Group 11 complexes with the bis(3,5-dimethylpyrazol-1-yl)methane ligand. How secondary bonds can influence the coordination environment of Ag(I): the role of coordinated water in [Ag2(mu-L)2(OH2)2](OTf)2

The complexation properties of the ligand bis(3,5-dimethylpyrazol-1-yl)methane (L) towards group 11 metals have been studied. The reaction in a 1 : 1 molar ratio with [Cu(NCMe)4]PF6 or Ag(OTf) complexes gives the mononuclear [CuL(NCMe)]PF6 (1), with crystallographic mirror symmetry, or dinuclear [Ag2(mu-L)2](OTf)2 (2) (OTf = trifluoromethanesulfonate) in which the ligand bridges both silver centres, an unprecedented mode of coordination for this type of ligands. Compound 2 crystallizes with two water molecules and forms a supramolecular structure through classical hydrogen bonding. The reaction in a 2 : 1 ratio affords in both cases the four-coordinated derivatives [ML2]X (M = Cu, X = PF6 (3); Ag, X = OTf 4). The treatment of [Ag(OTf)(PPh3)] with the ligand L gives [AgL(PPh3)]OTf (5). The gold(I) derivative [Au2(C6F5)2(mu-L)] (6) has also been obtained by reaction of L with two equivalents of [Au(C6F5)(tht)]. These complexes present a luminescent behaviour at low temperature; the emissions being mainly intraligand but enhanced after coordination of the metal. Compounds 1-4 have been characterized by X-ray crystallography. DFT studies showed that, in the silver complex 2, coordination of H2O to Ag in the binuclear complex is favoured by formation of a hydrogen-bonding network, involving the triflato anion, and releasing enough energy to allow distortion of the Ag2 framework.     

Synthesis, characterization, and chiral properties of CoIII2AgI3 pentanuclear, CoIII4ZnII4 octanuclear, and CoIII mononuclear complexes with aza-capped hexadentate-N3S3 thiolate ligands: crystal structures of

The reaction of an S-bridged Co2(III)Ag3(I) pentanuclear complex, [Ag3[Co(aet)3]2][BF4]3 (aet = NH2CH2CH2S-), with paraformaldehyde in basic acetonitrile, followed by adding aqueous ammonia, produced an aza-capped Co2(III)-Ag3(I) complex, [Ag3[Co(L)]2]3+ ([1]3+) (L = N(CH2NHCH2CH2S-)3). The crystal structure of [1]3+ was determined by X-ray crystallography. [1][PF6]3 x H2O, empirical formula C18H44Ag3Co2F18N8OP3S6, crystallizes in the tetragonal space group 142m with a = 13.012(1) A, c = 24.707(2) A, and Z = 4. In [1]3+ the two aza-capped [Co(L)] units are linked by three Ag(I) atoms, such that the two Co(III) atoms are encapsulated in a macrobicyclic metallocage, [Ag3(I)(L)2]3-. [1]3+ was converted to an aza-capped Co4(III)Zn4(II) octanuclear complex, [Zn4O[Co(L)]4]6+ ([2]6+), by reaction with I- in the presence of Zn2+ and ZnO in water. The crystal structure of [2]6+ was also determined by X-ray crystallography. [2][PF6]6 x 8H2O, empirical formula C36H100Co4F36N16O9P6S12Zn4, crystallizes in the monoclinic space group P2(1/n) with a = 14.33(7) A, b = 25.67(10) A, c = 24.83(6) A, beta = 101.3(3) degrees , and Z = 4. In [2]6+ each of four [Co(L)] units is bound to each trigonal Zn3(II) face of the tetrahedral [Zn4(II)O]6+ core, such that each Co(III) atom is encapsulated in a macrobicyclic [Zn4(II)O(L)] fragment. Treatment of [2]6+ with a basic aqueous solution resulted in a cleavage of the Zn-S bonds to produce an aza-capped Co(III) mononuclear complex, [Co(L)] ([3]), from which [1]3+ is readily reproduced by the reaction with Ag+ in water. All the reactions were found to proceed with retention of the absolute configuration (delta or lambda) of the Co(III) chiral centers; deltadelta-[1]3+, deltadeltadeltadelta-[2]6+, and A-[3] were derived from deltadelta-[Ag3[Co(aet)3]2]3+. The contributions to circular dichroism (CD) from the triple helicity in [1]3+, besides from the asymmetric N and S donor atoms and the Co(III) chiral centers in [1]3+ and [2]6+, were estimated by comparing the CD spectra of deltadelta-[1]3+, deltadeltadeltadelta-[2]6+, and delta-[3].     

含酰胺和席夫碱单元的杯[4]芳烃衍生物的合成与配合性能

杯[4]-1,3-二乙酸乙酯衍生物1与水合肼反应生成杯[4]芳烃酰肼衍生物2, 然后进一步与相应的芳醛反应, 高产率地合成了三个新型的含酰胺和席夫碱单元的杯[4]芳烃衍生物3a～3c和一例新型杯[4]冠醚4. 阳离子萃取实验表明新型杯芳烃衍生物比只含有酰胺基或席夫碱基的杯芳烃衍生物有更强的软金属离子配合性能, 杯[4]冠醚4还对Ag^＋有较好的选择性萃取能力.     

Silver(I) complexes with oxazoline-containing tripodal ligands: structure variation via counter anions and reaction conditions

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.     

Syntheses and structures of Ag(I)-containing coordination polymers and Co(II)-containing supramolecular complex based on novel fulvene ligands

Three new rigid conjugated fulvene ligands L1-L3 were synthesized. L1 and L3 have been prepared by an aroylation reaction of cyclohexyl-substituted cyclopentadienyl anions. L2 was prepared by the reaction of L1 with PhNHNH2 in hot enthanol. Six new coordination polymers, namely [Ag(C25H20N2O2)(ClO4)] x 3.5C6H6 (1), [Ag2(mu-C31H24N4)(eta2-C6H6)(H2O)](ClO4)2 x (C6H6) x (H2O)0.5 (3), [Ag(C31H24N4)]SbF6 x solvate (4), [Ag(C31H24N4)](SbF6)2 x 2C6H6 x CH2Cl2 (5), [Ag(C25H20N2O2)2]SbF6 (6), and [Ag(C25H20N2O2)2]SbF6 (7), and one seven-membered cobaltacycle-containing complex, namely Co(C25H20N2O2)2(C2H5OH)2 (2), were obtained through self-assembly based on these three new fulvene lignads. L2-L3 and compounds 1-7 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The results indicate that the coordination chemistry of new fulvene ligands is versatile. They can bind metal ions not only through the terminal N-donors and fulvene carbon atoms into organometallic coordination polymers but also through the two chelating carbonyl groups into unusual seven-membered metallo-ring supramolecular complexes. In the solid state, ligands L1-L3 are luminescent. A blue-shift in the emission was observed between the free ligand L1 and the one incorporated into Co(II)-containing complex 2, and a red-shift in the emission was observed between the free ligand L3 and the one incorporated into Ag(I)-containing polymeric compounds 6 and 7.     

二(氢过碘酸)合银(III)配离子氧化愈创甘油醚的反应动力学及机理

在碱性介质中, 用传统的分光光度法研究了Ag(III)配离子, 即[Ag(HIO6)2]5-, 氧化药物分子愈创甘油醚的动力学及其机理. 用质谱鉴定了氧化产物；反应对Ag(III) 和愈创甘油醚均为一级；在温度25.0-40.0 ℃范围内, 通过分析[OH-]和[IO-4]tot对反应速率的影响, 二级速率常数有以下表达式：k′=(ka+kb[OH-])K1/{f([OH-])[IO-4]tot+K1}, 在25.0 ℃及离子强度0.30 mol·L-1时, 对此反应有ka=(2.6±1.2)×10-2 mol-1·L·s-1, kb=(2.8±0.1) mol-2·L2·s-1, 及K1=(4.1±0.4)×10-4 mol·L-1, 求出了涉及ka, kb的活化参数, 并据此推出反应机理为反应体系中的[Ag(HIO6)2]5-配离子在前期平衡后, 反应活性中心与药物分子形成Ag(III)-过碘酸-愈创甘油醚分子三元配合物, 配位甘油醚分子通过两个平行途径将两电子传递给中心原子Ag：一个途径无OH-离子参与, 另一途径有OH-参与完成.     

Synthesis and structure of polymeric networks of silver hexafluoroacetylacetonate complexes of THF, toluene, and vinyltrimethylsilane

The reaction of 1,1,1,5,5,5-hexafluoroacetylacetone (Hhfac) with Ag2O in the presence of L=THF, toluene, and Me3SiCH=CH2 was studied to obtain [Ag(hfac)L]x complexes for use as chemical vapor deposition precursors. The structures and volatilities of these three complexes were compared to those of the previously synthesized Ag(hfac)(Me3SiC triple bond CSiMe3), 1, which was also crystallographically characterized for comparison. The reaction of Ag2O with Hhfac in THF forms the polymeric complex [Ag4(hfac)4(THF)2]infinity, 2, which has tetrametallic subunits with hfac ligands that bridge via oxygen and carbon. Both 4- and 5-coordinate silver metal centers are found in 2. Ag2O reacts with Hhfac in toluene to form a complex with a similar tetrametallic unit [Ag4(hfac)4(toluene)2]infinity, 3. In this case, the tetrametallic subunits are assembled via bridging toluene molecules, and each silver is 6-coordinate. In the presence of excess vinyltrimethylsilane (vtms), Ag2O and Hhfac form [Ag3(hfac)3(vtms)]infinity, 4, which contains trimetallic subunits assembled via oxygen atoms of bridging hfac ligands and 5- and 6-coordinate silver.     

Self-assembly of multinuclear coordination species with chiral bipyridine ligands: silver complexes of 5,6-CHIRAGEN(o,m,p-xylidene) ligands and equilibrium behaviour in solution

The complexation reactions between Ag- and a series of enantiopure ligands belonging to the CHIRAGEN (from CHIRAlity GENerator) family (L1, L2, L3, based on (-)-5,6-pinene bipyridine) have been studied in solution. It has been shown that the length of the bridge plays a fundamental role in the self-assembly processes leading to different compounds: mononuclear complexes (with L3), mixtures of polynuclear complexes (with L2) and circular helicates (with L 1). Although the absolute configuration of the chiral centres in all three ligands is the same, the metal-centred chirality of L3 (delta) is inverted with respect to that in the other two complexes with L1 and L2 (delta). The metal configuration is thus opposite in the mononuclear complex with respect to the polynuclear species. Detailed thermodynamic studies were carried out for the Ag+ and L1 ligand system by 1H and 109Ag NMR spectroscopy (as a function of concentration, temperature and pressure). At low temperature and high pressure, the [Ag6L1(6)]6+ hexanuclear circular helicate forms a tetranuclear circular helicate [Ag4L1(4)]4+: 2[Ag6L1(6)]6+ <=> 3 [Ag4L1(4)]4+. The thermodynamics parameters, obtained by temperature and pressure variation, have the following values: K298 = (8.7 +/- 0.7) x 10(-5) mol x kg(-1), deltaHo = -15.65 +/- 0.8 kJ x mol(-1), deltaSo = -130.2 +/- 3 J x mol(-1) x K(-1) and deltaVo(256 K)= -160 +/- 12 cm3 x mol(-1). The reaction volume calculated according to Connolly's method indicates that the calculated structure of [Ag4L1(4)]4+ is plausible. Both the signs and large magnitudes of deltaSo and deltaVo are counterintuitive, yet can be understood by modelling methods.     

Vapochromic behavior of {Ag2(Et2O)2[Au(C6F5)2]2}n with volatile organic compounds

The vapochromic behaviors of {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1), Me2CO (2), THF (3), CH3CN (4)) were studied. {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1)) was synthesized by the reaction of [Bu4N][Au(C6F5)2] with AgOClO3 in 1:1 molar ratio in CH2Cl2/Et2O (1:2). 1 was used as starting material with THF to form {Ag2L2[Au(C6F5)2]2}n (L = THF (3)). 3 crystallizes in the monoclinic space group C2/c and consists of tetranuclear units linked together via aurophilic contacts resulting in the formation of a 1D polymer that runs parallel to the crystallographic z axis. The gold(I) atoms are linearly coordinated to two pentafluorophenyl groups and display additional Au...Ag close contacts within the tetranuclear units with distances of 2.7582(3) and 2.7709(3) A. Each silver(I) center is bonded to the two oxygen atoms of the THF molecules with a Ag-O bond distance of 2.307(3) A. TGA analysis showed that 1 loses two molecules of the coordinated solvent per molecular unit (1st one: 75-100 degrees, second one: 150-175 degrees C), whereas 2, 3, and 4 lose both volatile organic compounds (VOCs) and fluorinated ligands in a less well defined manner. Each complex loses both the fluorinated ligands and the VOCs by a temperature of about 325 degrees C to give a 1:1 gold/silver product. X-ray powder diffraction studies confirm that the reaction of vapors of VOCs with 1 in the solid state produce complete substitution of the ether molecules by the new VOC. The VOCs are replaced in the order CH3CN > Me2CO > THF > Et2O, with the ether being the easiest to replace. {Ag2(Et2O)2[Au(C6F5)2]2}n and {Ag2(THF)2[Au(C6F5)2]2} n both luminesce at room temperature and at 77 K in the solid state. Emission maxima are independent of the excitation wavelength used below about 500 nm. Emission maxima are obtained at 585 nm (ether) and 544 nm (THF) at room temperature and at 605 nm (ether) and 567 nm (THF) at 77 K.     

Anion- and solvent-directed assembly in silver bis(thioimidazolyl)methane chemistry and the silver-sulfur interaction

The effect of metal complexation on the structure and properties of the electroactive bis(1-methylthioimidazolyl)methane linkage isomers CH2(N-tim)2 (L1) and CH2(S-tim)2 (L2) has been explored. Coordination polymers {[Ag(L1)2]X}n (X = BF4, PF6) are formed by bridging L1 between tetrahedral silver centers giving two-dimensional cationic sheets composed of AgS(4) linkages; the anions are sandwiched between sheets. Cyclic dimers {[Ag2(L2)2]X2} (X = BF4, PF6, OSO2CF3) are formed when L2:AgX ratios are lower than 1.5. When L2:AgPF6 was 1.5 or higher, the complex [Ag4(L2)5](PF5)4 could be isolated as a solvate. The NMR, IR, electrochemical, and ESI+ mass spectral data of this latter compound indicate that extensive dissociation to the cyclic dimer and free ligand occurs in solution. Finally, a Cambridge Structural Database search was performed to provide insight into reasonable silver-sulfur bond distances, since literature values appeared to vary widely between 2.3 and 3.2 A. It was found that these distances increase with increasing coordination number of silver. The average distances for 2-, 3-, 4-, 5-, and 6-coordinate silver were found to be 2.40, 2.52, 2.62, 2.70, and 2.75 A, respectively.     

Calix[4]bis(thiacrown): assembly of an endocyclic disilver(I) complex and exocyclic 3D copper(I) coordination polymers

Calix[4]bis(thiacrown-5) (L) with 1,3-alternating conformation was employed as a strong dinucleating ligand for the soft metal ions AgI and CuI. The reaction of L with AgPF6 afforded a discrete endo-coordinated disilver(I) complex 1, [Ag2L](PF6)2. In contrast, mixed products (2a + 2b) consisting of 3D networks were obtained from the reaction of L and CuI; 2b linked with a Cu4I4 cubane unit was shown to generate photoluminescence, while 2a linked with a Cu2I2 rhomboid unit does not.     

The stepwise formation of mixed-metal coordination networks using complexes of 3-cyanoacetylacetonate

The complexes [Cu(L(1))2] 1, [Fe(L(1))3] 3 and [Al(L(1))3] 4 [L(1) = CH(3)C(O)C(CN)C(O)CH(3)] have been prepared for use as metallo-ligands in mixed-metal coordination networks. Surprisingly, the nature of the copper precursor is important in the synthesis of 1, with the reaction between Cu(NO3)2.3H2O, HL(1) and NEt3 giving [Cu6(micro(3)-OMe)4(micro-OMe)2(L(1))6] 2 instead of the anticipated 1, which was obtained with CuCl2.2H2O under the same conditions. Compound 1 reacts with AgNO3 to form [Cu(L(1))2.AgNO3](infinity) 5, the structure of which contains one-dimensional chains in which Ag+ ions bridge between molecules of 1. These chains are cross-linked into ladders by bridging nitrates. The product obtained from the reaction of 3 and AgNO3 is crucially dependent on the solvent used. The reaction in methanol-acetone gives [Fe(L(1))3.AgNO3](infinity) 6, {[Fe2(micro-OMe)2(L(1))4.2AgNO3].CH(3)C(O)CH(3)}(infinity) 7 and [Fe2(micro-OMe)2(L(1))4.AgNO3](infinity) 8. Compounds 6 and 8 both have one-dimensional chain structures, whereas 7 has a two-dimensional layer structure. The reaction in methanol gives 6 and 8 as the major products and, in addition, small quantities of {[AgFe2(micro-OMe)2(L(1))4]OH.0.4H2O](infinity) 9. Compound 9 has a three-dimensional structure based on doubly interpenetrated PtS nets. Compounds 7-9 contain Fe2(micro-OMe)2(L(1))4 dimers, but the coordination properties of the dimers differ, with all the cyanides coordinated in 7 and 9 but one uncoordinated in 8. The orientation of the cyanide groups depends on the relative chirality of the iron centres. A transmetallation reaction occurs between 4 and AgNO3 to give [Ag(L(1))](infinity) 10, which has a two-dimensional layer structure. Compounds 2, 3 and 5-10 have been characterised by X-ray crystallography.     

Assembly of a heterobinuclear 2-D network: a rare example of endo- and exocyclic coordination of Pd(II)/Ag(I) in a single macrocycle

The S3O2 macrocycle L1 was synthesized by a dithiol-dihalide coupling reaction under high-dilution conditions. The reaction of L1 with K2PdCl4 afforded an exocoordinated complex 1, [cis-Cl2Pd(L1)], which can then be manipulated to provide a heterobinuclear complex 3, {[Pd(L1)Ag(NO3)(2.5)](NO3)(0.5)}n, utilizing endocyclic Pd(II) and exocyclic Ag(I) in a single macrocycle through a successive reaction with AgNO3. The network of 3 contains a unique honeycomb-like 2-D sheet made up of the repeating unit [Ag6(NO3)6].     

The cyclic "silver-diphos" motif [Ag2(mu-diphosphine)2]2+ as a synthon for building up larger structures

The dinuclear, cyclic structural motif [Ag2(diphosphine)2](2+), here termed the "silver-diphos" motif, previously observed in many diphosphine-silver complexes, has been investigated as a synthon for building up larger structures such as coordination cages and polymers. A series of ligands containing one to four meta-substituted diphosphine groups, attached via a central core, has been synthesized from the corresponding fluoroarenes by reaction with KPPh2. Upon reaction with silver salts, the target synthon is adopted by meta-substituted diphosphines 1,3-bis(diphenylphosphino)benzene (L1), 2,6-bis(diphenylphosphino)benzonitrile (L2), and 3,5-bis(diphenylphosphino)benzamide (L3), each of which gives a single species in solution consistent with the expected dimeric complexes [Ag2L2(anion)2]. X-ray crystal structures of [Ag2(L1)2(OTf)2] and [Ag2(L2)2(SbF6)2] confirm the adoption of the silver-diphos motif in the solid state. Amide-functionalized diphosphine L3 forms a hydrogen-bonded chain structure in the solid state via the amide group. A discrete boxlike cage [Ag4(L4)2][SbF6]4 based on two silver-diphos synthons is formed when the tetraphosphine Ph2Sn{3,5-bis(diphenylphosphino)benzene}2 (L4) reacts with silver(I). Its single-crystal X-ray structure reveals a central cavity of minimum diameter, ca. 5.0 A, which contains a single SbF6(-) counterion disordered over two sites. In contrast to the highly selective behavior of the di- and tetra-phosphines L1-L4, the heptaphosphine P{3,5-bis(diphenylphosphino)benzene}3 L5 and the hexaphosphine PhSn{3,5-bis(diphenylphosphino)benzene}3 L6 give dynamic mixtures upon reaction with silver salts in solution. This nonspecific behavior is rationalized by the fact that their diphosphine groups are not appropriately disposed to form stable discrete structures based on the silver-diphos synthon. By contrast, the octaphosphine Sn{3,5-bis(diphenylphosphino)benzene}4 L7 does selectively form a single, discrete, highly symmetrical product in solution, [Ag4(L7)(OTf)4]. In this case, the ligand unexpectedly adopts an interarm tetra-chelating coordination mode, resulting in a continuous 24-membered ring around the periphery of the molecule. To understand the adoption of this unusual coordination mode, the alternative diphosphine Ph2Sn(3-diphenylphosphinobenzene)2 L8, which models a single interarm chelating site of L7, was also investigated. By contrast to L7, its coordination was nonspecific, giving mixtures of silver complexes upon reaction with AgOTf. The selective interarm chelation by L7 may therefore be stabilized by the continuous coordination ring in [Ag4(L7)(OTf)4]; that is, the four chelating sites can be thought of as acting in a cooperative manner. Alternatively, interarm steric repulsions between phenyl groups may favor interarm chelation. Overall, we conclude that, if the diphosphine groups are appropriately articulated to act independently (i. e., they are adequately separated and oriented), the silver-diphos synthon can be a useful tool for the coordination-based self-assembly of larger structures.     

Coordination networks through the dimensions: from discrete clusters to 1D, 2D, and 3D silver(I) coordination polymers with rigid aliphatic amino ligands

The use of a ligand directed strategy in the assembly of discrete clusters, 1D chains, 2D layers, and 3D networks using aliphatic N-donor ligands has been investigated. The ligands are a family of amines with rigid backbones [cis,cis-1,3,5-triaminocyclohexane (cis-tach), cis,trans-1,3,5-triaminocyclohexane (trans-tach), cis-1,3-diaminocyclohexane (cis-dach), and cis-3,5-diaminopiperidine (cis-dapi)], and their complexation with Ag(I) salts results in a diverse set of architectures with the following compositions: [Ag3(cis-tach)2]F3.4CH(3)OH.0.5H2O (1), [Ag3(cis-tach)2]F3.6H2O (2), ([Ag(cis-dach)]ClO4)n (3), ([Ag(cis-tach)]NO3)n (4), ([Ag(trans-tach)]PF6)n(5), and ([Ag(cis-dapi)]CF3SO3)n (6). Structural analysis shows that compounds 1 and 2 are discrete M(3)L(2) cage-type clusters with varying solvent molecule content. Short Ag...Ag contacts (3.021(8) A) are observed to dimerize discrete units in compound 2. Compound 3 is a 1D zigzag chain formed by coordination to the two primary amines of cis-dach, whereas the tridentate ligands in compounds 4 and 5 (cis-tach and trans-tach, respectively) are able to form tubular architectures by virtue of their ability to "wrap" round the channel walls. An infinite 2D coordination network is demonstrated by compound 6, in which the three coplanar amino donors of cis-dapi coordinate to the trigonal planar Ag(I) ions to form a layered structure of 6(3) topology. These are compared with a previously reported 3D structure, ([Ag(trans-tach)]NO3)n (7), that belongs to this family of architectures.     

Betaine-induced assembly of neutral infinite columns and chains of linked silver(I) polyhedra with embedded acetylenediide

Ten polymeric silver(I) double salts containing embedded acetylenediide: [(Ag2C2)2(AgCF3CO2)9(L1)3] (1), [(Ag2C2)2(AgCF3CO2)10(L2)3]H2O (2), [(Ag2C2)(AgCF3CO2)4(L3)(H2O)]0.75 H2O (3), [(Ag2C2)(1.5)(AgCF3CO2)7(L4)2] (4), [(Ag2C2)(AgCF3CO2)7(L5)2(H2O)] (5), [(Ag2C2) (AgC2F5CO2)7(L1)3(H2O)] (6), [(Ag2C2)(AgCF3CO2)7(L1)3(H2O)]2 H2O (7), [(Ag2C2)(AgC2F5CO2)6(L3)2] (8), [(Ag2C2)2(AgC2F5CO2)12(L4)2(H2O)4]H2O (9), and [(Ag2C2)(AgCF3CO2)6(L3)2(H2O)]H2O (10) have been isolated by varying the types of betaines, the perfluorocarboxylate ligands employed, and the reaction conditions. Single-crystal X-ray analysis has shown that 1-4 all have a columnar structure composed of fused silver(I) double cages, with C2(2-) species embedded in its stem and an exterior coat comprising anionic and zwitterionic carboxylates. For 5 and 6, single silver(I) cages are linked into a beaded chain through both types of carboxylate ligands. In 7, two different coordination modes of L1 connect the silver(I) polyhedra into a chain. For 8, the mu(2)-O,O' coordination mode of L3 connects the silver(I) double cages into a chain. Compound 9 exhibits a two-dimensional architecture generated from the cross-linkage of double cages by C2F5CO2-, L4, and [Ag2(C2F5CO2)2] units. Similar to 9, 10 is also a two-dimensional structure, which is formed by connecting the chains of linked double cages through [Ag2(CF3CO2)2] bridging.     

Well-resolved, new water morphologies obtained by modification of the hydrophilic/hydrophobic character and shapes of the supporting layers

The planar coordination complexes [Ag2L2] (L = ophen or obpy, where Hophen = 1H-[1,10]phenanthrolin-2-one and Hobpy = 1H-[2,2']bipyridinyl-6-one) contain both hydrophilic and hydrophobic functional groups. Crystallization of these structurally related complexes in an aqueous medium gives [Ag2(ophen)2]2 x 6H2O (1), [Ag2(obpy)2]3 x 18H2O (2), and [Ag2(obpy)2]2 x 14.5H2O (3). Novel water morphologies are observed in these crystalline hydrates, similar 2D metal-organic layers in which the planar [Ag2L2] complexes as building blocks are stacked alternately together and provide hydrogen bond acceptor sites (O atoms) for anchoring 1D water chains or 2D water layers on their surfaces. In the wavelike metal-organic framework of 1, the wide hydrophobic region renders the formation of 1D water tapes containing four- and six-membered water rings, whereas more complex 2D water layers are sandwiched in 2 and 3, owing to the fact that the surfaces of the supporting layers are more hydrophilic than 1.     

Ring-opening polymerisation of silver-diphosphine [M2L3] coordination cages to give [M2L3]infinity coordination polymers

[M2L3] coordination cages and linear [M2L3]infinity polymers of the rigid, bridging diphosphines bis(diphenylphosphino)acetylene (dppa) and trans-1,2-bis(diphenylphosphino)ethylene (dppet) with silver(I) salts have been investigated in the solution and solid states. Unlike flexible diphosphines, 1:1 dppa/AgX mixtures do not selectively form discrete [Ag2(diphos)2(X)2] macrocycles; instead dynamic mixtures of one-, two- and three-coordinate complexes are formed. However, 3:2 dppa/AgX ratios (X = SbF6. BF4, O3SCF3 or NO3) do lead selectively to new [M2L3] triply bridged cage complexes [Ag2(dppa)3(X)2] 1a-d (X = SbF6 a, BF4 b, O3SCF3 c, NO3 d), which do not exhibit Ag-P bond dissociation at room temperature on the NMR time scale (121 MHz). Complexes la-d were characterised by X-ray crystallography and were found to have small internal cavities, helical conformations and multiple intramolecular aromatic interactions. The nucleophilicity of the anion subtly influences the cage shape: Increasing nucleophilicity from SbF6 (1a) through BF4 (1b) and O3SCF3 (1c) to NO3 (1d) increases the pyramidal distortion at the AgP3 centres, stretching the cage framework (with Ag...Ag distances increasing from 5.48 in 1a to 6.21 A in 1d) and giving thinner internal cavities. Crystal packing strongly affected the size of the helical twist angle, and no correlation between this parameter and the Ag-Ag distance was observed. When crystalline 1c was stored in its supernatant for 16 weeks, conversion occured to the isostoichiometric [M2L3]infinity coordination polymer [Ag(dppa)2Ag(dppa)(O3SCF3)2]infinity (1c'). X-ray crystallography revealed a structure with ten-membered Ag2(dppa)2 rings linked into infinite one-dimensional chains by a third dppa unit. The clear structural relationship between this polymer and the precursor cage 1c suggests a novel example of ring-opening polymerisation. With dppet, evidence for discrete [M2L3] cages was also found in solution, although 31P NMR spectroscopy suggested some Ag-P bond dissociation. On crystallisation, only the corresponding ring-opened polymeric structures [M2L3]infinity could be obtained. This may be because the greater steric bulk of dppet versus dppa destabilises the cage and favours the ring-opening polymerisation.     

一维链状Ag(Ⅰ)席夫碱配合物的合成和结构表征

以2-醛基吡啶和1,2-二(对氨基苯氧基)乙烷进行缩合得到Schiff碱配体L,然后与AgSbF6进行配位反应,得到了席夫碱配合物[Ag(L) SbF6]n,用元素分析、FT-IR和X-射线单晶衍射进行了表征.结果表明,配合物属于单斜晶系,P21/n空间群,每个Ag(Ⅰ)的配位环境均为扭曲四面体,每个配体L通过其两端的2个N原子同2个金属离子配位桥联形成一维螺旋链结构.     

Silver(I) complexes of fixed, polytopic bis(pyrazolyl)methane ligands: influence of ligand geometry on the formation of discrete metallacycles and coordination polymers

Reactions of the arene-linked bis(pyrazolyl)methane ligands m-bis[bis(1-pyrazolyl)methyl]benzene, (m-[CH(pz)2]2C6H4, Lm), p-bis[bis(1-pyrazolyl)methyl]benzene, (p-[CH(pz)2]2C6H4, Lp), and 1,3,5-tris[bis(1-pyrazolyl)methyl]benzene (1,3,5-[CH(pz)2]3C6H3, L3) with AgX salts (pz = 1-pyrazolyl; X = BF4- or PF6-) yield two types of molecular motifs depending on the arrangement of the ligating sites about the central arene ring. Reactions of the m-phenylene-linked Lm with AgBF4 and AgPF6 afford complexes consisting of discrete, metallacyclic dications: [Ag2(mu-Lm)2](BF4)2 (1) and [Ag2(mu-Lm)2](PF6)2 (2). When the p-phenylene-linked Lp is treated with AgBF4 and AgPF6, acyclic, cationic coordination polymers are obtained: {[Ag(mu-Lp)]BF4}infinity (3) and {[Ag(mu-Lp)]PF6}infinity (4). Reaction of the ligand L3, containing three bis(pyrazolyl)methane units in a meta arrangement, with an equimolar amount of AgBF4 again yields discrete metallacyclic dications in which one bis(pyrazolyl)methane unit on each ligand remains unbound: [Ag2(mu-L3)2](BF4)2 (5). Treatment of L3 with an excess of AgBF4 affords a polymer of metallacycles, {[Ag3(mu-L3)2](BF4)3}infinity (6), with one of the bis(pyrazolyl)methane units on each ligand bound to a silver cation bridging two metallacycles. The supramolecular structures of the silver(I) complexes 1-6 are organized by noncovalent interactions, including weak hydrogen bonding, pi-pi, and anion-pi interactions.