Synthesis and crystal structures of four mixed-ligand silver(I) complexes with sandwich-like structure

The reaction of AgNO₃, with combinations of 4,4′-bipyridine (bpy), 1,2-di(4-pyridyl)ethylene (dpe), hexanedioic acid (HA), pyridine-3,5-dicarboxylic acid (pdc) and 3,3′4,4′-biphenyltetracarboxylic acid (bptc) in aqueous alcohol at room temperature produces block-like crystals of [Ag₂(bpy)₂](HA)₂·6H₂O, [Ag₂(bpy)₂(H₂O)](pdc)·3H₂O, [Ag₄(bpy)₄](bptc)·14H₂O and [Ag₂(dpe)₂(H₂O)₂](HA)·6H₂O. All four compounds consist of parallel 1D infinite bpy/dpe-silver cationic chains, interspersed with organic anions that play the role of charge compensation in the crystal structure. The lattice water molecules are situated among the framework of the crystal structure and stabilized by rich hydrogen-bonding interactions, which may play a role in the orientation of the organic anions in the crystal packing.     

Synthesis, structure, and luminescent properties of three silver(I) complexes with organic carboxylic acid and 4,4′-bipyridine-like ligands

The reactions of AgNO₃ with combinations of 1,2-bis(4-pyridyl)ethane(bpa)/4,4′-bipyridine (bpy), 4,4′-stilbenedicarboxylic acid (H₂sda)/2,2′-diphenylaminedicarboxylic acid (H₂dpadc)/2,6-naphthalenedicarboxylic acid (H₂ndc) in aqueous alcohol/ammonia at room temperature produce block-like crystals of [Ag₂(bpa)_1.5(sda)_0.5](sda)_0.5·7H₂O, [Ag₂(bpa)₂(H₂O)₃](dpadc), [Ag₂(bpy)₂](ndc)·4H₂O. All three complexes consist of 1D infinite silver–ligand cationic chains, interspersed with organic carboxylate anions that provide charge compensation in the crystal structures. The lattice water molecules are situated among the framework of the crystal structure and show rich hydrogen-bonding interactions, which help to orientate the organic carboxylate anions in the crystal packing, and the presence of Ag···N and Ag···Ag contacts contributes to strengthen the frameworks. The luminescent properties and thermogravimetric analyses of the three complexes are also presented.     

Synthesis, characterization, and luminescent properties of a series of silver(I) complexes with organic carboxylic acid and 1,3-bis(4-pyridyl)propane ligands

The reaction of AgNO₃ with combinations of 1,3-bis(4-pyridyl)propane (bpp), pyridine-3,5-dicarboxylic acid (H₂pdc), oxybis(benzoic acid) (H₂oba), and 4,4′-oxidiphthalic acid (H₄odpt) in aqueous alcohol/ammonia at room temperature produces crystals of [Ag₂(bpp)₂](pdc)·8H₂O, [Ag₂(bpp)₂(H₂O)](oba)·5H₂O, and [Ag₂(bpp)₂(H₂O)₂](odpt)·2H₂O. All three complexes consist of 1D infinite silver-bpp cationic chains, interspersed with organic carboxylate anions that provide charge compensation in the crystal structures. The lattice water molecules are situated among the framework of the crystal structure and show rich hydrogen-bonding interactions, which serve to orientate the organic carboxylate anions in the crystal packing, while the presence of Ag···N and Ag···Ag contacts strengthens the frameworks. The luminescent properties of the complexes have been investigated.     

Silver-based coordination complexes of carboxylate ligands: crystal structures,luminescence and photocatalytic properties

The complexes [Ag₄(dpe)₄]·(btec) (1) and [Ag₄(bpy)₄]·(btec)·12H₂O (2) (dpe = 1,2-di(4-pyridyl)ethylene, bpy = 4,4′-bipyridine, H₄btec = 1,2,4,5-benzenetetracarboxylic acid) have been synthesized in aqueous alcohol/ammonia by slow evaporation at room temperature and characterized by elemental analysis, single-crystal X-ray diffraction, FTIR, UV–Vis and luminescence spectroscopies. Both complexes are composed of 1D infinite cationic [Ag/dpe(bpy)] _n ⁿ⁺ chains and discrete btec^4? anions. Their three-dimensional supramolecular structures are built up of cationic sheets formed from [Ag/dpe(bpy)] _n ⁿ⁺ units via weak Ag…Ag and Ag…N interactions, plus anionic btec^4? sheets featuring electrostatic, π–π and hydrogen bonding interactions. Both complexes exhibited photocatalytic activity for the decomposition of methyl orange under UV light irradiation.     

Self-assembly luminescent complexes with [Ag2 (μ-dppm)2 (MeCN)2](SbF6)2 and tptz as components

[Ag₂(μ-dppm)₂(tptz)(MeCN)](SbF₆)₂·2H₂O·2MeCN (1), [Ag₂(μ-dppm)₂(tptz)₂](SbF₆)₂·1.75H₂O (2) and [Ag₂(μ-dppm)(tptz)₂](SbF₆)₂· 2MeCN (3) were synthesized by self-assembly with metal diphosphine [Ag₂(μ-dppm)₂ (MeCN)₂](SbF₆) ₂ and tptz as components in different molar ratios [(dppm = bis(diphenylphosphino)methane and tptz = 2,4,6-tris(2′-pyridyl)-1,3,5-triazine)] and characterized by IR spectra, elemental analysis, ¹H NMR spectra, ³¹P NMR spectra and Visible–Ultraviolet spectra. Structures of all the complexes were determined by X-ray analysis. π − π interactions were found in complex (3). Further studies show that all the complexes were of well luminescent properties both in solution and solid state.     

Ag(I)配位聚合物[Ag2(bpp)2(H2O)]·pydc·7H2O的合成、表征及性质研究

水热合成了基于吡啶-3,5-二羧酸(H2pydc)的含Ag(I)配位聚合物 [Ag2(bpp)2(H2O)]·pydc·7H2O (1) (其中bpp = 1,3-双(4-吡啶)丙烷)。X射线单晶结构分析表明,在一维化合物1中,发现了包含(H2O)12水簇单元的二维氢键层状结构。有趣的是,在该二维层中, 每个pydc2-阴离子作为“桥”连接了两个(H2O)12单元和两个自由水分子。另外,对化合物1的荧光、热重、粉末衍射等也进行了研究和讨论。     

Three Mn(II) complexes with 1,3-bis(4-pyridyl)propane and their supramolecular nets

Three complexes, [Mn(bpp)₄(H₂O)₂](ClO₄)₂?·?1.5H₂O (1), [Mn(bpp)₃Br₂]?·?2H₂O (2), and [Mn(bpp)₂(H₂O)₂](ClO₄)?·?I?·?H₂O?·?bpp (3) (bpp?=?1,3-bis(4-pyridyl)propane), were synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 is mononuclear where M(II) is coordinated to a monodentate TT-bpp, three monodentate TG-bpp, and two water molecules. Complex 2 possesses a single-stranded helical chain formed from MnN₄Br₂ octahedra by a single TT-bpp, with pendant monodentate TG-bpp ligands. Complex 3 consists of a ribbon-type double-stranded chain formed from MnN₄O₂ octahedra by double TG-bpp ligands. 2-D supramolecular architectures of 1–3 are formed by hydrogen bonds. The fluorescence of the three complexes comes from the π*–π transition of the ligand.     

Crystal Structures and Photoluminescence Properties of Zinc(II) and Cadmium(II) Coordination Polymers with “Y”‐Shaped Ligands

Three Zn^II and Cd^II complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L₁)(2,2′‐bpy)₂(H₂O)] · 2H₂O ( 1 ), [Zn(L₁)(bpp)(H₂O)] ( 2 ), and [Cd(L₁)(H₂O)] · H₂O ( 3 ) [H₂L₁ = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H ··· O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.8²). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1 – 3 were also investigated.     

Influence of organic carboxylic acids on self-assembly of silver(I) complexes containing 1,2-bis(4-pyridyl)ethane ligands

Four silver(I) complexes, namely [Ag₂(bpe)₂](bdc)·8H₂O (1), [Ag₂(bpe)₂(da)]·4H₂O (2), [Ag₄(bpe)₃(bptc)]·9H₂O (3), and Ag(bpe)₂(bpdc)₂ (4), have been successfully synthesized by the reactions between AgNO₃, 1,2-bis(4-pyridyl)ethane (bpe) and different carboxylic acids, including 1,3-benzenedicarboxylic acid (H₂bdc), diphenic acid (H₂da), 3,3′,4,4′-biphenyltetracarboxylic acid (H₄bptc), and 2,2′-bipyridine-3,3′-dicarboxylic acid (H₂bpdc). All four compounds were characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. In (1), the Ag(I) atoms, in linear geometry, are joined into 1-D infinite cationic bpe-silver chains, and discrete bdc²⁻ anions compensate the charge of the crystal structure. In (2), the Ag(I) atoms, adopting tetrahedral and trigonal geometries, are linked by bpe and da²⁻ ligands into neutral double chains. In (3), the Ag(I) atoms, in T-shaped and linear environments, are coordinated by bpe and multidentate bptc⁴⁻ ligands to construct a 2-D network. And in (4), the Ag(I) atoms, with trigonal and T-shaped coordination geometries, are coordinated by bpe and bpdc²⁻ ligands to build up a 3-D framework. The different anions play different and important roles in directing the final crystal structures.     

Syntheses,Structures and Spectroscopic Studies of Silver(I) Coordination Polymers Bridged by Flexible Bidentate Ligands

The reaction of Ag₂SO₄ and bpp (bpp = 1,3‐bis(4‐pyridyl)propane) in H₂O afforded the complex [Ag₂(bpp)₂(SO₄) · 6.5H₂O·CH₃OH]_n, 1. The IR and TGA have been recorded and the structure has been determined. Crystal data for 1: Space group C₂/c, a = 17.885(4), b = 25.230(6), c = 8.832(2) Å, β = 105.437(4)°. V = 3841(1) ų, Z = 8 with final residuals R1 = 0.0710 and wR2 = 0.1620. The complex shows a three‐dimensional supramoleclar structure constructed with two‐dimensional infinite [Ag₂(bpp)₂]_n sheetlike layers pillared by Ag‐Ag interactions and Ag····O (SO₄) interactions in the solid state.     

Syntheses and crystal structures of four new fpa-metal complexes through in situ ligand reaction

Four new fpa-metal complexes, [Co(fpa)₂(H₂O)₂] (1), [Cu(fpa)₂(H₂O)] (2), [Zn₂(fpa)₄(bpp)₂] _n (3), and {[Zn(bpy)(H₂O)₄]?·?2(fpa)} _n (4), have been synthesized and fully characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, and thermogravimetric analysis (TGA), (Hfpa?=?2,2-difluoro-2-(pyridine-2-yl)acetate, bpp?=?1,3-bis(4-pyridyl)propane, bpy?=?4,4′-bipyridine). X-ray diffraction analyses reveal that 1 and 2 with 0-D structures are both extended into 3-D supramolecular networks through hydrogen bonds and π···π interactions. Complex 3 with chiral centers possesses a 1-D structure constructed by two kinds of bpp molecules and four kinds of fpa^? molecules with different conformations, with bbp and fpa^? bridging and capped ligands, respectively. In 4, bpy links [Zn(H₂O)₄]²⁺ into a 1-D polymeric cationic chain and uncoordinated fpa^? compensates the framework charge. The results of TGA reveal that fpa^? decomposes through two processes. Both 3 and 4 show strong fluorescence in the solid state at room temperature.     

Porous homo- and heterochiral cobalt(II) aspartates with high thermal stability of the metal-organic framework

Metal-organic coordination polymers with the compositions [Co₂(L-asp) ₂-(bpy)] · MeOH · H₂O (1), [Co₂(L-asp)₂(bpe)] · 0.28(bpe) · H₂O (2), and [Co₂(d-asp)(l-asp)-(bpa)] · 0.25(bpa) · 1.5H₂O (3) (H₂asp is aspartic acid, bpy is 4,4′-bipyridine, bpe is trans-bis(4- pyridyl)ethylene, and bpa is 1,2-bis(4-pyridyl)ethane) were synthesized on heating cobalt(II) as-partate and N-donor ligands (bpy, bpe, or bpa) in an aqueous-methanol mixture. The structures of compounds 1⁗ash;3 were established by X-ray diffraction analysis and confirmed by X-ray powder crystallography, IR spectroscopy, thermogravimetry, and elemental analysis. The stability of the synthesized coordination polymers was studied. It was shown that they retain the framework structure on heating to 300 °C.     

Ag (I)–organodiimine coordination complex polymers: structural influences of ligand geometries and charge-compensating oxoanions

Hydrothermal synthesis has been exploited in the preparation of two new materials of the Ag(I)-organodiimine class of materials. By exploiting variations in ligand geometry and tether length and the structural influence of different oxoanions, the inorganic oxides [Ag(dpe)(NO₃)](dpe=1,2-bias(4-pyridyl)ethane) and [Ag₂(2,4′-bpy)₂(SO₄)(H₂O)]·5H₂O(2·5H₂O) were isolated. Compound 1 was prepared in the reaction of Ag(NO₃), dpe, and H₂O in the mole ratio 1:1:500 at 120°C for 24 h, while compound 2 was prepared from Ag₂SO₄, 2,4′-bpy, and H₂O under similar conditions. The structure of 1 is constructed from {Ag(dpe)}_nⁿ⁺ chains linked through η², μ²–NO₃⁻ groups into a two-dimensional network. The structure of 2·5H₂O consists of one-dimensional sinusoidal chains. The Ag(I) sites exhibit two distinct geometries: one is ‘T’-shaped through bonding to two nitrogen donors from two 2,4′-bpy groups and a sulfate oxygen; the second site is also ‘T’-shaped through bonding to two pyridyl nitrogen atoms and an aqua ligand.     

Syntheses and crystal structures of three structurally similar dinuclear silver(I) complexes

Three terephthalato-bridged dinuclear silver(I) complexes with the formulae Ag₂(5map)₄(tphth), [Ag₂(6map)₄(tphth)] · 2H₂O, and [Ag₂(4map)₄(tphth)] · 2H₂O (5map = 5-methyl-2-aminopyridine, 6map = 6-methyl-2-aminopyridine, 4map = 4-methyl-2-aminopyridine, tphth = terephthalate), have been synthesized and characterized by elemental analysis and single crystal X-ray diffraction. The Ag atom in each of the complexes is three-coordinate in a trigonal geometry with one carboxylate O atom and two pyridine N atoms. The characteristic difference among the complexes is the positions for the methyl groups of the aminopyridine ligands. The crystals of the complexes are stabilized by intermolecular N–H···O and O–H···O hydrogen bonds. Electronic supplementary material  The online version of this article () contains supplementary material, which is available to authorized users.     

Supramolecular structures of Mn2+, Co2+ and Zn2+ complexes containing 1,3-bis(4-pyridyl)propane and aminosalicylate anion

In this study, the synthesis, spectroscopic properties and crystal structures of three new supramolecular compounds named [Mn₂(bpp)₄(H₂O)₄](AS)₄·H₂O (1), [Co₂(bpp)₄(H₂O)₄](AS)₄·H₂O (2) and [Zn(bpp)(AS)₂] (3), have been described, where bpp is 1,3-bis(4-pyridil)propane and AS^?  is aminosalicylate anion. By analysing the similarities between the X-ray powder diffraction results, it has been observed that compounds 1 and 2 are isomorphous, exhibiting an orthorhombic system with space group Pccn; for compound 3, another orthorhombic system was observed, with space group Aba2, which displays coordination between the Zn²⁺ metal ion and the aminosalicylate anion; this can be considered the first case in the literature involving the direct coordination to the metal ion. The vibrational spectra of compounds 1 and 2 are very similar. In the Raman spectra, the main bands are observed at ca. 1625 and 1020 cm^? 1, referring to the ^? O–C = O and CC/CN stretching modes of AS^?  and bpp ligands, respectively.     

Three silver(I) coordination polymers assembled from 2-sulfoterephthalic acid and N-donor ligands: syntheses, crystal structures, and luminescence properties

The reactions of silver nitrate with 2-sulfoisophthalic acid (H₃stp) in the presence of N-donor ligands produced three coordination polymers; [Ag₃(stp)(pyz)_0.5]_n (1), {[Ag₄(dpp)₄]·2(Hstp)·9H₂O}_n (2), and {[Ag(bpe)]₂[Ag₂(bpe)₂]₂·2(stp)·19H₂O}_n (3) [pyz = pyrazine, bpp = 1,2-bis(4-pyridyl)propane, bpe = 1,2-di(4-pyridyl)-ethylene]. The complexes have been characterized by single-crystal X-ray diffraction, physico-chemical, and spectroscopic methods. Single-crystal X-ray diffraction reveals that complex 1 is a 2D silver carboxylate-sulfonate layered structure, in which the 2D layers are further linked by the N-donor atoms of pyz ligands into a 3D supramolecular structure. Complex 2 is an infinite 1D chain arrangement with the [Ag₂(dpp)₂]²⁺ unit in which weak Ag···Ag or Ag···O interactions extend the chains into 2D structures. Complex 3 has a 3D supramolecular structure constructed by hydrogen bonding, π–π stacking, and Ag···O interactions to link the ligands, metal atoms, and water molecules together. The luminescence properties of the complexes were investigated.     

Structural variability of Ag(I) metal–organic networks: C–H⋯π and metal⋯π interactions

The synthesis and X-ray structural characterization of two silver(I) coordination polymers, [Ag₂(bpp)₂(Phdac)]·5H₂O (1) and [Ag₂(bpp)(HSSal)] (2), are reported, where bpp = 4,4′-trimethylene dipyridine, H₂Phdac = 1,4-phenylenediacetic acid, and H₃SSal = 5-sulfosalicylic acid. X-ray crystallography reveals that the structures are stabilized through hydrogen bonding interactions. The C–H?π and metal?π interactions of aromatic molecules play a crucial role in building a layered framework. Intricate combinations of the weak non-covalent interactions have been analyzed to explore cooperativity and competitiveness in the solid-state structures.     

A self-assembled (H2O)20(CH3OH)4 binary cluster containing a grail-shaped hexadecameric water cluster trapped in the cavity of a metal-ligand hybrid

A discrete centrosymmetric(H2O)20(CH3OH)4 binary cluster was confined in the cavity of a metal-ligand hybrid [Ag4(bpda)2(bpp)4·14H2O·2CH3OH] n(1)(where bpp = 1,3-bis(4-pyridyl)propane and H 2 bpda = 2,2’-biphenyldicarboxylic acid).The novel mixed water-methanol cluster consists of one grail-shaped hexadecameric cluster,four dangling water and four hanging methanol molecules.The(H 2 O) 16 cluster is composed of two pairs of edge-sharing(H2O) 5 rings attached to one(H2O) 4 core with twenty hydrogen bonds.Alternatively,the(H2O) 16 cluster is structurally similar to a complicated hydrocarbon generated by undergoing [2+2] cycloaddition of 1,2,3,4,5,6-hexahydropentalene,which reveals the resemblance between water clusters and organic compounds.     

2,2'-联吡啶-3,3',6,6'-四羧酸过渡金属配合物的合成、结构及性质

以2,2'-联吡啶-3,3',6,6'-四羧酸(H₄bptc)为配体,通过水热合成的方法与过渡金属盐合成了3个配合物,其分子式分别为[Co₂(H₂bptc)₂(H₂O)₄]·bpe·9H₂O(1),[Ni₂(H₂bptc)₂(H₂O)₄]·bpe·9H₂O(2),[Ni₂(H₂bptc)₂(H₂O)₄]·0.5bpp·7H₂O(3)(bpe=1,2-二(4-吡啶基)乙烯,bpp=1,2-二(4-吡啶基)乙烷)。用红外光谱,X-射线单晶衍射对化合物的晶体结构进行了表征,并对这3个配合物的热稳定性进行了测试。化合物1~3为单核结构的配合物,它们均通过分子间氢键形成三维超分子结构。     

Synthesis and crystal structure of three mixed-ligand silver(I) complexes constructed from 1,2-Di(4-pyridyl)ethylene and different organic carboxylate anions

The reaction of AgNO₃ with 1,2-di(4-pyridyl)ethylene (Dpe) and 2,3-pyrazinedicarboxylic acid (H₂Pzdc) or 2,2′-bipyridyl-4,4′-dicarboxylic acid (H₂Bpdc) or salicylic acid (HSa) in alcohol aqueous solution produces block-like crystals of [Ag₂(Dpe)₂]Ppzdc) · 6H₂O (I), [Ag₃(Dpe)₃](Bpdc)(NO₃) · 4H₂O (II), and [Ag₂(Dpe)₂](Sa)(NO₃) · 3H₂O (III) at room temperature. Crystal I is monoclinic: space group P2₁/m, a = 7.5370(7), b = 17.2309(16), c = 12.5131(11) Å, β = 98.3780(10)°, V = 1607.7(3) ų, Z = 2. Crystal II is triclinic: space group $P\bar 1$ , a = 8.8260(8), b = 11.1149(11), c = 13.3751(14) Å, α = 102.0140(10)°, β = 105.696(2)°, γ = 99.5940(10)°, V = 1200.4(2) ų, Z = 1. Crystal III is triclinic: space group $P\bar 1$ , a = 7.3600(6), b = 2.7549(11), c = 18.2241(16) Å, α = 106.225(2)°, β = 98.0150(10)°, γ = 99.5400(10)°, V = 1588.5(2) ų, Z = 2. All the three complexes contain sandwich-like crystal structures, in which anionic sheets built up from different anions (Pzdc^2?, Bpdc^2?, Sa^?) and lattice water molecules via rich hydrogen-bonding interactions are inserted between the cationic silver complexes layers. The lattice water molecules are situated among the framework of the crystal structure and stabilized by rich hydrogen-bonding interactions, and lattice water molecules may play a role in the orientation of the organic anions in the crystal packing.