Synthesis,characterization and crystal structures of organolead dithiolate compounds displaying transannular interactions D···Pb (D = O,S)

Treatment of Ph₂PbCl₂ with O(C₆H₄SH)₂ (1a), S(C₆H₄SH)₂ (2a) and S(C₆H₃SH)₂O (3a) afforded the stable organolead compounds [{O(C₆H₄S)₂}PbPh₂] (1b), [{S(C₆H₄S)₂}PbPh₂] (2b) and [{S(C₆H₃S)₂O}PbPh₂] (3b). X-ray structure determinations of dithiolate-diphenyl lead compounds 1b–3b revealed that the trichalcogenated ligands are tridentate in 1b and 2b, and bidentate in 3b. The lead atom acts as an acceptor atom exhibiting weak intramolecular transannular interactions with the donor D atom, with tetrahedral distortions of 48% for 1b, 51% for 2b and 45% for 3b. The local geometry at the lead atom is described as monocapped tetrahedral. The crystal packing of title compounds is stabilized by several non-bonded interactions.     

Supramolecular assembly of organic bicapped Keggin polyoxometalate

Two novel supramolecular assemblies of organic bicapped Keggin polyoxometalates (pbpy)₈H₃[PW₁₂O₄₀]·2H₂O (1) and (pbpy)₄H[PMo₁₂O₄₀(VO)] (2) (pbpy=5-phenyl-2-(4-pyridinyl)pyridine) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Crystallographic data for compound (1), C₁₂₈H₁₀₃N₁₆O₄₂PW₁₂, triclinic, space group : a=13.4759(8) Å, b=14.6395(11) Å, c=16.5743(10) Å, α=95.764(2)°, β=102.166(2)°, γ=92.9870(10)°, Z=1, V=3171.1(4) Å³; for compound (2), C₆₄H₄₉N₈O₄₁PMo₁₂V, triclinic, space group : a=11.5377(11) Å, b=12.7552(8) Å, c=14.9599(10) Å, α=72.270(4)°, β=88.916(2)°, γ=67.865(4)°, Z=1, V=1931.0(3) Å³. X-ray analyses show that both 1 and 2 represent rare organic bicapped Keggin structures and are supported by supramolecular interactions to extend into a 3D framework. In particular, the unusual structure feature of compound 2 contains a simultaneously organic and inorganic capped structure.     

Copper phosphonates with dinuclear and layer structures: a structural and magnetic study

Hydrothermal reactions of copper (II) nitrate with 1-hydroxycyclohexanephosphonic acid [C₆H₁₀(OH)PO₃H₂] or Δ¹-cyclohexenephosphonic acid [C₆H₉PO₃H₂] have resulted in three new copper phosphonates, namely, Cu(C₆H₁₀(OH)PO₃)(H₂O)₂ (1), Cu(C₆H₁₀(OH)PO₃) (2) and Cu(C₆H₉PO₃)(H₂O) (3). Compound 1 has a dinuclear structure in which two {CuO₅} square pyramids are bridged by two {CPO₃} tetrahedra through corner sharing. The dimers are connected through intermolecular hydrogen bonds, forming supramolecular layers. Both compounds 2 and 3 show layer structures typical for metal mono-phosphonates, in which the inorganic metal-containing layers are separated by cyclohexane or cyclohexene groups. The magnetic studies show that ferromagnetic interactions are mediated between copper centers in compound 1. In compounds 2 and 3, antiferromagnetic interactions are dominant.     

Solvothermal syntheses and crystal structures of new Cu(II) complexes with phenylsuccinic acid

Five new Cu(II) complexes [Cu(psa)(phen)] · 3H₂O (1), [Cu(psa)(2bpy)] · 0.5H₂O (2), [Cu(psa)(2bpy)(H₂O)] · 3H₂O (3), [Cu(psa)(4bpy)] · H₂O (4), and [Cu(psa)_0.5(N₃)(2bpy)] (5) (H₂psa = phenylsuccinic acid, phen = 1,10-phenanthroline, 2bpy = 2,2′-bipyridine, and 4bpy = 4,4′-bipyridine) were obtained under solvothermal conditions and characterized by single-crystal X-ray diffraction. Complexes 2 and 3 were formed by one-pot reaction. In complex 2, Cu(II) ion is four-coordinated and locates at a slightly distorted square center. In complex 3, the coordinated water molecule occupies the axial site of Cu(II) ion forming a tetragonal pyramid geometry. Complexes 1 and 3 are of 1D chain structures, and extended into 2D supramolecular network by hydrogen bonds. Complex 2 is of zipper structure, and further assembled into 2D supramolecular network by hydrogen bonds and π–π stacking interactions. Complex 4 is a 3D CdSO₄-like structure with twofold interpenetration, while complex 5 is a dinuclear compound. The different structures of complexes 1–5 can be attributed to using the auxiliary ligands, indicating an important role of the auxiliary ligands in assembly and structure of the title complexes.     

Structure modulation of metal–organic frameworks via reaction pH: Self-assembly of a new carboxylate containing ligand N-(3-carboxyphenyl)iminodiacetic acid with cadmium(II) and cobalt(II) salts

Self-assembly of a new carboxylate containing ligand, N-(3-carboxyphenyl)iminodiacetic acid (H₃L), with Cd(II) and Co(II) salts under different reaction pH results in the formation of four new coordination polymers, namely [Cd(HL)(H₂O)] (1), [Co(HL)(H₂O)] (2), [Cd(HL)(H₂O)₄] (3) and [Cd₃(L)₂(H₂O)₉] · 7H₂O (4). Single crystal X-ray diffraction analysis indicates that 1 and 2 are isomorphous and isostructural with a 2D wave-like network structure, while 3 has a 1D zigzag chain structure. The complexes 1–3 were obtained at low pH (<7) which makes the ligands only partly deprotonated. However, complex 4, obtained at pH 7 with all the carboxylate groups deprotonated, exhibits a 2D network structure. The results suggest that the reaction pH is one of the key factors in the formation of the coordination architectures. In addition, the photoluminescence properties of the free ligand (H₃L) and complexes 1, 3 and 4 were studied in the solid state at room temperature. Moreover, the magnetic property of complex 2 was investigated.     

Structural chemistry of mononuclear, tetranuclear and hexanuclear organotin(IV) carboxylates from the reaction of di-n-butyltin oxide or diphenyltin oxide with rhodanine-N-acetic acid

Three new organotin(IV) carboxylates, {[n-Bu₂Sn(O₂CC₄H₄NOS₂)]₂O}₂ (1), n-Bu₂Sn(O₂CC₄H₄NOS₂)₂ (2) and [PhSn(O)O₂CC₄H₄NOS₂]₆ · 3H₂O (3) were synthesized by the reaction of di-n-butyltin/diphenyltin oxide and rhodanine-N-acetic acid. The complexes 1-3 are characterized by elemental, IR, ¹H, ¹³C and ¹¹⁹Sn NMR and X-ray crystallography diffraction analyses. The complex 1 has a tetranuclear structure based on a planar four-membered Sn₂O₂ ring, while complex 2 is a hexa-coordinated monomer. As for complex 3, it adopts the hexameric drum-shaped structure. The supramolecular structure of 1 has been found to consist of one-dimensional molecular chain built up by intermolecular non-bonded S?O interactions. The salient feature of the supramolecular structure of complex 2 is that of a one-dimensional polymer, in which intermolecular Sn?O, S?O and S?S interactions are recognized.     

Synthesis, structures, luminescent and magnetic properties of four coordination polymers with the flexible 1,3-phenylenediacetate ligands

Four coordination polymers, [Zn(pda)(bpy)(H₂O)]_n·nH₂O (1), [Cd(pda)(prz)(H₂O)]_n (2), [Co₃(μ₃-OH)₂(pda)₂(pyz)]_n·2nH₂O (3) and [Pr₂(pda)₃(H₂O)₂]_n (4) (H₂pda=1,3-phenylendiacetic acid, bpy=4,4′-bipyridine, prz=piperazine and pyz=pyrazine) have been hydrothermally synthesized and characterized. Complex 1 is a 1D wheel-like chain structure, which is further extended into a 3D metal-organic supramolecular framework by H-bonds and π-π stacking interactions. Complex 2 is a 1D ladder-like chain structure, which is also further extended into a 3D metal-organic supramolecular framework by H-bonds. Complex 3 possess a 2D sheet structure with infrequent two pairs of double-helix chains. Complex 4 features a 3D structure. Both 1 and 2 display strong blue fluorescent emission at room temperature. Magnetic susceptibility measurements of complexes 3 and 4 exhibit antiferromagnetic interactions between the nearest metal ions, with C=9.99 and 3.43 cm³ mol⁻¹ K, and θ=−23.9 and −46.3 K, respectively.     

Syntheses,characterization, and luminescent properties of four alkaline earth metal–organic frameworks based on two similar N-containing carboxylates

Four coordination polymers {[Ca(3-pa)₂(H₂O)₂]·3H₂O} (1), {[Sr(3-pa)₂(H₂O)₂]·3H₂O} (2), {[Ca(4-pa)₂(H₂O)₄]} (3) and {[Sr(4-pa)(H₂O)₆]·[4-pa]} (4), (3-pa = pyridine-3-carboxylate, 4-pa = pyridine-4-carboxylate) have been synthesized and structurally characterized. Lots of noncovalent interactions were found in the four compounds, aiding the formation of high-dimensional architectures from the low-dimensional structures. Complex 1 and 2 feature similar 1-D chain structures, which adopt face-to-face orientation to form an interesting 2-D network with pipe-like motif. Chain-like water clusters consisting of infinite tetragonal unit are trapped and stabled in the vacuums of the pipelines. The 2-D sheets are further connected into 3-D architecture by noncovalent interactions. Complex 3 has a discrete mononuclear structure, which is further connected into a 3-D framework by hydrogen bonds and π···π interactions. In complex 4, the zigzag-like chain structure units are parallel to each other and pack in ABAB mode to give rise to a 2-D network, which is stabled by π···π stacking and hydrogen bonds. The counteranions in 4 are hosted between the nets and act as “glue” linking the 2-D networks into a 3-D architecture. In addition, the photoluminescence properties of the compounds have been investigated.     

Three inorganic-organic hybrids of bismuth(III) iodide complexes containing substituted 1,2,4-triazole organic components with charaterizations of diffuse reflectance spectra

The reactions of two kinds of substituted 1,2,4-triazoles with BiI₃ yielded three inorganic-organic hybrids: [HL1]₄[Bi₆I₂₂]·[L1]₄·4H₂O (1) (L1=3-(1,2,4-triazole-4-yl)-1H-1,2,4-triazole); [HL2]₄[Bi₆I₂₂]·6H₂O (2); [HL2]₂[Bi₂I₈]·[L2]₂ (3) (L2=(m-phenol)-1,2,4-triazole). Both 1 and 2 have polynuclear anions of [Bi₆I₂₂]^4- to build up the inorganic layers and substituted 1,2,4-triazoles as the organic layers. Hybrid 3 consists of two BiI₅ square pyramids as inorganic layers. There exist hydrogen bondings and I?I interactions in the structures of 1, 2 and 3. Optical absorption spectra of 1, 2 and 3 reveal the presence of sharp optical gaps of 1.77, 1.77 and 2.07 eV, respectively, suggesting that these materials behave as semiconductors.     

Synthesis, crystal structures and characterization of four coordination polymers based on 5-amino-2,4,6-triiodoisophthalic acid

One homochiral 1D coordination polymer [Cu(ATIBDC)(2,2′-bipy)]·3H₂O·CH₃OH (1) and three achiral 1D coordination polymers: [Cd(ATIBDC)(2,2′-bipy)(H₂O)]·3H₂O (2), [Cd(ATIBDC)(phen)(H₂O)]·4H₂O (3), and [Mn(ATIBDC)(phen)₂]·5H₂O (4) have been synthesized and characterized (H₂ATIBDC=5-amino-2,4,6-triiodoisophthalic acid, 2,2′-bipy=2,2′-bipyridine, and phen=1,10-phenanthroline). Extended high dimensional network architectures are further constructed with the help of weak secondary interactions, such as hydrogen bonding, aromatic stacking, and halogen bonding (C-I…π and C-I…N/O). Complex 1 crystallizes in the monoclinic system with chiral space group P2(1) and exhibits a right-handed 2₁ helical chain structure. The homochirality of 1 was confirmed by CD spectrum. Interestingly, two new configurations of decameric water cluster are found in 3 and 4. The acyclic tetrameric cluster (H₂O)₃(CH₃OH) in 1 and (H₂O)₄ in 2 array into highly ordered helical infinite chains. Thermal stabilities of all the complexes have been studied. Solid state fluorescent properties of the Cd(II) complexes have been explored.     

Different aliphatic dicarboxylates affected assemble of new coordination polymers constructed from flexible-rigid mixed ligands

In this article, seven coordination polymers: [Cd(C₅H₆O₄)(C₁₀H₈N₂)]_n (1), [Zn(C₅H₆O₄)(C₁₀H₈N₂)]_n (2), [Cd(C₆H₈O₄)(C₁₀H₈N₂)]_n (3), {[Mn(C₁₀H₈N₂)(H₂O)₄] (C₄H₄O₄)·4H₂O}_n (4), [Mn₅(C₄H₄O₄)₄(O)]_n (5), [Cd(C₄H₄O₄)(C₁₀H₈N₂)(H₂O)]_n (6) and [Zn(C₆H₆O₄)(C₁₂H₈N₂)(H₂O)]_n (7) were synthesized and characterized by single-crystallographic X-ray diffraction. Compounds 1 and 2 are two-dimensional layers connected by glutarate anions and 4,4′-bpy. Unlike compounds 1 and 2, compound 3 is a two-fold interpenetration network. Compound 4 is a one-dimensional chain-like structure, which is further extended to two-dimensional supramolecular layer structure with hydrogen bond. During the synthesis of compound 4, to our surprise, we got compound 5; compound 5 is an interesting three-dimensional network composed of pentanuclear Mn(II) building units and succinate anions. Compound 6 is also a two-dimensional supramolecular layer structure composed of one-dimensional chain-like structure with hydrogen bonds and Π-Π interactions. Compound 7 is also a one-dimensional chain-like structure, which is further connected with the same kind of interaction to generate two-dimensional supramolecular layer structure. Furthermore, compounds 1 and 2 both exhibit fluorescent property at room temperature.     

A series of Cd(II) complexes with π-π stacking and hydrogen bonding interactions: Structural diversities by varying the ligands

Seven new Cd(II) complexes consisting of different phenanthroline derivatives and organic acid ligands, formulated as [Cd(PIP)₂(dnba)₂] (1), [Cd(PIP)(ox)]·H₂O (2), [Cd(PIP)(1,4-bdc)(H₂O)]·4H₂O (3), [Cd(3-PIP)₂(H₂O)₂]·4H₂O (4), [Cd₂(3-PIP)₄(4,4′-bpdc)(H₂O)₂]·5H₂O (5), [Cd(3-PIP)(nip)(H₂O)]·H₂O (6), [Cd₂(TIP)₄(4,4′-bpdc)(H₂O)₂]·3H₂O (7) (PIP=2-phenylimidazo[4,5-f]1,10-phenanthroline, 3-PIP=2-(3-pyridyl)imidazo[4,5-f]1,10-phenanthroline, TIP=2-(2-thienyl)imidazo[4,5-f]1,10-phenanthroline, Hdnba=3,5-dinitrobenzoic acid, H₂ox=oxalic acid, 1,4-H₂bdc=benzene-1,4-dicarboxylic acid, 4,4′-H₂bpdc=biphenyl-4,4′-dicarboxylic acid, H₂nip=5-nitroisophthalic acid) have been synthesized under hydrothermal conditions. Complexes 1 and 4 possess mononuclear structures; complexes 5 and 7 are isostructural and have dinuclear structures; complexes 2 and 3 feature 1D chain structures; complex 6 contains 1D double chain, which are further extended to a 3D supramolecular structure by π-π stacking and hydrogen bonding interactions. The N-donor ligands with extended π-system and organic acid ligands play a crucial role in the formation of the final supramolecular frameworks. Moreover, thermal properties and fluorescence of 1-7 are also investigated.     

Synthesis, structure and electrochemical property of diphenylacetypene-substituted diiron azadithiolates as active site of Fe-only hydrogenases

The model complexes 1-3 of functionalized azadithiolate (ADT)-bridged Fe-only hydrogenases, [Fe₂(Co)₆(μ-ADT)C₆H₄CCR] [R = C₆H₄NO₂-4 (1), C₆H₅ (2), C₆H₄OCH₃-4 (3)] have been synthesized in high yields under mild conditions by using Sonogashira reaction. Spectroscopic study and X-ray crystal structural analysis of 1 demonstrate that the model complexes retain the butterfly structure of 2Fe2S model analogues. The intermolecular C-H?O, C-H?π hydrogen bonding and π-π interactions play important roles in molecular packing of 1. In the presence of HOAc, complex 1 features the catalytic electrochemical proton reduction.     

Structural characterization of rare intramolecularly (1,4-Te?N) bonded diorganotellurides and their monomeric complexes with mercury(II) halides: Metal assisted C-H?X (Hg) interactions leading to supramolecular architecture

Monomeric tellurides 4-RC₆H₄(SB)Te [SB = 2-(4,4′-NO₂C₆H₄CHNC₆H₃-Me); R = H, 1a; Me, 1b; OMe, 1c], which incidentally represent the first example of a telluride with 1,4-Te?N intramolecular interaction, have been prepared and characterized by solution and solid-state ¹²⁵Te NMR, ¹³C NMR and X-ray crystallography. Interplay of weak C-H?O and C-H?π interactions in the crystal lattice of 1b and 1c are responsible for the formation of supramolecular motifs. These tellurides undergo expected oxidative addition reactions with halogens and interhalogens and also interact coordinatively with mercury(II) halides to give 1:2 complexes, HgX₂[4-RC₆H₄(SB)Te]₂ (X = Cl, R = H, 2a; Me, 2b; OMe, 2c and X = Br, R = H, 3a; Me, 3b; and OMe, 3c) with no sign of Te-C bond cleavage, as has been reported for some 1,5-Te?N(O) intramolecularly bonded tellurides. The complexes 2a and 3c are the first structurally characterized monomeric 1:2 adducts of mercury(II) halides with Te ligands. The 1,4-Te?N intramolecular interactions in the solid-state are retained in the complexes highlighting simultaneously the Lewis acid and base character of the Te(II) atom. Packing of molecules in the crystal lattice of 2a and 3c reveals that non-covalent C-H?Cl/Br interactions involving metal-bound halogen atoms possess significant directionality and in combination with coordinative covalent interactions may be of potential use in creating inorganic supramolecular synthons.     

Synthesis, characterization, structures and cytotoxic activity of palladium(II) and platinum(II) complexes containing bis(2-pyridylmethyl)amine and saccharinate

New palladium(II) and platinum(II) complexes containing bis(2-pyridylmethyl)amine (bpma) and saccharinate (sac), [Pd(bpma)(sac)](sac)·2H₂O (1), [Pt(bpma)(sac)](sac)·2H₂O (2), [Pd(bpma)Cl](sac)·2H₂O (3) and [Pt(bpma)(sac)]Cl·1.5H₂O (4), were synthesized and characterized by elemental analysis, IR, NMR and TG-DTA. A single-crystal X-ray analysis of 3 and 4 proved a distorted square-planar geometry around the metal ions with one tridentate bpma ligand and one Cl or sac monoanion. The [Pd(bpma)Cl]⁺ ions in 3 form dimers by intermolecular N-H?Cl and Pd?Pd interactions. The cations reside in the centers of a hydrogen-bonded honeycomb network formed by the uncoordinated sac ions and the lattice water molecules, while the cations of 4 are connected by N-H?Cl and OW-H?O hydrogen bonds into one-dimensional chains. Cyclic planar tetrameric and trimeric water clusters were observed in 3 and 4, respectively. Cytotoxicity of 1-4 was tested against A549, C6 and CHO cells. Although 2 and 4 have no cytotoxicity, the best results were achieved for 1 and 3. In particular, the cyctotoxic activity of 3 is comparable to cisplatin.     

Syntheses and characterization of inorganic–organic hybrids with 4-(isonicotinamido)phthalate and some divalent metal centers

Four new inorganic–organic hybrid frameworks [Mn(L)(H₂O)₂]_n (1), {[Co(L)(H₂O)₃]·2H₂O·CH₃OH}_n (2), {[Zn(L)(H₂O)]·H₂O}_n (3) and [Cd(HL)₂]_n (4) [H₂L = 4-(isonicotinamido)phthalic acid] have been synthesized and characterized by single-crystal X-ray diffraction analysis. Complex 1 has three-dimensional (3D) structure and topology related to SrAl₂ (sra) with Schläfli symbol of (4²·6³·8). And 2 displays (3,3)-connected two-dimensional (2D) network with (4,8²) topology, while 3 exhibits a uninodal (3,3)-connected (6,3) 2D network, which is further linked by N–H?O hydrogen bonding interactions to give 3D structure with hms topology and Schläfli symbol of (6³)(6⁹·8). Complex 4 with partial deprotonated HL⁻ ligands also has a 2D network structure. In addition, the magnetic property of 1, nonlinear optical property of 3 and photoluminescence of 3 and 4 were investigated.     

Heteronuclear M(II)-Ln(III) (M = Co, Mn; Ln = La, Pr, Sm, Gd, Dy and Er) coordination polymers: Synthesis, structures and magnetic properties

Thirteen novel 3d-4f heteronuclear coordination polymers based on the pyridine-2,6-dicarboxylic acid (H₂pda) and imidazole ligands, HIm[(pda)₃MLn(Im)₂(H₂O)₂]·3H₂O (Im = imidazole; M = Co, Ln = Pr (1), Gd (2), Dy (3), Er (4); M = Mn, Ln = Pr (5), Sm (6), Gd (7), Dy (8), Er (9)), HIm[(pda)₃CoSm(Im)₂(H₂O)₂]·2H₂O (10), [(Im)₄M(H₂O)₂][(pda)₄La₂(H₂O)₂]·2H₂O (M = Co (11), Mn (12)), and [(pda)₆Co₃Pr₂(H₂O)₆]·6H₂O (13), have been prepared and structurally characterized. X-ray crystallographic analyses revealed that these complexes display four different types of structures. Complexes 1-9 are isostructural, and possess 1-D chain structures constructed by alternately arrayed nine-coordinated Ln(III) (Ln = Pr, Sm, Gd, Dy, Er) and six-coordinated M(II) (M = Mn, Co) ions. Complex 10 exhibits a unique one-dimensional structure, in which two independent chains are parallel viewed down the a-axis and anti-parallel viewed down the c-axis. Complexes 11 and 12 are isostructural and display 1-D homometallic chain structures. Complex 13 is a 3D framework fabricated through PrN₃O₆ and CoO₆ polyhedrons as building blocks. The variable-temperature solid-state dc magnetic susceptibilities of complexes 2, 3, 4, 9 and 13 have been investigated. Antiferromagnetic exchange interactions were determined for these five complexes.     

Syntheses, structures and photoluminescence of a series of coordination frameworks based on dicarboxylate anion and bis(imidazole) ligand

In this article, ten new coordination frameworks, namely, [Ni(H₂O)₆]·(L3) (1), [Zn(L3)(H₂O)₃] (2), [Cd(L3)(H₂O)₃]·5.25H₂O (3), [Ag(L1)(H₂O)]·0.5(L3) (4), [Ni(L3)(L1)] (5), [Zn(L3)(L1)_0.5]·H₂O (6), [Cd(L3)(L1)_0.5(H₂O)] (7), [CoCl(L3)_0.5(L1)_0.5] (8), [ZnCl(L3)_0.5(L2)_0.5] (9), and [CoCl(L3)_0.5(L2)_0.5] (10), where L1 = 1,1′-(1,4)-butanediyl)bis(imidazole), L2 = 1,1′-(1,4-butanediyl)bis(2-ethylbenzimidazole) and H₂L3 = 3,3′-(p-xylylenediamino)bis(benzoic acid), have been synthesized by varying the metal centers and nitrogen-containing secondary ligands. These structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses and IR spectra. In 1, the L3 anion is not coordinated to the Ni(II) center as a free ligand. The Ni(II) ion is coordinated by water molecules to form the cationic [Ni(H₂O)₆]²⁺ complex. The hydrogen bonds between L3 anions and [Ni(H₂O)₆]²⁺ cations result in a three-dimensional (3D) supramolecular structure of 1. In compounds 2 and 3, the metal centers are linked by the organic L3 anions to generate 1D infinite chain structures, respectively. The hydrogen bonds between carboxylate oxygen atoms and water molecules lead the structures of 2 and 3 to form 3D supramolecular structures. In 4, the L3 anion is not coordinated to the Ag(I) center, while the L1 ligands bridge adjacent Ag(I) centers to give 1D Ag-L1 chains. The hydrogen bonds among neighboring L3 anions form infinite 2D honeycomb-like layers, in the middle of which there exist large windows. Then, 1D Ag-L1 chains thread in the large windows of the 2D layer network, giving a 3D polythreaded structure. Considering the hydrogen bonds between the water molecules and L3 anions, the structure is further linked into a 3D supramolecular structure. Compounds 5 and 7 were synthesized through their parent compounds 1 and 3, respectively, while 6 and 9 were obtained by their parent compound 2. In 5, the L3 anions and L1 ligands connect the Ni(II) atoms to give a 3D 3-fold interpenetrating dimondoid topology. Compound 6 exhibits a 3D three-fold interpenetrating α-Po network structure formed by L1 ligands connecting Zn-L3 sheets, while compound 7 shows a 2D (4,4) network topology with the L1 ligands connecting the Cd-L3 double chains. In compound 8, the L1 ligands linked Co-L3 chains into a 2D layer structure. Two mutual 2D layers interpenetrated in an inclined mode to generate a unique 3D architecture of 8. Compounds 9 and 10 display the same 2D layer structures with (4,4) network topologies. The effects of the N-containing ligands and the metal ions on the structures of the complexes 1-10 were discussed. In addition, the luminescent properties of compounds 2-4, 6, 7 and 9 were also investigated.     

Syntheses,supramolecular structures and properties of six coordination complexes based on 5-sulfosalicylic acid and bipyridyl-like chelates

Six new complexes constructed by 5-sulfosalicylic acid and bipyridyl-like ligands (2,2′-bipy and 1,10-phen), namely [Cu₄(OH)₂(ssal)₂(phen)₄ · 7H₂O] (1), [Cu₄(OH)₂(ssal)₂(bipy)₄ · 2H₂O] (2), [Cd(Hssal)(bipy)] (3), [Cd(HL)₂(phen)₂] (4), [Cr(ssal)(bipy)(H₂O)₂ · 2H₂O] (5) and [Cr(ssal)(phen)₂] (6) (H₃ssal = 5-sulfosalicylic acid, H₂L = p-hydroxybenzenesulfonic acid, bipy = 2,2′-bipy, phen = 1,10-phen) were prepared under hydrothermal conditions and their structures were determined by single-crystal X-ray diffraction. Complexes 1 and 2 are both tetranuclear copper complexes with a stepped topology. In complex 3, a new coordination mode of the Hssal²⁻ group is reported in this work. During the synthetic process of complex 4, in situ decarboxylation of 5-sulfosalicylic acid into p-hydroxybenzenesulfonic acid is involved. Two chromium 5-sulfosalicylates (5 and 6) are reported for the first time. These new complexes display different supramolecular structures by O–H?O, C–H?O hydrogen bonds as well as π?π, C–H?π and O?π interactions. The results of magnetic determination show that ferromagnetic interactions exist in complex 1, however, antiferromagnetic interactions exist in 2.     

Syntheses and characterization of novel lanthanide adamantine-dicarboxylate coordination complexes

Hydrothermal reactions of 1,10-phenanthroline (phen), 1,3-adamantanedicarboxylic acid (H₂L) and lanthanide chlorides yielded six compounds: [Ln(L)(HL)(phen)] (Ln=Pr, 1; Nd, 2), [Ln(L)(HL)(phen)(H₂O)] (Sm, 3; Eu, 4), [Tb(L)(HL)(phen)(H₂O)]₂·2H₂O (5), [Er₃(L)₄(OH)(phen)]₂ (6). Compounds 1-4 are structurally featured by one-dimensional polymeric chains; 5 hold binuclear structure constructed from eight-coordinated lanthanide center LnN₂O₆ of distorted bicapped trigonal prism bridged by dicarboxylate ligands; 6 shows that erbium ions are in mono and bicapped trigonal prismatic geometries, respectively, which are further connected by μ₃-OH to give rise to trinuclear structure. Thermogravimetric analyses of 1, 3 and 5 were performed. Fluorescent measurements of 4 and 5 were carried out, respectively.