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1.
Nitrogen donor tetradentate ligands 4,4'-bipyridazine (bpdz) and pyridazino[4,5-d]pyridazine (pp) were prepared by inverse electron demand Diels-Alder cycloaddition reactions of 1,2,4,5-tetrazine. Examination of their behaviour towards silver(i) ions revealed a special potential of the ligands for the design of 3D coordination frameworks involving characteristic polynuclear and polymeric silver(i)-pyridazine motifs and multiple coordination of the ligands. Ag(4)(pp)(5)(ClO(4))(4) and Ag(4)(pp)(5)(SiF(6))(BF(4))(2).4H(2)O adopt a unique 3D trinodal 4,4,5-connected topology based upon five-fold coordination of the metal ions and tetradentate bridging function of the organic modules. Complexes Ag(3)(L)(3)(SO(3)CF(3))(3).nH(2)O and Ag(4)(L)(3)(X)(4).nH(2)O (L = bpdz, pp; X = BF(4)(-), 0.5SiF(6)(2-)) illustrate formation of highly-connected frameworks incorporating trinuclear clusters as an origin of the net connectivity. In the carboxylate complexes Ag(2)(L)(R(F)COO)(2) (R(F) = CF(3), C(2)F(5), C(3)F(7)) the pyridazine and acido ligands act as complementary linkers for generation of 3D frameworks involving helicate motifs. Fused bicyclic pyridazine pp is a unique system combining very efficient sigma(N)-donor ability and pronounced pi-acidity. The coordination frameworks commonly exhibit strong anion-pi interactions, including unprecedented examples of double anion-pi,pi binding that occur between pyridazino[4,5-d]pyridazine as a double pi,pi-receptor for geometry complementary SiF(6)(2-) anions.  相似文献   

2.
The two flexible multidentate ligands 1,3-bis(8-thioquinolyl)propane (C3TQ) and 1,4-bis(8-thioquinolyl)butane (C4TQ) were reacted with AgX (X = CF(3)SO(3)(-) or ClO(4)(-)) to give four new complexes: ([Ag(C3TQ)](ClO(4)))(n)() 1, ([Ag(C3TQ)](CF(3)SO(3)))(n)() 2, ([Ag(2)(C4TQ)(CF(3)SO(3))(CH(3)CN)](CF(3)SO(3)))(n)() 3, and ([Ag(C4TQ)](ClO(4)))(n)() 4. All complexes have been characterized by elemental analysis, IR, and (1)H NMR spectroscopy. Single-crystal X-ray analysis showed that chain structures form for all complexes in which the quinoline rings interact via various intra- (1) or intermolecular (2, 3, and 4) pi-pi aromatic stacking interactions, which in the latter cases results in multidimensional structures. Additional weak interactions, such as Ag.O and Ag.S contacts and C-H.O hydrogen bonding, are also present and help form stable, crystalline materials. It was found that the (CH(2))(n) spacers (n = 3 or 4) affect the orientation of the two terminal quinolyl rings, thereby significantly influencing the specific framework structure that forms. If the same ligand is used, on the other hand, then the different counteranions have the greatest effect on the final structure.  相似文献   

3.
Five novel silver(I) coordination polymers with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3- thienyl)ethene (cis-dbe) were synthesized and are characterized in this paper. Treatment of AgCF(3)SO(3) or AgCF(3)CO(2) with cis-dbe afforded [Ag(2)(cis-dbe)(CF(3)SO(3))(2)] (1) and [Ag(2)(cis-dbe)(CF(3)CO(2))(2)] (2), and both complexes exhibit a 1-D infinite chain structure with two cyano groups and two thienyl groups of the ligand bridging four metal ions. Reaction of AgC(n)()F(2)(n)(+1)CO(2) with cis-dbe gave rise to an unprecedented cocrystallization of a 2-D sheet structure, [Ag(2)(cis-dbe)(C(n)F(2)(n)(+1)CO(2))(2)], where n = 2 (3), 3 (4), and 4 (5). Upon irradiation with 450 nm light, these five silver(I) complexes turned orange or red from yellow, and the color reverted to yellow on exposure to 560 nm light, indicative of the reversible cyclization/ring-opening reaction occurring in the crystalline phase. Furthermore, different anions gave not only the different structural dimensions but also the different photoresponsive patterns. The correlation between the crystal structures and the photochromic reactivity is discussed.  相似文献   

4.
For the purpose of investigating the coordination behavior of the sterically congested alkenes and exploring the possibility of cofacial complexation in the polycyclic aromatic system for formation of extended polymeric networks, tetraphenylethylene (tphe) and 1,1,4,4-tetraphenyl-1,3-butadiene (tphb) have been studied with regard to their complexation with a silver(I) ion. The crystal structures of [Ag(tphe)(ClO4)(p-xylene)], [Ag2(tphe)(ClO4)2], [Ag4(tphe)(CF3SO3)4], [Ag2(tphb)(ClO4)2], and [Ag2(tphb)(CF3SO3)2], together with the metal-free ligands tphe and tphb, have been determined by single-crystal X-ray diffraction. The pi-electron-rich cleft in organic components is found to offer a potential site for complexation, which can be utilized to generate an interesting array of organometallic compounds with one- and two-dimensional frameworks.  相似文献   

5.
Seward C  Chan J  Song D  Wang S 《Inorganic chemistry》2003,42(4):1112-1120
The reaction of AgX, where X = trifluoroacetate (CF(3)CO(2)(-), tfa), nitrate (NO(3)(-)), trifluoromethanesulfonate (triflate, CF(3)SO(3)(-), OTf), hexafluorophosphate (PF(6)(-)), or perchlorate (ClO(4)(-)), with 2,2',3' '-tripyridylamine (tpa) yields five novel silver(I) complexes, which have been structurally characterized. The five complexes have the same 1:1 stoichiometry of Ag/tpa but exhibit different modes of coordination, depending upon the counterion present in the compound. Compound 1, [Ag(tpa)(tfa)](n)(), forms a 1D coordination polymer of [Ag(tpa)(tfa)](2) dimer units linked through bridging tfa counterions. Compound 2, [Ag(tpa)(CH(3)CN)(NO(3))](n), forms a zigzag chain 1D coordination polymer exclusively through Ag-N bonds. In compounds 1 and 2, each tpa ligand is bound to two Ag(I) ions via a 2-py and a 3-py group. Compound 3, [Ag(tpa)(OTf)](n), forms a ribbonlike 1D coordination polymer, in which each tpa ligand binds to three different silver centers via all three pyridyl groups, and the counterion remains coordinated to the Ag(I) center. Compounds 4, [Ag(tpa)(CH(3)CN)](n)(PF(6))(n), and 5, [Ag(tpa)(CH(3)CN)](n)() (ClO(4))(n), display ribbonlike structures resembling that of 3, except that the counterions are not coordinated. All complexes are luminescent in acetonitrile solution, with emission maxima in the near-UV region (lambda(max) = 366, 368, 367, 367, and 368 nm for 1-5, respectively). At 77 K, the emission maxima are red-shifted to lambda(max) = 452, 453, 450, 450, and 454 nm for 1-5, respectively.  相似文献   

6.
As a continuation of the study on the construction of the multidecker aromatic compounds with pi-pi interactions, the anthracene derivatives 9,10-dimethylanthracene (dman), 9,10-diphenylanthracene (dpan), and 7,12-dimethylbenz[a]anthracene (dmban) have been studied toward complexation with the silver(I) ion. The crystal structures of [Ag(dman)(0.5)(p-xylene)(ClO(4))], [Ag(2)(dpan)(0.5)(C(6)H(6))(0.5)(CF(3)SO(3))(2)], and [Ag(2)(dmban)(2)(ClO(4))(2)](p-xylene), together with the metal-free ligand dpan, have been determined by single-crystal X-ray diffraction. These pi-electron-rich aromatic compounds are found to have great promise as an approach to the effective self-assembly of high nuclearity in a multilayer fashion.  相似文献   

7.
Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene L(1), 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L(2), and 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene L(3)) and one tripodal ligand 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L(4) have been prepared. Reaction of these shape-specific designed ligands with different metal salts affords a series of discrete molecular architectures: [Ag(2)L(1)(2)](BF(4))(2) 1, [Ag(2)L(2)(2)](CF(3)SO(3))(2) 2, [CF(3)SO(3)(-) subset Ag(2)L(3)(2)]CF(3)SO(3) 3, [CF(3)SO(3)(-) subset Ag(2)L(3)(3)]CF(3)SO(3) 4, [ClO(4)(-) subset Cu(2)L(2)(4)](ClO(4))(3) 5, [4H(2)O subset Ni(2)L(2)(4)Cl(4)].6H(2)O 6, [BF(4)(-) subset Ag(3)L(4)(2)](BF(4))(2) 7, [ClO(4)(-) subset Ag(3)L(4)(2)](ClO(4))(2) 8, and [CuI(3)(2-) subset Cu(3)L(4)(2)](2)[Cu(2)I(4)] 9. The compounds were characterized by elemental analysis, ESI-MS, IR, and NMR spectroscopy, and X-ray crystallography. 1 is a dinuclear metallacycle with 2-fold rotational symmetry in which two syn-conformational L(1) ligands are connected by two linearly coordinated Ag(+) ions. 2 and 3 are structurally related, consisting of rectangular structures assembled from two linearly coordinated Ag(+) ions and two L(2) or L(3) ligands. The structure of 4 is a trigonal prismatic box consisting of two Ag(+) ions in trigonal planar coordination linked by three L(3) ligands, while the structures of 5 and 6 are tetragonal prismatic cages constructed by two square planar Cu(2+) or Ni(2+) ions linked by four L(2) ligands. The topologies of 7-9 are similar to that of 4; however, these three structures are assembled from three linearly coordinated Ag(+) or Cu(+) ions and two tripodal ligands, representing an alternative strategy to assembling a trigonal prism. (1)H NMR and ESI-MS were utilized to elucidate the solution structures of these macrocycles.  相似文献   

8.
Bu XH  Xie YB  Li JR  Zhang RH 《Inorganic chemistry》2003,42(23):7422-7430
In our efforts to systematically investigate the effects of the linker units of flexible ligands and other factors on the structures of Ag(I) complexes with thioethers, five new flexible pyridyl thioether ligands, bis(2-pyridylthio)methane (L(1)()), 1,3-bis(2-pyridylthio)propane (L(3)()), 1,4-bis(2-pyridylthio)butane (L(4)), 1,5-bis(2-pyridylthio)pentane (L(5)), and 1,6-bis(2-pyridylthio)hexane (L(6)), have been designed and synthesized, and the reactions of these ligands with Ag(I) salts under varied conditions (varying the solvents and counteranions) lead to the formation of eight novel metal-organic coordination architectures from di- and trinuclear species to two-dimensional networks: [Ag(3)(L(1)())(2)(ClO(4))(2)](ClO(4)) (1), [[AgL(3)](ClO(4))]( infinity ) (2), [[Ag(2)(L(4))(2)](ClO(4))(2)(CHCl(3))]( infinity ) (3), [[AgL(4)](ClO(4))(C(3)H(6)O)]( infinity ) (4), [[Ag(2)L(4)](NO(3))(2)]( infinity ) (5), [Ag(2)L(4)()(CF(3)SO(3))(2)]( infinity ) (6), [[AgL(5)](ClO(4))(CHCl(3))](2) (7), and [[AgL(6)()](ClO(4))]( infinity ) (8). All the structures were established by single-crystal X-ray diffraction analysis. The coordination modes of these ligands were found to vary from N,N-bidentate to N,N,S-tridentate to N,N,S,S-tetradentate modes, while the Ag(I) centers adopt two-, three-, or four-coordination geometries with different coordination environments. The structural differences of 1, 2, 3, 7, and 8 indicate that the subtle variations on the spacer units can greatly affect the coordination modes of the terminal pyridylsulfanyl groups and the coordination geometries of Ag(I) ions. The structural differences of 3 and 4 indicate that solvents also have great influence on the structures of Ag(I) complexes, and the differences between 3, 5, and 6 show counteranion effects in polymerization of Ag(I) complexes. The influences of counterions and solvents on the frameworks of these complexes are probably based upon the flexibility of ligands and the wide coordination geometries of Ag(I) ions. The results of this study indicate that the frameworks of the Ag(I) complexes with pyridyl dithioethers could be adjusted by ligand modifications and variations of the complex formation conditions.  相似文献   

9.
Reaction of [2.2]paracyclophane (pcp) with silver(I) trifluoroacetate (AgCF(3)CO(2)) and silver(I) pentafluoroproprionate (AgC(2)F(5)CO(2)) has led to isolation of three novel intercalation polymers: [Ag(4)(pcp)(CF(3)CO(2))(4)](C(6)H(6)) (1), [Ag(4)(pcp)(CF(3)CO(2))(4)](C(6)H(3)Me(3)) (2), and [Ag(4)(pcp)(C(2)F(5)CO(2))(4)](pcp) (3). Structure studies using single crystal X-ray diffraction have shown that all compounds contain two-dimensional layered frameworks based on cation-pi interactions, in which pcp exhibits an unprecedented micro-tetra-eta(2) coordination mode. Guest molecules which weakly interact with the host pcp via C-H.pi interactions are intercalated between layers. The guest-eliminated complexes (1a and 2a) and guest-reincorporated ones (1b or 1c and 2b or 2c), accompanied by small structural changes, were confirmed by (1)H NMR, thermogravimetric analysis, mass spectra, and X-ray powder diffraction patterns. The structural changes from 1 --> 1a --> 1c (=1) can take place reversibly in the process of exposure of 1a to benzene vapor. The original framework of complex 2 is also completely recovered by immersing 2a in mesitylene as well as exposing it to mesitylene vapor.  相似文献   

10.
Studies on the subtle effects and roles of polyatomic anions in the self-assembly of a series of AgX complexes with 2,4'-Py(2)S (X(-) = NO(3)(-), BF(4)(-), ClO(4)(-), PF(6)(-), CF(3)CO(2)(-), and CF(3)SO(3)(-); 2,4'-Py(2)S = 2,4'-thiobis(pyridine)) have been carried out. The formation of products appears to be primarily associated with a suitable combination of the skewed conformers of 2,4'-Py(2)S and a variety of coordination geometries of Ag(I) ions. The molecular construction via self-assembly is delicately dependent upon the nature of the anions. Coordinating anions afford the 1:1 adducts [Ag(2,4'-Py(2)S)X] (X(-) = NO(3)(-) and CF(3)CO(2)(-)), whereas noncoordinating anions form the 3:4 adducts [Ag(3)(2,4'-Py(2)S)(4)]X(3) (X(-) = ClO(4)(-) and PF(6)(-)). Each structure seems to be constructed by competition between pi-pi interactions of 2,4'-Py(2)S spacers vs Ag.X interactions. For ClO(4)(-) and PF(6)(-), an anion-free network consisting of linear Ag(I) and trigonal Ag(I) in a 1:2 ratio has been obtained whereas, for the coordinating anions NO(3)(-) and CF(3)CO(2)(-), an anion-bridged helix sheet and an anion-bridged cyclic dimer chain, respectively, have been assembled. For a moderately coordinating anion, CF(3)SO(3)(-), the 3:4 adduct [Ag(3)(2,4'-Py(2)S)(4)](CF(3)SO(3))(3) has been obtained similarly to the noncoordinating anions, but its structure is a double strand via both face-to-face (pi-pi) stackings and Ag.Ag interactions, in contrast to the noncoordinating anions. The anion exchanges of [Ag(3)(2,4'-Py(2)S)(4)]X(3) (X(-) = BF(4)(-), ClO(4)(-), and PF(6)(-)) with BF(4)(-), ClO(4)(-), and PF(6)(-) in aqueous media indicate that a [BF(4)(-)] analogue is isostructural with [Ag(3)(2,4'-Py(2)S)(4)]X(3) (X(-) = ClO(4)(-) and PF(6)(-)). Furthermore, the anion exchangeability for the noncoordinating anion compounds and the X-ray data for the coordinating anion compounds establish the coordinating order to be NO(3)(-) > CF(3)CO(2)(-) > CF(3)SO(3)(-) > PF(6)(-) > ClO(4)(-) > BF(4)(-).  相似文献   

11.
Fang XQ  Deng ZP  Huo LH  Wan W  Zhu ZB  Zhao H  Gao S 《Inorganic chemistry》2011,50(24):12562-12574
Self-assembly of silver(I) salts and three ortho-hydroxyl and carboxyl groups decorated arenesulfonic acids affords the formation of nine silver(I)-sulfonates, (NH(4))·[Ag(HL1)(NH(3))(H(2)O)] (1), {(NH(4))·[Ag(3)(HL1)(2)(NH(3))(H(2)O)]}(n) (2), [Ag(2)(HL1)(H(2)O)(2)](n) (3), [Ag(2)(HL2)(NH(3))(2)]·H(2)O (4), [Ag(H(2)L2)(H(2)O)](n) (5), [Ag(2)(HL2)](n) (6), [Ag(3)(L3)(NH(3))(3)](n) (7), [Ag(2)(HL3)](n) (8), and [Ag(6)(L3)(2)(H(2)O)(3)](n) (9) (H(3)L1 = 2-hydroxyl-3-carboxyl-5-bromobenzenesulfonic acid, H(3)L2 = 2-hydroxyl-4-carboxylbenzenesulfonic acid, H(3)L3 = 2-hydroxyl-5-carboxylbenzenesulfonic acid), which are characterized by elemental analysis, IR, TGA, PL, and single-crystal X-ray diffraction. Complex 1 is 3-D supramolecular network extended by [Ag(HL1)(NH(3))(H(2)O)](-) anions and NH(4)(+) cations. Complex 2 exhibits 3-D host-guest framework which encapsulates ammonium cations as guests. Complex 3 presents 2-D layer structure constructed from 1-D tape of sulfonate-bridged Ag1 dimers linked by [(Ag2)(2)(COO)(2)] binuclear units. Complex 4 exhibits 3-D hydrogen-bonding host-guest network which encapsulates water molecules as guests. Complex 5 shows 3-D hybrid framework constructed from organic linker bridged 1-D Ag-O-S chains while complex 6 is 3-D pillared layered framework with the inorganic substructure constructing from the Ag2 polyhedral chains interlinked by Ag1 dimers and sulfonate tetrahedra. The hybrid 3-D framework of complex 7 is formed by L3(-) trianions bridging short trisilver(I) sticks and silver(I) chains. Complex 8 also presents 3-D pillared layered framework, and the inorganic layer substructure is formed by the sulfonate tetrahedrons bridging [(Ag1O(4))(2)(Ag2O(5))(2)](∞) motifs. Complex 9 represents the first silver-based metal-polyhedral framework containing four kinds of coordination spheres with low coordination numbers. The structural diversities and evolutions can be attributed to the synthetic methods, different ligands and coordination modes of the three functional groups, that is, sulfonate, hydroxyl and carboxyl groups. The luminescent properties of the nine complexes have also been investigated at room temperature, especially, complex 1 presents excellent blue luminescence and can sensitize Tb(III) ion to exhibit characteristic green emission.  相似文献   

12.
The designed synthesis and structural characterization of two metal cluster-centered metallosupramolecular architectures are reported. In complex [(CF(3)SO(3))Ag(4)((t)BuC≡C)(Py8)](CF(3)SO(3))(2) (1) and [(CF(3)SO(3))Ag(4){C≡C-(m-C(6)H(4))-C≡C-(m-C(6)H(4))-C≡C-(m-C(6)H(4))-C≡C}Ag(4)(CF(3)SO(3))(Py8)(2)](CF(3)SO(3))(4) (2), organic acetylide ligands are utilized to induce the formation of polynuclear silver aggregates, which are encapsulated into the central cavity of the neutral macrocyclic compound azacalix[8]pyridine (Py8). The tetrasilver cluster centered [2]- and [3]-pseudo-rotaxane structures are obtained and fully characterized by X-ray crystallography, ESI mass spectrometry, and (1)H NMR spectroscopy.  相似文献   

13.
Silver(I) coordination complexes with the versatile and biomimetic ligands 1,2,4-triazolo[1,5-a]pyrimidine (tp), 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine (dmtp) and 7-amine-1,2,4-triazolo[1,5-a]pyrimidine (7atp) all feature dinuclear [Ag(2)(μ-tp)(2)](2+) building units (where tp is a triazolopyrimidine derivative), which are the preferred motif, independently of the counter-anion used. According to AIM (atoms in molecules) and ELF (electron localization function) analyses, this fact is due to the great stability of these dinuclear species. The complexes structures range from the dinuclear entities [Ag(2)(μ-tp)(2)(CH(3)CN)(4)](BF(4))(2) (1), [Ag(2)(μ-tp)(2)(CH(3)CN)(4)](ClO(4))(2) (2), [Ag(2)(μ-7atp)(2)](ClO(4))(2) (3) and [Ag(2)(μ-dmtp)(2)(CH(3)CN)](PF(6))(ClO(4)) (4) over the 1D polymer chain [Ag(2)(μ-CF(3)SO(3))(2)(μ-dmtp)(2)](n) (5) to the 3D net {[Ag(2)(μ(3)-tp)(2)](PF(6))(2)·~6H(2)O}(n) (6) with NbO topology.  相似文献   

14.
Metal complexation studies were performed with the ditopic pyrimidine-hydrazone (pym-hyz) strand 6-hydroxymethylpyridine-2-carboxaldehyde (2-methyl-pyrimidine-4,6-diyl)bis(1-methylhydrazone) (1) and Pb(ClO(4))(2)·3H(2)O, Pb(SO(3)CF(3))(2)·H(2)O, Zn(SO(3)CF(3))(2), and Zn(BF(4))(2) to examine the ability of 1 to form various supramolecular architectures. X-ray crystallographic and NMR studies showed that coordination of the Pb(II) salts with 1 on a 2:1 metal/ligand ratio in CH(3)CN and CH(3)NO(2) resulted in the linear complexes [Pb(2)1(ClO(4))(4)] (2), [Pb(2)1(ClO(4))(3)(H(2)O)]ClO(4) (3), and [Pb(2)1(SO(3)CF(3))(3)(H(2)O)]SO(3)CF(3) (4). Two unusually distorted [2 × 2] grid complexes, [Pb1(ClO(4))](4)(ClO(4))(4) (5) and [Pb1(ClO(4))](4)(ClO(4))(4)·4CH(3)NO(2) (6), were formed by reacting Pb(ClO(4))(2)·6H(2)O and 1 on a 1:1 metal/ligand ratio in CH(3)CN and CH(3)NO(2). These grids formed despite coordination of the hydroxymethyl arms due to the large, flexible coordination sphere of the Pb(II) ions. A [2 × 2] grid complex was formed in solution by reacting Pb(SO(3)CF(3))(2)·H(2)O and 1 on a 1:1 metal/ligand ratio in CH(3)CN as shown by (1)H NMR, microanalysis, and ESMS. Reacting the Zn(II) salts with 1 on a 2:1 metal/ligand ratio gave the linear complexes [Zn(2)1(H(2)O)(4)](SO(3)CF(3))(4)·C(2)H(5)O (7) and [Zn(2)1(BF(4))(H(2)O)(2)(CH(3)CN)](BF(4))(3)·H(2)O (8). (1)H NMR studies showed the Zn(II) and Pb(II) ions in these linear complexes were labile undergoing metal ion exchange. All of the complexes exhibited pym-hyz linkages in their cisoid conformation and binding between the hydroxymethyl arms and the metal ions. No complexes were isolated from reacting either of the Zn(II) salts with 1 on a 1:1 metal/ligand ratio, due to the smaller size of the Zn(II) coordination sphere as compared to the much larger Pb(II) ions.  相似文献   

15.
Upon reacting P(4)S(3) with AgAl(hfip)(4) and AgAl(pftb)(4) [hfip = OC(H)(CF(3))(2); pftb = OC(CF(3))(3)], the compounds Ag(P(4)S(3))Al(hfip)(4) 1 and Ag(P(4)S(3))(2)(+)[Al(pftb)(4)](-) 2 formed in CS(2) (1) or CS(2)/CH(2)Cl(2) (2) solution. Compounds 1 and 2 were characterized by single-crystal X-ray structure determinations, Raman and solution NMR spectroscopy, and elemental analyses. One-dimensional chains of [Ag(P(4)S(3))(x)](infinity) (x = 1, 1; x = 2, 2) formed in the solid state with P(4)S(3) ligands that bridge through a 1,3-P,S, a 2,4-P,S, or a 3,4-P,P eta(1) coordination to the silver ions. Compound 2 with the least basic anion contains the first homoleptic metal(P(4)S(3)) complex. Compounds 1 and 2 also include the long sought sulfur coordination of P(4)S(3). Raman spectra of 1 and 2 were assigned on the basis of DFT calculations of related species. The influence of the silver coordination on the geometry of the P(4)S(3) cage is discussed, additionally aided by DFT calculations. Consequences for the frequently observed degradation of the cage are suggested. An experimental silver ion affinity scale based on the solid-state structures of several weak Lewis acid base adducts of type (L)AgAl(hfip)(4) is given. The affinity of the ligand L to the silver ion increases according to P(4) < CH(2)Cl(2) < P(4)S(3) < S(8) < 1,2-C(2)H(4)Cl(2) < toluene.  相似文献   

16.
A self-assembly of AgClO(4) with a Schiff-base ligand N,N'-bis(pyridin-2-ylmethylene)benzene-1,4-diamine (1) gave a 1D zigzag polymeric array [[Ag(2)(C(18)H(14)N(4))(2)](ClO(4))(2)(CH(3)CN)](n) (3), while the self-assembly of AgClO(4) with 3,3'-dimethyl-N,N'-bis(pyridin-2-ylmethylene)biphenyl-4,4'-diamine (2) afforded the molecular rectangle [[Ag(2)(C(26)H(22)N(4))(2)](ClO(4))(2)] (4). The structures of 3 and 4 were characterized by single-crystal X-ray diffraction analysis. Structural data for 3 indicate that the Ag(I) ion is coordinated by two ligands of 1 in a distorted tetrahedral fashion thereby leading to a 1D zigzag polymeric array. The zigzag chains are interdigitated with weak pi-pi stacking interactions. The structure of 4 consists of a discrete molecular rectangle where the silver atom has a distorted square-planar coordination with the pyridyl ligands and azomethine nitrogen atoms of 2. An intramolecular pi-pi interaction between the phenyl rings of adjacent Schiff-base 2 functions to stabilize the rectangular architecture. The Ag(I)-Schiff-base coordination polymer 3 is not stable in solution. The degradation and reorganization of 3 to form a [2 x 2] grid architecture [[Ag(4)(C(26)H(22)N(4))(4)](ClO(4))(4)] (3g) was supported in a FAB-MS study. The rectangular structure of 4 remains intact in solution at ambient temperature. The complexes 3g and 4 exhibit unusual luminescence behavior in solution at room temperature with significantly red-shifted emission in the visible region.  相似文献   

17.
This paper reports novel silver polymers, built with iodine--silver interactions, with interesting structural motifs. Four silver(I) coordination polymers of the aryl iodide derived ligands, triiodobenzoic acid (HL1), tris(4-iodophenyl)amine (L2), and 5,7-diiodo-8-hydroxyquinoline (HL3), have been synthesized and characterized by X-ray crystallography. Treatment of Ag(CH3COO) with HL1 yielded [Ag(L1)] (1), whose structural analysis revealed 2D layers of ladders connected through weak Ag...I interaction. Reactions of AgClO4 and L2 in benzene and nitrobenzene afforded, respectively, two different products, [Ag(L2)(H2O)]ClO4.C6H6(2) and [Ag(L2)(ClO4)](3). While the structure of 2 could be described as a 2D layer of square and octagons perpendicular to [100], complex 3 is formed by 2D layers of the same topology of 2 (8(2).4), alternating as ABAB. In contrast, complex 4, [Ag2(H2L3)(CF3SO3)3], obtained by reaction of Ag(CF3SO3) and HL3, was found to consist of a 2D layer based on columnar arrays AgH2L3-Ag(triflate). The solid-state FT-IR and 109Ag NMR spectra of theses complexes are discussed on the basis of their crystal structures.  相似文献   

18.
The new ligands 1,1,4,4-tetra(1-pyrazolyl)butane [CH(pz)(2)(CH(2))(2)CH(pz)(2), L2] and 1,1,5,5-tetra(1-pyrazolyl)pentane [CH(pz)(2)(CH(2))(3)CH(pz)(2), L3] have been prepared to determine the structural changes in silver(I) complexes, if any, that accompany the lengthening of the spacer group between two linked bis(pyrazolyl)methane units. Silver(I) complexes of both ligands with BF(4)(-) and SO(3)CF(3)(-) as the counterion have the formula [Ag(2)(micro-L)(2)](counterion)(2). These complexes have a cyclic dimeric structure in the solid state previously observed with the shorter linked ligand CH(pz)(2)CH(2)CH(pz)(2). Similar chemistry starting with AgNO(3) for L2 yields a complex of the empirical formula [Ag(2)[micro-CH(pz)(2)(CH(2))(2)CH(pz)(2)](3)](NO(3))(2) that retains the cyclic dimeric structure, but bonding of an additional ligand creates a coordination polymer of the cyclic dimers. In contrast, coordination of the nitrate counterion to silver in the complex of L3 leads to the formation of the coordination polymer of the empirical formula [Ag(micro-CH(pz)(2)(CH(2))(3)CH(pz)(2))]NO(3). All six new complexes have extended supramolecular structures based on noncovalent interactions supported by the counterions and the functional groups designed into the ligands.  相似文献   

19.
Four new potentially polytopic nitrogen donor ligands based on the 1,3,5-triazine fragment, L(1)-L(4) (L(1) = 2-chloro-4,6-di(1H-pyrazol-1-yl)-1,3,5-triazine, L(2) = N,N'-bis(4,6-di(1H-pyrazol-1-yl)-1,3,5-triazin-2-yl)ethane-1,2-diamine, L(3) = 2,4,6-tris(tri(1H-pyrazol-1-yl)methyl)-1,3,5-triazine, and L(4) = 2,4,6-tris(2,2,2-tri(1H-pyrazol-1-yl)ethoxy)-1,3,5-triazine) have been synthesized and characterized. The X-ray crystal structure of L(3) confirms that its molecular nature consists of a 1,3,5-triazine ring bearing three tripodal tris(pyrazolyl) arms. L(1), L(2), and L(4) react with Cu(I), Cu(II), Pd(II) and Ag(I) salts yielding mono-, di-, and oligonuclear derivatives: [Cu(L(1))(Cy(3)P)]ClO(4), [{Ag(2)(L(2))}(CF(3)SO(3))(2)]·H(2)O, [Cu(2)(L(2))(NO(3))(2)](NO(3))(2)·H(2)O, [Cu(2)(L(2))(CH(3)COO)(2)](CH(3)COO)(2)·3H(2)O, [Pd(2)(L(2))(Cl)(4)]·2H(2)O, [Ru(L(2))(Cl)(OH)]·CH(3)OH, [Ag(3)(L(4))(2)](CF(3)SO(3))(3) and [Ag(3)(L(4))(2)](BF(4))(3). The interaction of L(3) with Ag(I), Cu(II), Zn(II) and Ru(II) complexes unexpectedly produced the hydrolysis of the ligand with formation, in all cases, of tris(pyrazolyl)methane (TPM) derivatives. In detail, the already known [Ag(TPM)(2)](CF(3)SO(3)) and [Cu(TPM)(2)](NO(3))(2), as well as the new [Zn(TPM)(2)](CF(3)SO(3))(2) and [Ru(TMP)(p-cymene)]Cl(OH)·2H(2)O complexes have been isolated. Single-crystal XRD determinations on the latter derivatives confirm their formulation, evidencing, for the Ru(II) complex, an interesting supramolecular arrangement of the anions and crystallization water molecules.  相似文献   

20.
Seven new silver(I) complexes of the formula [Ag2(L)2(CF3SO3)2] (1), [Ag2(L)2(CH3SO3)2] (2) [Ag2(L)2](BF4)2 (3), [Ag3(L)2(NO3)2]NO3.5H2O (4), [Ag2(L)(NO3)2].CH3OH (5), [Ag2(L)2](ClO4)2 (6) and [Ag3(L)2(CH3CN)3](ClO4)3 (7) have been synthesized by reactions of 1,3,5-tris(2-oxazolinyl)benzene (L) with varied silver(I) salts under different conditions. The influences of counter anions and reaction conditions on the structure of the complexes are discussed. Three complexes , 1, 2 and 3 with two kinds of different 1D chain structures were obtained under the same synthetic conditions by using different silver(I) salts, and the ligand L was found to adopt bis-monodentate (1 and 2) and tris-monodentate (3) coordination modes respectively. On the other hand, by using the same silver(I) nitrate or silver(I) perchlorate but different reaction solvents, 4 and 5 or 6 and 7 were isolated respectively. Complexes 4and 5 have different 1D chain structures, and 6 is isostructural with . However, 7 is a tri-nuclear, propeller-shaped M3L2 supramolecular capsule in which L adopts a cis,cis,cis-conformation, while the ligand L in 3-6 has cis,trans,trans-conformation. The results revealed that the nature of the counter anions, such as their size, coordination ability and coordination mode, and the reaction conditions all have great impact on the structure of the complexes. The complexes were also characterized by electrospray mass spectrometry. Furthermore, complex 7 exhibited modest second-harmonic-generation (SHG) efficiency.  相似文献   

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