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Metal-coordinated frameworks derived from small peptidic ligands have received much attention thanks to peptides' vast structural and functional diversity. Various peptides with partial conformational preferences have been used to build metal-peptide frameworks, however, the use of conformationally constrained β-peptide foldamers has not been explored yet. Herein we report the first metal-coordination-mediated assembly of β-peptide foldamers with 12-helical folding propensity. The coordination of Ag+ to the terminal pyridyl moieties afforded a set of metal-peptide frameworks with unique entangled topologies. Interestingly, formation of the network structures was accompanied by notable conformational distortions of the foldamer ligands. As the first demonstration of new metal-peptide frameworks built from modular β-peptide foldamers, we anticipate that this work will be an important benchmark for further structural evolution and mechanistic investigation.

Four new MnII- and CoII-containing magnetic coordination polymers, [{Mn(Br-isa)(bpe)·1/2H2O}n (1), {Co(Br-isa)(bpe)1.5·1/2H2O}n (2), [{Mn(Br-isa)(4-bpmh)}4·6H2O]n (3), and [{Co(Br-isa)(4-bpmh)}2·21/2H2O]n (4)] [isa = isophthalic acid, bpe = 1,2-bis-(4-pyridyl)ethylene and 4-bpmh = N,N′-bispyridine-4-yl-methylene-hydrazine], have been synthesized at room temperature, using 5-bromo isophthalic acid (Br-H2isa) and two different N-donating ancillary ligands. The complexes have been characterized by single-crystal X-ray diffraction and other physicochemical techniques. Structure determination reveals two-dimensional (2D) coordination network architectures for all the complexes. In 1, 3, and 4, MnII and CoII dinuclear units are connected via Br-H2isa ligands to form infinite 1D chains. The ancillary N,N′-donor spacer ligands interconnect the 1D chains into 2D coordination layers. Complex 2, on the other hand, can be viewed as being composed of cationic [{Co(bpe)}4]8+ square units that are joined by anionic Br-i...

The design of redox-active metal-organic frameworks and coordination networks (CNs), which exhibit metal- and/or ligand-centered redox activity, has recently received increased attention. In this study, the redox-active metalloligand (RML) [Me4N]3fac-[CrIII(mp)3] (1) (mp = 2-mercaptophenolato) was synthesized and characterized by single-crystal X-ray diffraction analysis, before its reversible ligand-centered one-electron oxidation was examined by cyclic voltammetry and spectroelectrochemical measurements. As complex 1 contains OS coordination sites in three directions, complexation with K+ ions led to the formation of a two-dimensional honeycomb sheet-structured [K3fac-{CrIII(mp)3}(H2O)6]n (2·6H2O), which is the first example of a redox-active CN constructed from a RML with o-disubstituted benzene ligands. Herein, we unambiguously demonstrate the ligand-centered redox activity of the RML, which is incorporated in the redox-active CN 2·6H2O in the solid state.

A comparative investigation of the coordination behaviour of the regio-isomers (o-L and p-L) of the tribenzo-O2S2-macrocycle (L) is reported. On silver(I) complexation, the macrocycle incorporating an o-xylyl group (o-L) yields a discrete endo/exocyclic tetranuclear bis(macrocycle) complex. On the other hand, the corresponding p-xylyl analogue (p-L) gives a 2D square-grid coordination network via exocyclic coordination.

Heating of a pink two-dimensional Co(II) coordination network {[Co2(μ2-OH2)(bdc)2(S-nia)2(H2O)(dmf)]·2(dmf)·(H2O)}n (1) built from 1,4-benzenedicarboxylic acid (H2bdc) residues and thionicotinamide (S-nia) ligands initiates a single-crystal-to-single-crystal transition accompanied by removal of both coordinated and co-crystallized solvents. In the dry blue form, [Co(bdc)(S-nia)]n (dry_1), the Co(II) centers changed from an octahedral to a square pyramidal configuration.

Upon combining enantiopure bis-4-pyridylphenyl-substituted cyclotetrapeptides with HgCl2 and CdCl2, homochiral 1D zigzag coordination polymers were obtained, while the use of a bis-4-pyridyl-substituted cyclotetrapeptide with HgCl2 led to the formation of a different type of 1D coordination network.

Although the cyclo-P6 complex [(Cp*Mo)2(μ,η6:η6-P6)] (1) was reported 30 years ago, little is known about its chemistry. Herein, we report a high-yielding synthesis of 1, the complex 2, which contains an unprecedented cyclo-P10 ligand, and the reactivity of 1 towards the “naked” cations Cu+, Ag+, and Tl+. Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo-P6 middle deck, the [M(1)2]+ complexes are described which show distorted square-planar (M=Cu(4 a), Ag(4 b)) or distorted tetrahedral coordinated (M=Cu(5)) M+ cations. The choice of solvent enabled control over the reaction outcome for Cu+, as proved by powder XRD and supported by DFT calculations. The reaction with Tl+ affords a layered two-dimensional coordination network in the solid state.

Two CdII coordination polymers, namely {[Cd(L434)(Br)(N3)](H2O)1.75}n (1) and [Cd(L434)(I)(N3)(H2O)]n (2) (L434 = 3,5-bis(4-pyridyl)-4-(3-pyridyl)-1,2,4-triazole) have been synthesized by reaction of L434 with CdBr2 or CdI2 in the presence of NaN3 under the same conditions. Single-crystal X-ray diffraction analyses indicate that complex 1 shows a 3D coordination network with unusual gra topology, whereas 2 has a 1D ladder-like coordination chain. The structural distinction on the two complexes, including the different coordination environments of CdII and binding modes of L434 and N3−, can be ascribed to the usage of different halide anions from Br− to I−. In addition, the solid-state properties for complexes 1 and 2 such as thermal stability and fluorescence properties have also been investigated.

Four new coordination networks, namely, {[Cd 3 (titb) 2 (SO 4 ) 2 (NO 3 )]·(NO 3 )·(H 2 O)} n ( 1 ), {[Co 3 (titb) 2 (L 1 ) 2.5 Cl]·(H 2 O) 4 } n ( 2 ), {[Co 3 (titb) 2 (L 2 ) 3 (H 2 O)]·(H 2 O) 4 } n ( 3 ) and {[Co 2 (titb) 2 (HL 3 )(H 2 O) 3 ]Cl} n ( 4 ) (titb = 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, H 2 L 1 = octanedioic acid, H 2 L 2 = 4,4′-(2,2′-oxybis(ethane-2,1-diyl)bis(oxy))dibenzoic acid and H 4 L 3 = benzene-1,2,4,5-tetracarboxylic acid) have been successfully synthesized hydrothermally and structurally characterized by elemental analysis, IR spectra and X-ray diffraction analyses. All compounds contain M II /titb units, including 0D molecular cage for 1 , 1D ladder-like chain for 3 and 2D sheets for 2 and 4 , and all the counteranions (sulfate or carboxylate anions) act as a connector to pillar the M II /titb units to generate the 1D to 3D frameworks. Compound 1 exhibits a 1D chain based on discrete Cd 3 (titb) 2 molecular cage connected by sulfates. Compound 2 is described in terms of 2D Co 3 (titb) 2 sheet further linked by finite hexanuclear (Co 6 L 1 5 ) chain to form a complicated 3D framework with pentanodal (3,4)-connected topology. Compound 3 is a 2D double-layer formed by the 1D Co 3 (titb) 2 ladder-like chain connected by both pairs of (Co2L 2 Co3L 2 ) n left-, right-handed helical chains and 1D (Co1L 2 ) n linear chain. Compound 4 is tetranodal (3,5)-connected array based on Co 2 (titb) 2 double-layered sheet pillared by HL 4 ligands. Furthermore, the thermal and photoluminescent properties have also been studied.

Reactions of the flexible N,N′-di(3-pyridyl)suberoamide (L) with Cu(II) salts in the presence of the isomeric phenylenediacetic acids under hydrothermal conditions afforded three new coordination networks, {[Cu(L)(1,2-pda)]·H2O}n (1,2-H2pda = 1,2-phenylenediacetic acid), 1, {[Cu(L)(1,3-pda)]·2H2O}n (1,3- H2pda = 1,3-phenylenediacetic acid), 2, and {[Cu(L)(1,4-pda)]·2H2O}n (1,4-H2pda = 1,4-phenylenediacetic acid), 3, which have been structurally characterized by X-ray crystallography. Complex 1 forms a single 3,5-coordinated 3D net with the (42·65·83)(42·6)-3,5T1 topology, which can be further simplified as a 6-coordinated (412·63)-pcu topology. Complex 2 is a 5-fold interpenetrated 3D structure with the (65·8)-cds topology, which exhibits the maximum number of interpenetration presently known for cds and complex 3 is the first 1D self-catenated coordination network. The ligand isomerism of the phenylenediacetate ligands is important in determining the structural types of the Cu(II) coordination networks based on the flexible L ligands.

A chiral-at-metal Ir(III) organometallic metallatecton was synthesised as a racemic mixture and as enantiopure complexes and combined with Cu(II) to afford a heterobimetallic (Ir,Cu) grid-type 2D coordination network.

A Zn-based porphyrin containing metal–organic material (porphMOM-1) was transformed into a novel Cu-based porphyrin-encapsulating metal–organic material (porph@HKUST-1-β) via a one-pot post-synthetic modification (PSM) process involving both metal ion exchange and linker installation of trimesic acid. HKUST-1-β is the first example of yao topology and is to our knowledge the first supramolecular isomer of the archetypal coordination network HKUST-1.

A range of supramolecular complexes of O3S2-donor (L1-L3) and O2S3-donor (L4) macrocycles with different ring sizes (L1: 16-membered, L2: 17-membered, L3 and L4: 18-membered) were synthesized and structurally characterized. For the 11 complexes (1–11), the structural topologies and the types of coordination modes including mono- to multinuclear and endo- to exocyclic ones via M–S bonds have been discussed in terms of the possible exocoordination modes proposed. The reactions of L1, L3, and L4 with the silver(I) salts (BF4– and CF3COO–) afforded four complexes 1–4 with different topologies: two endocyclic mononuclear complexes [Ag(L1)NO3] (1) and [Ag(L1)]BF4 (2), and two exocyclic complexes [Ag(L3)(CF3COO)]n (3) and [Ag2(L4)2(CF3COO)2] (4) with a two-dimensional (2D) coordination network and cyclic dimer structures, respectively. In the reactions with copper(I) iodide, L1–L4 afforded the Cu4I4-cubane linked 2D coordination polymer {[(Cu4I4)(L1)2]·CH2Cl2}n (5), one-dimensional (1D) tubular coordination poly...

A series of reactions of different silver thiolates, AgSR (R = Mes (mesityl), Nph (naphthyl), Cy (cyclohexyl)), with bidentate phosphanes was performed yielding a bunch of new compounds, which were characterized by single crystal X-ray diffraction. Depending on the nature of the thiolate and the phosphane the solid state structure of the products varies from discrete complexes or clusters to a 3-dimensional coordination network. The mesityl group favors the formation of trinuclear units which are then linked in one, e.g. [Ag 3 (SMes) 3 (dpph) 2 ] ( 5 ), two, e. g. [Ag 3 (SMes) 3 (dpppt) 2 ] ( 4 ), or three dimensions [Ag 3 (SMes) 3 (dppb) 2 ] ( 3 ), via the phosphanes. With naphthyl and cyclohexyl groups mostly clusters are formed which are either isolated with some phosphanes in their ligand sphere, e.g. [Ag 12 (SCy) 12 (dpppt) 2 ] ( 13 ), or additionally linked by the phosphanes to form 1-dimensional chains, e.g. [Ag 12 (SCy) 12 (dppo)] ( 17 ).

Single-crystal X-ray analysis of a series of six silver(I) trifluoroacetate complexes containing designed ligands each composed of a functionalized cis- or trans-stilbene skeleton bearing two terminal ethynyl groups at variable ring positions provided detailed information on the influence of ligand disposition and orientation, coordination preferences, and coexistence of different types of silver(I)–carbon bonding (silver–ethynide, silver–ethenyl and silver–aromatic) in the construction of a coordination network, which are consolidated by argentophilic and weak intra/intermolecular interactions. The complex 3(Ag2L6)·14AgCF3CO2·[Ag2(CH3CN)3](CF3CO2)2·4H2O·6CH3CN [H2L6 = (E)-1,2-bis(4-ethynylphenyl)ethene] is the first reported example in which an ethynide terminal is bound by six silver(I) ions.

A metal-bearing coordination network synthesised from Re(2,2′-bipyridine-5,5′-dicarboxylate)(CO)3Cl bridging ligands and Cu(II) nodes, [{Cu(DMF)(H2O)[LRe(CO)3Cl]}·DMF]∞ReCu, undergoes an irreversible photoinduced charge transfer process. We demonstrate using time-resolved IR spectroscopy the nature of this photoinduced process and how, under suitable conditions, it is possible to initiate irreversible modification of the crystal through induction of the charge transfer process. As a result we are able to use the photoinduced process, which arises purely as a result of the structure of the coordination network, to write on crystals.

Self-assembly of the trigonal 1,3,5-benzenetricarboxylate (H3btc) and copper salt in the presence of large trigonal N-containing ligand yields a fascinating entangled network, [Cu(Hbtc)(Htpba)]·1.5H2O (1) (Htpba = 4-([4,2′:6′,4″-terpyridin]-4′-yl) benzoic acid). Compound 1 exhibits a novel (2D → 3D) polythreaded network that is first assembled from 2D layers with two types of lateral arms. By inspection of the structure of 1, it is believed that the trigonal ligands with uncoordinated groups acting as dangling lateral arms play an important role in the formation of polythreaded network. The magnetic properties of compound 1 have been studied in the temperature range 2–300 K.

Two Co(II) coordination polymers [Co(3-pmna)(2)(H2O)(2)](n), (1) and {[Co-2(4-pmna)(4)(H2O)]center dot 0.25H(2)O}(n) (2), where 3-Hpmna = 2-(3-pyridylmethylthio)nicotinic acid and 4-Hpmna = 2-(4-pyridylmethylthio)nicotinic acid, were synthesized and fully characterized. 1 displays chain structure, while 2 exhibits 3D coordination network composed of dimer units. Magnetic studies reveal spin-canting behaviors in 1. (C) 2013 Elsevier B.V. All rights reserved.

A series of 2-dimensional (4,4) nets formed in reactions of Co(NCS)2 with divergent 4′-functionalized-4,2′:6′,4″-terpyridine ligands is reported, and the effects of the 4′-substituent R (ligand 1, R = tBu; 5, R = MeO; 6, R = EtO; 7, R = nPrO) on the packing of the nets are described. The 2D-coordination networks in [{Co(NCS)2(6)2}·4CHCl3]n and [{Co(NCS)2(7)2}·4CHCl3]n are essentially isostructural. On going to [{Co2(NCS)4(5)4}·2CHCl3·1.5MeOH]n, modification of both the geometry of the rhombuses that comprise the network, and the packing occurs. All three structures feature head-to-tail π-stacking of 4′-(4-alkoxyphenyl) units, but with variation in their relative orientations. In contrast, [{Co(NCS)2(1)2}·0.5H2O]n comprises double layers of (4,4) nets with hydrophobic coatings of tert-butyl groups, leading to alternating wide and close spacings between adjacent nets.

Six new silver(I) double salts containing embedded 1,3-butadiyne-1,4-diide (C42–) and various types of ancillary heteroaromatic N-donor ligands, namely [{(Ag2C4)0.5(AgNO3)3(L1)}·H2O]n (1; L1 = 3-chloropyridine), [(Ag2C4)2(AgCF3CO2)9(L1)7(H2O)]n (2; L1 = 3-chloropyridine), [(Ag2C4)2(AgCF3CO2)9(L2)7(H2O)]n (3; L2 = 3-bromopyridine), [{(Ag2C4)(AgCF3CO2)5(L3)1.5(H2O)2}·H2O]n (4; L3 = 2-methylpyrazine), [(Ag2C4)(AgCF3CO2)6(L4)6] (5; L4 = 2-cyanopyridine), and [(Ag2C4)(AgCF3CO2)10(L5)8] (6; L5 = imidazole) have been synthesized and characterized by X-ray crystallography. Complex 1 exhibits a two-dimensional coordination network in which the basic building unit is a [Ag4C4Ag4] aggregate. Isomorphous complexes 2 and 3 feature a composite-chain structure with trifluoroacetate and halogen-substituted pyridine ligands surrounding a columnar silver backbone. Complex 4 is a three-dimensional coordination framework composed of silver columns cross-linked by external silver atoms and 2-methylpyrazine bridges. Complex 5 ...

Different combinations of three building blocks, namely the coordination moiety [copper(II)- 4 , 4 ′- bpy ], a carboxylato co-ligand (formato or acetato) and an anion (ClO 4 − , NO 3 − or PF 6 − ), lead to the formation of the three compounds, namely {[Cu 3 ( 4 , 4 ′- bpy ) 3 (μ-OOCH) 4 (H 2 O) 2 ](ClO 4 ) 2 (H 2 O) 6 } n ( 1 ), {[Cu( 4 , 4 ′- bpy )(μ-OOCH)(NO 3 )]} n ( 2 ) and {[Cu 2 ( 4 , 4 ′- bpy ) 2 (μ-OOCCH 3 ) 3 ](PF 6 )(H 2 O)} n ( 3 ). The molecular structures determined by single-crystal X-ray diffraction reveal notable (4,4) topology, regardless of the different monocarboxylato groups (formato for 1 and 2 and acetato for 3 ) and anions. Compound 1 , synthesized from Cu(II), 4 , 4 ′- bpy , ClO 4 − and formate as co-ligand, exhibits a 2D coordination network based on trinuclear chain secondary building units. With coordinating NO 3 − anions (instead of non-coordinating ClO 4 − ), a distinct structural motif, i.e. a 2D framework assembled from dinuclear chain secondary building units, is obtained (compound 2 ). The replacement of the formate ligands by acetate units in compound 3 , gives rise to a 2D framework which is assembled from tetranuclear chain secondary building units. The three new coordination compounds have been characterized and tested for their catalytic properties. All compounds show catalytic activities for the selective cyanosilylation of aldehydes.

Three ligands bearing terminal ethynide moiety attached via pendent arm to a phenyl skeleton have been used in synthesis of three silver (I) complexes, namely, [(AgL1)(AgCF3CO2)3]n (1), {[(AgL2)(AgCF3CO2)6(H2O)2]·(H2O)6}n (2) and [(AgL3)·(AgCF3CO2)5(H2O)]n (3), in which several unconventional intermolecular interactions (silver-ethynyl, silver–aromatic, argentophilicity and C−H···π) have been shown to play vital role in the formation and stabilization of supramolecular structures. In 1, butterfly-shaped Ag4 baskets are interconnected together by trifluoroacetate groups to lead to a layer structure, which is also consolidated by silver–aromatic interactions, adjacent layers are then linked into a three-dimensional supramolecular architecture through weak C−H···F hydrogen bonding. In 2, ladder type chains are associated into three-dimensional supramolecular architecture through a rich hydrogen-bonding system. In 3, square-pyramidal Ag5 baskets are also fused together by the trifluoroacetate groups with the assistance of argentophilic interactions and silver–aromatic interaction give rise to a 2D coordination network, which are further united by C−H···π interaction to produce a three-dimensional supramolecular framework.

Reaction of Co(NCSe)2 with 1,2-bis(4-pyridyl)ethylene (bpe) leads to the formation of [Co(NCSe)2(1,2-bis(4-pyridyl)ethylene)]n, in which Co(NCSe)2 chains are linked by the bpe ligands into a two-dimensional (2D) coordination network. This compound shows metamagnetic behavior with slow relaxation of the magnetization above the critical field (HC) and dominating antiferromagnetic exchange below HC. This is a very rare phenomenon which was never observed before in a 2D selenocyanato coordination polymer.

The synthesis, structure and magnetic property of a new coordination network {[Co2(bcp)2(bpt)2]·2H2O}n (1) (H2bcp = 1,3-bis(4-carboxy-phenoxy)propane and bpt = 2,5-bis(4-pyridyl)-1,3,4-thiadiazole), is reported. Complex 1 shows a 3D 48.66.8 topology with unusual self-penetration, in which represents a new example of 6-connected networks. In addition, the magnetic property of 1 has also been investigated.

Five novel one-dimensional cerium(III) carboxylate coordination polymers, [Ce(O2CCH2CHMe2)3(EtOH)2]n (1), {[Ce(O2CCH2Me)3(H2O)]·0.5(4,4′-bpy)}n (2; 4,4′-bpy = 4,4′-bipyridine), {[Ce2(O2CCHMe2)6(H2O)3]}n (3), {[Ce3(O2CCHMe2)9(nPrOH)4]}n (4), and {[Ce3(O2CCHMe2)9(HO2CCHMe2)2(H2O)2]·2Me2CHCO2H}n (5), showcase the surprisingly consistent tendency of Ce(III) coordination network structures to adopt one-dimensional connection modes. The type of carboxylate as well as the reaction solvents determines the exact bridging versus end-on coordination modes for the carboxylates and, in turn, discriminate between linear, zigzag, and helical arrangements. Detailed magnetochemical analyses reveal pronounced single-ion effects and the expected weak antiferromagnetic coupling.

Five new Zn(II)/ODPT/bpe compounds, namely, {[Zn(bpe)(H2O)2](H2ODPT)·3H2O}n (1), {[Zn4(ODPT)2(bpe)3(H2O)2]2(bpe)·7H2O}n (2), {[Zn2(ODPT)(bpe)2]2·7H2O}n (3), {Zn4(ODPT)2(bpe)}n (4), and {Zn2(ODPT)(bpe)(H2O)2}n (5) (ODPT = 4,4′-oxidiphthalate, bpe =1,2-bis(4-pyridyl)ethane), have been synthesized through a hydrothermal method under different pH conditions, and characterized by single-crystal X-ray diffraction, element analysis, infrared spectra (IR), and thermogravimetric (TG) analyses. Compound 1 shows a 3D network framework constructed by the 1D linear [Zn(bpe)(H2O)4]n2+ cationic chains through extensive hydrogen-bonding. Compound 2 displays an unusual three-dimensional (3D) meso-racemic self-penetrating coordination network with distinct chiral information in the interpenetrating networks. Compound 3 features a novel 4-connected (4·62·83)(42·62·82) topology, also exhibiting an intriguing 3D self-penetrating structure formed by triple- and double-stranded helical chain motifs. Compounds 4 and 5 are based ...

The in situ reaction of Cd(ClO4)2·6H2O with 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride in the presence of lithium hydroxide affords a 2-D CdII coordination polymer, [Cd(L)(H2O)]∞ (1) (L = 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxylate), which exhibits an unusual (3,6)-connected (46.66.83)(43)2 CdI2-type topology. The luminescent and thermal properties of 1 were investigated.

The syntheses and crystal structures of Hg(CN) 2 ·(N 3 ) 2 ·Cu(C 5 H 5 N) 2 ( 1 ) and NaHg(CN) 2 ·(N 3 ) 2 ·Cu(N 3 )(C 3 H 10 N 2 ) 2 ( 2 ) are reported. The interplay between linear Hg(CN) 2 and N 3 - building units by way of long Hg⋯N secondary interactions leads to new types of hybrid inorganic–organic networks in these phases.

A series of five silver coordination polymers [(AgL1)·(AgCF3COO)5·(H2O)3] (1), [(AgL1)2·(AgCF3COO)11·(H2O)6] (2), [(AgL2)·(AgCF3COO)3·(H2O)] (3), [(AgL3)·(AgCF3COO)4·(CH3CN)2] (4), and [(AgL3)·(AgCF3COO)7·(CH3CN)2·(H2O)2] (5) have been constructed from three flexible anionic ligands HL1, HL2, and HL3 (HL1 = 1-chloro-2-(prop-2-ynyloxy)benzene, HL2 = 1-chloro-3-(prop-2-ynyloxy)benzene, HL3 = 1-chloro-4-(prop-2-ynyloxy)benzene). In these compounds, the invariable appearance of the μ4- and μ5-ligation modes of the ethynide moiety affirms the general utility of the flexible silver-ethynide supramolecular synthon o-, m-, p-Cl−C6H5OCH2C C⊃Agn (n = 4, 5) in coordination network assembly. Among them, Ag⋯Cl interaction plays a vital role in assembling the supramolecular structures in complexes 1−3.

Three new compounds of Co II , Ni II and Cu II with a flexible dicarboxylate building block 1,3-phenylenediacetate, along with 4,4′-bipyridine, or 4,4′-trimethylenedipyridine co-ligands, with the formula {[Co 2 (4,4′-bipy) 2 (1,3-pda) 2 ]·1.5H 2 O} n ( 1 ), {Ni(4,4′-bipy)(1,3-pdaH) 2 (CH 3 CH 2 OH) 2 } n ( 2 ), and {Cu(tmdp)(1,3-pda)} n ( 3 ), (where, 1,3-pda = 1,3-phenylenediacetate, 4,4′-bipy = 4,4′-bipyridine, and tmdp = 4,4′-trimethylenedipyridine) have been synthesized and structurally characterized. Compound 1 was synthesized hydrothermally at 180 °C, whereas 2 and 3 were synthesized at room temperature in H 2 O/ethanol medium. The 2D coordination network of 1 is formed by pillaring the 1D staircase Co 2 (1,3-pda) 2 chain by 4,4′-bipy, whereas the 3D supramolecular framework 2 is constituted by connecting the 2D H-bonded Ni(1,3-pdaH) 2 (C 2 H 5 OH) 2 sheets. Compound 3 shows an unusual 2D network which is built by the flexible 1,3-pda and tmdp linkers by connecting Cu 2 (1,3-pda) 2 dimeric building unit.

Eight new silver(I) double salts: AgL1·2AgCF3COO (1), AgL1·3AgNO3 (2), 2AgL2·5AgCF3COO·2CH3CN·H2O (3), 4AgL3·6AgCF3COO·5CH3CN (4), 4AgL4·6AgCF3COO·5CH3CN (5), 2AgL5·4AgCF3COO·NC(CH2)4CN (6), 2AgL5·4AgCF3COO·2CH3CN (7) and AgL6·2CF2(CF2COOAg)2·2CH3CN (8) (L1 = 4-iodophenylethynide; L2 = 3,4-dichlorophenylethynide; L3 = 3-chlorophenylethynide; L4 = 3-bromophenylethynide; L5 = 2-chlorophenylethynide; L6 = 2-fluorophenylethynide) have been synthesised and characterized by X-ray crystallography. All compounds contain the silver–halophenylethynide supramolecular synthon RX−C C⊃Agn (n = 4, 5). In particular, the three-dimensional supramolecular structures in 1 and 2 are stabilized by strong Ag⋯I interactions, while that in 3 is consolidated by both Ag⋯Cl and van der Waals type F⋯Cl interactions. In isomorphous compounds 4 and 5, the presence of respective F⋯Cl or F⋯Br contact contributes to the stability of the network. The silver aggregates in 6, 7 and 8 are stabilized by Ag⋯Cl or Ag⋯F interactions between the ortho-halo substituent and the Agn basket.

The structures of three compounds from the system Ba(C2O4)m(HC2O4)n(H2C2O4)p(H2O)q have been structurally reinvestigated by low-temperature X-ray diffraction. Ba(C2O4)(H2O)2, 1, Ba(C2O4)(H2C2O4)(H2O)2, 2, and Ba(C2O4)0.5(HC2O4)(H2O), 3. The compounds are composed of three-dimensional coordination network structures with bridging oxalates and water molecules. Compound 1 is binodal, four and five connected with topology (4462)(4466)-tcs; 2 contains the common 66-dia net and 3 displays the new uniform network topology 610-loh. Together with the recently reported 610-ghw and 610-rld-z nets, and the 610-fnu net, the loh net forms a subclass of five-connected 610-nets based on the distorted trigonal bipyramidal coordination.

The reaction of Zn(II) nitrate with maleic acid (H(2)mal) / fumaric acid (H(2)fum) and 4,4'-dipyridyl disulfide (4-pds) resulted under same conditions in two distinct interpenetrated Compounds, namely [Zn(4-dps)(2)(H(2)O)(2)]-2Hmal (1) and [Zn(4-dps)(fum)] (2). In 1, Hmal anion adopts bridging mode based on hydrogen bonding, affording a 2-fold parallel interpenetrated 3D -> 3D alpha-Po net hydrogen-bonded framework, in which I D double-stranded chains lire formed, and then extended to a 3D supramolecular architecture combining second-sphere hydrogen-bonded interactions. For 2, fum dianion takes on bis-dentate bridging coordination fashion, furnishing a 2-fold interpenetrated 2D -> 2D (4,4) layered coordination network, in which the tetrahedral Zn(II) atoms are interlinked by 4-dps and fum. Additionally, the compound 2 shows strong fluorescence in the solid state at room temperature.

Three new silver-vanadate hybrid solids, [Ag(bpy)]4V4O12 x 2 H2O (I), [Ag(dpa)]4V4O12 x 4 H2O (II), and Ag4(pzc)2V2O6 (III) (bpy = 4,4'-bipyridine, dpa = 1,2-bis(4-pyridyl)-ethane, pzc = pyrazinecarboxylate), were synthesized by hydrothermal methods and characterized using single crystal X-ray diffraction (I, P2(1)/c, Z = 4, a = 11.375(2) A, b = 14.281(4) A, c = 13.598(3) A, beta = 91.46(1) degrees; II, P2(1)/c, Z = 8, a = 13.5748(3) A, b = 15.3372(4) A, c = 14.1854(3) A, beta = 114.1410(9) degrees; III, P1, Z = 2, a = 3.580(1) A, b = 11.839(4) A, c = 19.321(7) A, alpha = 89.110(7) degrees, beta = 87.719(9) degrees, gamma = 86.243(8) degrees), thermogravimetric analysis, and UV-vis diffuse reflectance. The structures of I and II are constructed from neutral {Ag4V4O12}n layers of clusters that are pillared via the coordination of organic ligands (bpy for I and dpa for II) to the Ag sites in each layer. Conversely, the structure of III is composed of a three-dimensional {Ag2(pzc)(+)}n coordination network with channels containing {VO3(-)}n chains. The lattice water molecules can be removed upon heating toor = 180 degrees C for I (reversibly) and toor = 120 degrees C for II (irreversibly). All three decompose with the removal of organic ligands at higher temperatures of200-300 degrees C. Their optical bandgap sizes were measured to be 2.77 eV for I, 2.95 eV for II, and 2.45 eV for III, which decrease most notably as a result of the band widening for the more extended vanadate structure in III. All three hybrid solids are photocatalytically active for the decomposition of methylene blue under UV light (lambda400 nm; 1.01, 0.64, and 2.65 mg L(-1) h(-1) for I, II, and III, respectively), while only III exhibits a high activity under visible-light irradiation (lambda400 nm; 1.20 mg L(-1) h(-1) ). These new hybrid solids are among the first reported to exhibit high photocatalytic activities under either ultraviolet or visible-light irradiation and have also been analyzed with respect to the effect of the different organic ligands on their atomic- and electronic-structures.

Five new pyridinethiolate-bridged 2D and 3D coordination networks of d10 metal halides formulated with [Cu2(SCN)(4-pyt)] (1), [Ag2Cl2(4-pytH)] (2), [Cu5(SCN)3(2-pyt)2] (3), [Cu4I4(2-pytH)] (4), and [Ag3Cl3(2-pytH)2] (5) (4-pyt = 4-pyridinethiolate, 2-pyt = 2-pyridinethiolate) have been solvothermally synthesized, in which the pyt or pytH ligands were generated via in situ cleavage of S–S bonds of 4,4′-dithiodipyridine (4-dtdp) or 2,2′-dithiodipyridine (2-dtdp) in the presence of Cu(I) or Ag(I) ions. Complexes 1 and 3 are a 3D coordination network, constructed with the interesting inorganic Cu–S coordination layers in a (6,3) topology net bridged by the 4-pyt and SCN ligands for 1 and constructed with the (CuSCN)n layers linked by the 2-pyt-supported (Cu6S6) units for 3. Complexes 2, 4, and 5 are 2D coordination layer structures, which are constructed with 1D (AgCl)n ladder chains linked by [Ag2(4-pytH)2] bridges for 2, with double step-ladder and zigzag (CuI)n chains linked by μ3-2-pytH bridges for 4, and...

A large family of crystalline compounds with silver acetylenediide (Ag 2 C 2 ) as a component have been synthesized and characterized. In most cases the C 2 2− species is enclosed in a silver(I) polyhedron of 6–10 vertices, which may be symbolized as C 2 @Ag n ( n = 6–10). In the present review, emphasis is laid on our systematic studies in the controlled generation and supramolecular assembly of C 2 @Ag n polyhedra to form discrete molecules and higher-dimensional aggregates with the aid of co-existing anions and ancillary ligands.

An aquo-accessible chromatic change in a crystal was induced by means of a reversible coordination geometry shift from octahedra in [Co(C 12 H 8 N 2 )(HO 3 P-C2H4-PO 3 H)(OH2)2] (1) to trigonal-bipyramid in [Co(C 12 H 8 N 2 )(HO 3 P-C2H4-P03H)] (2) at the cobalt(II) center; the crystal-to-crystal phase transition was confirmed by powder X-ray diffraction and solid-state UV-vis diffuse reflectance spectra.

Solvothermal reaction of 4,4'-dithiodipyridine (dtdp) with CuI at 120 or 160 degrees C results in the formation of three new coordination networks formulated with [Cu4I4(tdp)2] (1; tdp = 4,4'-thiodipyridine), [Cu5I5(ptp)2] (2), and [Cu6I6(ptp)2] [3; ptp = 1-(4-pyridyl)-4-thiopyridine]. The starting dtdp reagent was unprecedentedly converted into two tdp and ptp ligands via new in situ cleavage of both S-S and S-C(sp2) bonds and temperature-dependent in situ ligand rearrangement of dtdp. 1 is a two-dimensional (2D) Cu4I4 cubane-like coordination network of 2-fold interpenetration. While in 2, the Cu8I8 and Cu2I2 cluster units are alternately connected by the mu2-sulfur bridges into one-dimensional inorganic chains along the a axis, which are further joined by the ptp spacers into a three-dimensional (3D) coordination network of 2-fold interpenetration. 3 is a 3D non-interpenetrating coordination network constructed with 2D inorganic (Cu2I2)n layers and the ptp spacers. 1 displays an intense orange-red emission light with a maximum at ca. 563 nm. While luminescence quenching occurs in 2 and 3 by electron transfer of a photoelectron to the electronegative acceptor molecule of ptp.

International audience; Two tetrasubsituted derivatives of tetramercaptothiacalix[4]arene in 1,3-alternate conformation bearing either four (3-cyano)propyl (2) or (4-cyano)benzyl (3) moieties have been synthesized and characterized in solution as well as in the solid state by X-ray diffraction on single crystals. Their propensity to form coordination networks was investigated in the presence of silver cation as connecting metal and hexafluorophosphate as counter ion. Whereas the combination of AgPF6 and 2 bearing four (3-cyano)propyl groups leads to a 1D silver coordination network, for 3, containing four (4-cyano)benzyl units, a 3D diamond-like architecture is obtained.

International audience; An unprecedented two-dimensional honeycomb network based on fused triacontanuclear heterometallic wheels of 3.4 nm, {[Co2(Mn3O (N3)2(pic)6(NO3)]-}6 (Hpic = picolinic acid), has been assembled. The hexagonal {Co12Mn18} wheel motif is composed of six oxo-centered {Mn3} trinuclear and six {Co2} dinuclear moieties acting as nodes and linkers, respectively. The paramagnetic properties of this compound observed down to 1.8 K result from the competition of Mn...Mn, Mn...Co and Co...Co interactions in combination with spin–orbit coupling and single-ion behavior of the Co(II) centers.

Two cyano-bridged polymers, [Cu3(CN)3(phen)]n (1) and [Cu(CN)(phen)]n (2) (phen = 1,10-phenphralonine), were synthesized by the hydrothermal reaction of Cu(NO3)2· 3H2O, K3[Fe(CN)6] and phen and were characterized structurally by X-ray, IR and ERSC methods. Compound 1 shows a two-dimensional folded coordination network by Cu(I)CNCu(I) and Cu(I)Cu(I) interaction, while compound 2 exhibits an infinite helix chain by Cu(I)CN linkages. Copyright © 2005 John Wiley & Sons, Ltd.

The reactions of pyridine-2,4,6-tricarboxylic acid (ptcH3) and FeSO4 · 7H2O, CoCl2 · 6H2O or Cu(ClO4)2 · 6H2O gave rise to three novel coordination polymers {[M(H2O)6][M(ptc)(H2O)2]2 · 2H2O}n (M = Fe(II) (1), Co(II) (2)) and {[Cu3(ptc)2(H2O)8] · 4H2O}n (3). 1 and 2 are one-dimensional (1D) polymers while 3 exhibits two-dimensional (2D) coordination network, which are due to the different bonding modes of ptcH3 with metal(II) ions in 1–3.

A series of bis(arylthio)ethers, trans-1,4-bis(phenylthio)-2-butene (L1), trans-1,4-bis(2-pyridylthio)-2-butene (L2), trans-1,4-bis(2-pyrimidinylthio)-2-butene (L3), trans-1,4-bis(4-methyl-2-pyrimidinylthio)-2-butene (L4), and trans-1,4-bis(5-methyl-1,3,4-thiadiazolylthio)-2-butene (L5), have been designed and synthesized, and the reactions of these ligands with AgX salts (X = NO3-, ClO4-, or BF4-) lead to the formation of eight new metal−organic coordination polymers exhibiting from 1D to 3D frameworks. Single-crystal X-ray analysis showed that complexes 1, 2, and 4 exhibit 2D layer frameworks, and 3, 5, 6, and 8 have 1D chain structures, while 7 is a 3D coordination network. In these polymers, a variety of geometries of AgI and coordination modes of the organic ligands were observed due to the different numbers and relative orientation of N donors in the terminal groups of these ligands. In addition, the influences of counteranions and solvent coordination on the framework formations have been discussed...

The novel tridentate ligand 1,3,5-tris(4-cyano-phenoxymethyl)-2,4,6-trimethylbenzene (1) together with silver(I) triflate has afforded the interesting coordination polymer [Ag(1)(CF3SO3)]·0.5H2O, containing undulated (6,3) layers of hexagonal meshes, with alternating Ag and 1 triconnected centers, entangled into 2-fold parallely interpenetrated sheets, which, furthermore, are polycatenated to generate an unique three-dimensional array.

Neutral tetrakis-monodentate tectons 1 and 2, based on the pentaerythritol skeleton and bearing four nicotinoyl or isonicotinoyl groups respectively as coordination sites, have been prepared and their ability to generate coordination networks was studied in the presence of HgCl2 or CoCl2 behaving as metallatectons offering either a “V” or a square type geometry respectively. Whereas in the case of the tecton 1 offering four coordination sites in the same plane (square type geometry) a 1-D coordination network was observed in the presence of neutral HgCl2, in the presence of CoCl2 metallatecton presenting four available coordination sites occupying the corners of a square, a 2-D neutral coordination network was obtained. For tecton 2, possessing also four coordinating sites but occupying the apices of a pseudo tetrahedron, a 2-D network was obtained with HgCl2, whereas in the presence of CoCl2 a 3-D network was observed. In the latter case, a two-fold homo interpenetrating architecture was observed.

A lanthanum ternary complex {[La2(BTA)6(4,4′-bpdo)1.5]·1.5H2O}n (BTA=benzoyltrifluoroacetone, 4,4′-bpdo=4,4′-bipyridine dioxide) was prepared. Crystal analysis showed it has a unprecedented network structure. Two lanthanum ions were bridged by three terminal oxygen atoms from three 4,4′-bpdo molecules forming a binuclear coordination moiety [La2(BTA)6(4,4′-bpdo)1.5]·1.5H2O, and the latter then was linked by 4,4′-bpdo to form a complicated three-dimensional coordination network.

In the title three-dimensional tetrazolate-based coordination polymer, poly[bis(μ3-cyanido-κ3N:C:C)[μ5-5-(pyridin-4-yl)tetrazolato-κ5N:N′:N′′:N′′′:N′′′′]tricopper(I)], [Cu3(C6H4N5)(CN)2]n, there are two types of coordinated CuIatoms. One type exhibits a tetrahedral environment and the other, residing on a twofold axis, adopts a trigonal coordination environment. The closest Cu...Cu distance is only 2.531 (2) Å, involving a bridging cyanide C atom. All four tetrazolate and the pyridine N atom of the 4-(pyridin-4-yl)-1H-tetrazolate anion are coordinated to these CuIatoms and exhibit a μ5-bridging mode. The three-dimensional coordination network can be topologically simplified as a rarely observed (3,3,4,5)-connected network with the Schläfli symbol (4.6.84)2.(42.6.87).(6.82)3.

The synthesis of a new ligand based on a pyrene backbone bearing four pyrazolyl units is reported. Whereas this compound forms a discrete exo-binuclear complex with palladium, in the presence of silver a 1-D coordination network is obtained and structurally characterised in the solid state by X-ray diffraction method. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

The synthesis and structural characterization of novel organometallic coordination polymers are reported. The reaction of Cd(NO3)2 and 4,4′-bipy in CH3OH/H2O gave a 2D coordination network formulated as {[Cd(4,4′-bpy)2·(H2O)2](NO3)2·4H2O}10, which was used to capture an organic guest species (4-amino-benezopheone, C13H11NO (3)) to obtain {[Cd(4,4′-bpy)2(NO3)(H2O)]·NO3·(C13H11NO)2} (1). Using L (L=4,4′-trimethylenedipyridine) instead of 4,4′-bipy, {[Cd(L)2(H2O)2]·2H2O·2NO3·C13H11NO} (2) was synthesized, which has an interesting configuration.