8)].

A Tray‐Shaped, PdII‐Clipped Au3 Complex as a Scaffold for the Modular Assembly of [3×n] Au Ion Clusters

AbstractA tray‐shaped PdII3AuI3 complex (1) is prepared from 3,5‐bis(3‐pyridyl)pyrazole by means of tricyclization with AuI followed by PdII clipping. Tray 1 is an efficient scaffold for the modular assembly of [3×n] AuI clusters. Treatment of 1 with the AuI3 tricyclic guest 2 in H2O/CH3CN (7:3) or H2O results in the selective formation of a [3×2] cluster (1⋅2) or a [3×3] cluster (1⋅2⋅1), respectively. Upon subsequent addition of AgI ions, these complexes are converted to an unprecedented Au3–Au3–Ag–Au3–Au3 metal ion cluster.

Unprecedented application of flexible bis(pyridyl-tetrazole) ligands to construct helix/loop subunits to modify polyoxometalate anions.

By introducing the unprecedented and flexible isomeric bis(pyridyl-tetrazole) ligands into a polyoxometalates (POMs) system, three POM-based compounds, {Ag2(4-bptzb)2(H2O)2[H2PMo12O40]2}·4-bptzb·5H2O (1), [Ag4(3-bptzb)2(PMo(V)Mo(VI)11O40)]·2H2O (2), and Ag3(3-bptzb)2.5(H2O)2[H3P2W18O62] (3) [4-bptzb = 1,4-bis(5-(4-pyridyl)tetrazolyl)butane and 3-bptzb =1,4-bis(5-(3-pyridyl)tetrazolyl)butane], were synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction analyses. Compound 1 exhibits a dimeric structure constructed from two Keggin [PMo12O40](3-) anions and a binuclear [Ag2(trans-4-bptzb)2](2+) subunit in which the trans-4-bptzb acts as a bidentate bridging ligand with one tetrazolyl group. In 2, the 3-bptzb acts as a tetradentate bridging ligand with the tetrazolyl and pyridyl groups linking Ag(I) ions to generate a 3D metal-organic framework (MOF), which contains charming meso-helix chains. The Keggin anions acting as bidentate inorganic ligands reside in the distorted tetragonal channels of the MOF. In compound 3, the 3-bptzb adopts versatile coordination modes linking Ag(I) ions to first construct loop connecting loop 1D chains, which are linked by {Ag[P2W18O62]}n zigzag chains to form a scarce hamburger-style 2D sheet. These adjacent sheets are further fused by 3-bptzb ligands to construct a 3D framework. The influences of isomeric bptzb ligands and POMs on the construction of Ag-bptzb subunits and the whole structures of the title compounds are discussed. The electrochemical behaviors and electrocatalytic activities of compounds 2 and 3 and their corresponding parent POMs as well as the fluorescent properties of the title compounds have been studied in detail. In addition, the photocatalytic activities of compounds 2 and 3 and their corresponding parent POMs for decomposition of methylene blue, rhodamine B, and methyl orange under UV irradiation have also been investigated.

Ag I ‐Directed Triple‐Stranded Helicates with meta ‐Ethynylpyridine Ligands

A series of triple-stranded complexes, [1a3Ag]BF4, [1b3Ag]BF4, [2a3Ag2](BF4)2, [2b3Ag2](BF4)2, and [33Ag3](BF4)3, have been obtained through the self-assembly of AgI ions with p-phenylene ethynylpyridine ligands. X-ray crystallographic studies unambiguously demonstrated a AgI-directed monodentate triple-stranded helical structure in the solid state for 1b and 2b. A combination of NMR spectroscopy, HRMS (ESI), and isothermal titration microcalorimetry studies further confirmed that strands 1, 2, and 3 are also able to form triple-stranded helical structures in the presence of AgI ions in solution.

Regulated Incorporation of Two Different Metal Ions into Programmed Sites in a Duplex by DNA Polymerase Catalyzed Primer Extension

AbstractMetal‐mediated base pairs formed by the coordination of metal ions to natural or artificial bases impart unique chemical and physical properties to nucleic acids and have attracted considerable interest in the field of nanodevices. AgI ions were found to mediate DNA polymerase catalyzed primer extension through the formation of a C–AgI–T base pair, as well as the previously reported C–AgI–A base pair. The comparative susceptibility of dNTPs to AgI‐mediated enzymatic incorporation into the site opposite cytosine in the template was shown to be dATP>dTTP≫dCTP. Furthermore, two kinds of metal ions, AgI and HgII, selectively mediate the incorporation of thymidine 5′‐triphosphate into sites opposite cytosine and thymine in the template, respectively. In other words, the regulated incorporation of different metal ions into programmed sites in the duplex by DNA polymerase was successfully achieved.

Heterocyclic‐2‐thione Derivatives of Silver(I): The Methyl Substituent at N1atom of a Imidazoline‐2‐thione/Imidazolidine‐2‐thione Alters a Dimer [Ag2(HL)4(PPh3)2](NO3)2 into a Monomer [Ag(HL)2(PPh3)](NO3)

AbstractReactions of silver(I) nitrate with 1,3‐imidazolidine‐2‐thiones (LI‐NH, LI‐NMe), 1,3‐imidazoline‐2‐thiones (LII‐NH, LII‐NMe), and that of silver(I) acetate with thiazolidine‐2‐thione (LIII‐NH), or benz‐imidazoline‐2‐thione (LIV‐NH) and triphenylphosphine (PPh3) as co‐ligand (1:2:2 molar ratios) in acetonitrile, acetonitrile‐methanol, or acetonitrile‐acetone mixtures have yielded mono‐ and dinuclear complexes of stoichiometry: [Ag2{µ‐(LI‐NH‐S)}2(LI‐NH‐S)2(PPh3)2](NO3)2·2CH3OH (1), [Ag(LI‐NMe‐S)2(PPh3)](NO3) (2), [Ag2{µ‐(LII‐NH‐S)}2(LII‐NH‐S)2(PPh3)2](NO3)2·2CH3OH (3), [Ag(LII‐NMe‐S)2(PPh3)](NO3) (4), [Ag(LIII‐NH‐S)(LIII‐N‐S)(PPh3)2] (5), and [Ag(LIV‐NH‐S)2(PPh3)2](OAc)·H2O (6). In complex 5, one thio ligand is anionic (LIII‐N–), whereas all other complexes have neutral thio ligands bonded to AgI ion. The complexes were characterized using elemental analysis, IR, 1H and 31P NMR spectroscopy and single crystal X‐ray crystallography. It is interesting to note that LI‐NH and LII‐NH ligands formed dinuclear complexes 1 and 3 with four‐coordination around each metal center, whereas the presence of a methyl group at one nitrogen atom (i.e. LI‐NMe and LII‐NMe) yielded mononuclear complexes 2 and 4 with three‐coordination around each metal center. The ligands LIII‐NH and LIV‐NH behaved differently.

Sonochemical syntheses of one-dimensional silver(I) supramolecular polymer: A precursor for preparation of silver nanostructure

Nano-structures of one-dimensional supramolecular polymer, [Ag(Me-8-HqH)(Me-8-Hq)]n (1) [Me-8-HqH=2-methyl-8-hydroxyquinoline], have been synthesized by the reaction of Me-8-HqH and AgNO3 by sonochemical process. The single-crystal X-ray data of compound 1 shows that both two AgI ions are chelated by two Me-8-HqH and Me-8-Hq− molecules. Coordination number of AgI ions in compound 1 is four and they have AgO2N2 coordination sphere. The AgI complexes in 1 are linked to each other via hydrogen bonding and form a supramolecular chain structure. Thermal decomposition of compound 1 nanostructure in oleic acid results in formation of silver nano-structure. These nano-structures were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The thermal stability of compound 1 was studied by thermogravimetric (TG) and differential thermal analyses (DTA).

Homochiral Silver-Based Coordination Polymers Exhibiting Temperature-Dependent Photoluminescence Behavior

Homochiral coordination polymers based on zigzag or helical polymers are assembled from a semiflexible fluorescent bipyridyl ligand and linear coordinated Ag(I) ions; they exhibit unusual temperature-dependent photoluminescence behavior, including multistep changes in energy and intensity upon cooling.

Di-aqua-{μ2-N,N'-bis-[(cyclo-hexa-nyl-idene)amino]-oxamide}-bis-(tri-phenyl-phosphane)silver(I) dinitrate.

The dinuclear title compound, [Ag2(C14H22N4O2)(C18H15P)2(H2O)2](NO3)2, lies across an inversion center and consists of two [Ag(H2O)(PPh3)] units bridged by a bis­(cyclo­hexa­none)oxalydihydrazone ligand. The charge-balance is supplied by two nitrate anions. The symmetry-unique AgI ion is in a distorted tetra­hedral geometry coordinated by a P atom from a tri­phenyl­phosphane ligand, an O atom from a water mol­ecule and a bis­(cyclo­hexa­none)oxalydihydrazone ligand bidentate chelating through the O atom and one of N atoms. In the crystal, O—H⋯O and N—H⋯O hydrogen bonds link the components, forming chains along the b-axis direction. These chains are connected through weak C—H⋯O hydrogen bonds, leading to the formation of a two-dimensional supra­molecular network parallel to (001).

A series of bimetallic chain coordination polymers bearing [Ag(PPh3)2] chromophores: Synthesis, structure and luminescence

Abstract A series of three cyanide-bridged chain coordination compounds with the formulae [M(CN)2(PPh3)2Ag]n (M is Ag, Cu or Au) is presented. The compounds have been prepared by room temperature reactions of triphenylphosphane with the cyanide salts of silver(I), copper(I) and gold(I). The compounds are characterised with IR, elemental analyses, SEM-EDX and X-ray powder diffraction, and the molecular structures were elucidated by single crystal X-ray diffraction. The three compounds are best described as one-dimensional cyanide-bridged chain coordination polymers, where the tetrahedral AgI ions are coordinated by 2 triphenylphosphane ligands and 2 cyanides, forming a AgN2P2 chromophore. The linear Ag(I), Cu(I) and Au(I) centers are in two-coordinate geometry with C-bound cyanides. No aurophilic or argentophilic interactions are observed, but in the lattice only C-H…π and C-H…M hydrogen bonds are present. The solid-state luminescence properties of the three compounds are discussed and assigned, in agreement with DFT calculations, to MMLCT.

Dinuclear Macrocyclic Quinoline Bridged Mercury and Silver Bis(N‐heterocyclic Carbene) Complexes: Synthesis, Structure, and Spectroscopic Studies

AbstractQuinoline bridged imidazolium precursors 5,8‐bis(N‐R‐imidazolylidenylmethylene)quinoline PF6– salts [H2L](PF6)2 [R = Me (1a), R = naphthylmethyl (1b)] were prepared by quaternization of N‐methylimidazole and N‐naphthylmethylimidazole with 5,8‐bis(bromomethyl)quinoline, respectively. Reaction of the imidazolium ligands 1a and 1b with Hg(OAc)2 and Ag2O in acetonitrile gave the macrocyclic transition metal carbene complexes [Hg2L2](PF6)4 (2a and 2b) and [Ag2L2](PF6)2 (3a and 3b), respectively. All the N‐heterocyclic carbene complexes were characterized in detail by NMR, ESI‐MS, and elemental analysis. Structures of complexes 2a and 3a were determined by X‐ray diffraction studies. Structural studies revealed that the coordination arrangement of the central mercury atom in complex 2a displays a tricoordinate mode and the molecular conformation results in a“closed” form with the bridging quinoline functionality in the macrocycle, whereas the silver complex 3a does not show an coordiantion between the bridging quinoline and the AgI ion, which results in an “open” conformation of the macrocycle. The HgII and AgI NHC complexes showed similar UV absorption and luminescence in acetonitrile solutions.

Bis[2-(thiophen-2-yl)quinoxaline-κN4]silver(I) tetrafluoridoborate

In the title compound, [Ag(C12H8N2S)2]BF4, the two-coordinate AgI ion lies on a crystallographic inversion center and is linearly bonded to the N-donor atoms of two separate quinoxaline ligands. The thio­phenyl ring of the ligand is nearly coplanar with the quinoxaline ring system [dihedral angle = 9.15 (13)°]. In the crystal, the complex mol­ecules pack in layers parallel to (-102) and form weak π–π ring stacking inter­actions [minimum ring centroid separation = 3.7054 (17) Å]. The tetra­fluoridoroborate anion is equally disordered about an inversion center.

The non-centrosymmetric polymorph of (quinolin-8-ol-κ2N,O)(quinolin-8-olato-κ2N,O)silver(I)

The title compound, [Ag(C9H6NO)(C9H7NO)], crystallizes as a non-centrosymmetric polymorph. The structure was previously reported by Wu et al. [(2006). Acta Cryst. E62, m281–m282] in the centrosymmetric space group Pbcn. The AgI ion displays a distorted tetra­hedral coordination geometry defined by two N and two O atoms from a neutral quinolin-8-ol ligand (HQ) and a deprotonated quinolin-8-olate anion (Q−). The dihedral angle between the two ligands is 47.0 (1)°. Strong O—H⋯O hydrogen bonds link the mol­ecules into a supra­molecular chain along the a-axis direction.

Self-assembly of a molecular crown as a structural analogue of calix[4]arene to modify Keggin anions

Four Ag(I) ions are linked by four 5-phenyl-1H-tetrazole (Hptz) units to form a molecular crown [Ag4(ptz)4] as a structural analogue of calix[4]arene, which are further supported by Keggin anions to build a 2D layer containing two kinds of cycles, [Ag8(ptz)4(HPW(V)2W(VI)10O40)]·2H2O (1).

Coordination Polymers of Silver(I) with the Flexible Tritopic Ligand 1,3,5-Tri(4-cyanophenoxy)benzene: Guest Inclusion and Luminescent Properties

A new flexible tritopic ligand, 1,3,5-tri(4-cyanophenoxy)benzene (1), was synthesised by the reaction of phloroglucinol and para-fluorobenzonitrile. Compound 1 crystallises in the non-centrosymmetric space group Pna21. The reaction of ligand 1 with AgBF4 in the presence of different aromatic guest molecules was found to result in coordination polymers, namely, {[Ag3(1)2(BF4)3(H2O)2]·2C7H8·2CH2Cl2}n (2), {[Ag3(1)2(BF4)3(H2O)2]·2C6H6·2CH2Cl2}n (3). The crystal structures of 2 and 3 reveal that ligand 1 is linked by AgI ions into three-dimensional networks containing channels that are occupied by dichloromethane and aromatic guest molecules. The luminescent properties of crystalline 1 and 3 differ significantly.