Search

Hydrothermal reaction of metal oxalate (ox) salts and bis(4-pyridylmethyl)piperazine (bpmp) afforded a series of coordination polymers that were structurally characterized by single-crystal X-ray diffraction. {[Cd(H2O)4(bpmp)](ox)}n (1) and {[Co(H2O)4(bpmp)](ox)}n (2) show isostructural cationic one-dimensional (1D) coordination polymer chain motifs with unligated ox anions. A higher temperature polymorph of 2, {[Co(ox)(bpmp)]·3H2O}n (3), possesses a system of threefold interpenetrated three-dimensional (3D) diamondoid nets. {[Mn(H2O)4(bpmp)] [Mn2(ox)3]·5H2O}n (4) manifests a unique 1D + 2D → 3D polyrotaxane coordination polymer structure with 1D cationic [Mn(H2O)4(bpmp)]n chains threaded through apertures coursing through parallel stacks of anionic [Mn2(ox)3]n two-dimensional (2D) hexagonal layers. {[Cu2(ox)2(bpmp)]·6H2O}n (5) possesses 2D [Cu2(ox)2]n layers pillared by bpmp ligands into a 3D [Cu2(ox)2(bpmp)]n coordination polymer network with an unprecedented 4,4-connected self-penetrated (5383)2(5482) ...

Reaction in aqueous solution of cadmium nitrate, succinic acid (H2suc), and one of four possible isomeric dipyridylamide coligands has afforded a series of two-dimensional (2-D) and three-dimensional (3-D) coordination polymers. All were structurally characterized by single-crystal X-ray diffraction. [Cd(suc)(4-pina)]n (1, 4-pina = 4-pyridylisonicotinamide) displays a 3-D 6-connected self-penetrated 446108 mab topology, while {[Cd(suc)(3-pna)]·2.5H2O}n (2, 3-pna = 3-pyridylnicotinamide) has a simple 3-D non-interpenetrated 41263pcu network. The supramolecular isomer 2′ has exactly the same stoichiometry and overall pcu topology as 2 but shows a difference in succinate binding mode. Compounds 1, 2, and 2′ all show similar [Cd(suc)]n layers with embedded {Cd2O2} rhomboid dimers that serve as the 6-connected nodes. {[Cd(suc)(4-pna)(H2O)]·2H2O}n (3, 4-pna = 4-pyridylnicotinamide) manifests an extremely rare 2-D 4-connected 66 layer self-penetrated topology based on cross-pillared [Cd(suc)]n helical chains. Sl...

Hydrothermal synthesis has afforded six chiral divalent metal coordination polymers containing d-camphorate (d-cmph) and 4,4′-dipyridylamine (dpa) ligands, whose topologies depend largely on metal coordination geometry preference. Both cadmium derivatives {[Cd(dpa)(d-cmphH)2(H2O)]·0.875H2O}n (1) and {[Cd(d-cmph)(dpa)(Hdpa)]ClO4}n (1a) exhibit one-dimensional (1-D) chains with protonated pendant ligands; 1 possesses sinusoidal chains with a “wavelength” of over 67 A. [Zn2(d-cmph)2(dpa)(H2O)]n (2) exhibits a two-dimensional (2-D) 3,4-connected binodal net with (53)2(5482) topology. {[Ni(d-cmph)(dpa)]·3H2O}n (3) and {[M2(d-cmph)2(dpa)]·H2O}n (M = Co, 4; M = Cu, 5) manifest three-dimensional (3-D) networks. The nickel derivative has an uncommon 2-fold interpenetrated 4-connected 4284lvt topology, while the isostructural cobalt and copper complexes possess 6-connected pcu topologies based on {M2(OCO)4} paddlewheel dimers. Complexes 1/1a and 2 undergo visible light emission upon ultraviolet excitation. Variable...

Hydrothermal synthesis has afforded four divalent metal coordination polymers containing the aliphatic tricarboxylates tricarballylate (tca) or trans-aconitate (acon) and the kinked tethering co-ligand 4,4′-dipyridylamine (dpa). Diverse structural topologies are evident across this series, with coordination geometry and carboxylate binding mode serving important structure-directing roles. {[Cd2(tca)2(Hdpa)2]·7H2O}n (1) possesses one-dimensional (1-D) ribbon motifs with pendant Hdpa+ ligands and a new 4-connected supramolecular topology, along with co-crystallized water molecule tapes. {[Cd3(acon)2(dpa)2(H2O)2]·4H2O}n (2) has a 4,4-connected binodal lattice with frl (4264)4(6482) topology, while the structurally related phase {[Zn3(tca)2(dpa)2]·2H2O}n (3) has a 4,4-connected binodal lattice with a novel (426282)4(6284) topology. [Cu(Htca)(dpa)]n (4) manifests a 3,5-connected binodal net with rare (4.62)(4.6683) topology. Thermal stability of these materials is discussed. Complexes 1–3 undergo blue-violet l...

Hydrothermal reaction of divalent metal salts, adipic acid and bis(4-pyridylmethyl)piperazine (bpmp), resulted in the generation of a series of coordination polymers whose two-dimensional and three-dimensional topologies depend on coordination environment, adipate conformation and carboxylate binding mode, and piperazinyl ring protonation. {[Cd(adipate)(H2bpmp)(H2O)]SO4·4H2O}n (1) manifests simple (4,4) grid cationic layers, while its oxoanion-free congener [Cd(adipate)(bpmp)]n (2) has a 5-fold interpenetrated diamondoid lattice. {[Cu(adipate)(Hbpmp)(H2O)]ClO4·3H2O}n (3) displays {Cu2O2} dimer-based (4,4) grid cationic layers. The isostructural complexes [M(adipate)(bpmp)(H2O)]n (M = Co, 4; M = Ni, 5) possess anti−syn bridged one-dimensional [M(OCO)]n chains and rare 3,5-connected binodal nets with (4.62)(4.6683) topology. The cadmium derivatives 1 and 2 undergo blue-violet light emission on excitation with ultraviolet. Antiferromagnetic coupling is observed in 3, while ferromagnetic superexchange occurs ...

Hydrothermal reaction of zinc nitrate, pyromellitic acid (H4pyro), and isomeric bis(pyridylmethyl)piperazines has afforded a pair of three-dimensional (3D) coordination polymers with intriguing 3D ...

Several divalent copper coordination polymers containing both 5-sulfoisophthalate (sip) and bis(pyridyl)piperazine type co-ligands have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Across this series, the nature of the neutral co-ligands plays a crucial structure-directing role. Bis(3-pyridylmethyl)piperazine (3-bpmp) and its isomer bis(4-pyridylmethyl)piperazine (4-bpmp) afforded layered phases with different topologies. {[Cu(sip)(H3-bpmp)(H2O)]·3H2O}n (1) and {[Cu(sip)(H4-bpmp)(H2O)]·4H2O}n (2) both possess (4,4) grid topologies, although the latter exhibits mutually inclined 2D + 2D → 3D interpenetration. {[Cu(sip)(H4-bpmp)]·7.5H2O}n (3), which forms concomitantly with 2, has an uncommon (3,6) triangular grid layer based on {Cu2(OCO)2} dimers. A lower temperature pseudopolymorph, {[Cu6(sip)6(H24-bpmp)3(H2O)20]·4H2O}n (4), is an oligomeric molecular species. Employing bis(4-pyridylformyl)piperazine (4-bpfp) generated {[Cu4(sip)2(OH)2(H2O)3(4-bpfp)]·...

Hydrothermal synthesis has afforded a pair of dual-ligand divalent cadmium 4-methylphthalate (mph) two-dimensional (2-D) coordination polymers, wherein the length of the dipyridyl co-ligand plays a...

Hydrothermal reaction of zinc perchlorate, tricarballylic acid (H3tca), and bis(4-pyridylmethyl)piperazine (bpmp) resulted in generation of {[Zn3(tca)2(bpmp)(Hbpmp)2](ClO4)2·5H2O}n (1), which possesses an unprecedented self-penetrated two-dimensional (2-D) layered topology with threaded-loop type linkages. A similar reaction using zinc sulfate as precursor afforded the oxoanion-free phase {[Zn3(H2O)4(tca)2(bpmp)2]·8H2O}n (2), which manifests a new yet simple 3-fold interpenetrated (63)(658) 3,4-connected three-dimensional (3-D) binodal network. Both materials undergo blue-violet luminescence upon exposure to UV radiation.

Four divalent copper coordination polymers containing both 1,2-phenylenediacetate (1,2-phda) and dipyridyl-type coligands have been prepared and structurally characterized by single-crystal X-ray diffraction. {[Cu(1,2-phda)(dpa)]·H2O}n (1, dpa = 4,4′-dipyridylamine) possesses a simple (4,4) rhomboid polymeric grid structure but can be considered a (4,6)-connected binodal supramolecular lattice with (4462)(446108) fsc topology. Use of a longer dipyridyl ligand afforded [Cu2(1,2-phda)2(dpp)]n (2, dpp = 1,3-di(4-pyridyl)propane), which manifests a rare self-penetrated rob lattice (48668 topology) built from the linkage of copper dicarboxylate layers through crossed dpp tethers. [Cu(1,2-phda)(H2O)(4-bpmp)0.5]n (3, 4-bpmp = bis(4-pyridylmethyl)piperazine) forms a 5-connected Archimedean cem layer with 334453 topology. The topology of 3 can be alternately described as a 3,4-connected binodal layer with a V2O5-type network. Incorporation of nitrate counterions led to formation of {[Cu(1,2-phda)(H2O)(H4-bpmp)] (N...

Three cadmium coordination polymers incorporating both a flexible aliphatic α,ω-dicarboxylate and the hydrogen-bonding capable diimine 4,4′-dipyridylamine (dpa) have been prepared and structurally characterized. {[Cd(adp)(dpa)]}n (1, adp = adipate) adopts a doubly interpenetrated decorated primitive cubic three-dimensional (3D) coordination polymer network. {[Cd7(pim)6(dpa)6(H2O)2](ClO4)2·6H2O}n (2, pim = pimelate) exhibits a complex (8,10)-connected binodal self-penetrated cationic 3D network with (384145462)(31041851463) topology constructed from the linkage of oligomeric {Cd7(dpa)6(H2O)2}14+ secondary building units through pimelate ligands with different conformations. To the best of our knowledge, this is the highest-connected binodal self-penetrated lattice reported to date. Extending the length of the α,ω-dicarboxylate resulted in a CdSO4-type (658 topology) 4-connected 3D network in {[Cd(sub)(dpa)]·2H2O}n (3, sub = suberate). The length of the polymethylene unit within the dicarboxylate ligand, th...

Hydrothermal synthesis has afforded coordination polymers incorporating the kinked dipodal organodiimine 4,4′-dipyridylamine (dpa) and the flexible aliphatic dicarboxylate suberate dianion, with a general formulation of [M(sub)(dpa)(H2O)]n (sub = suberate, M = Co, 1; M = Ni, 2). Both 1 and 2 exhibit crystallographically disordered suberate ligands, producing a three-dimensional “ligand vacancy” α-Po coordination polymer network composed of two different types of [M(sub)(dpa)(H2O)]n idealized layers.

Two cadmium glutarate coordination polymers incorporating the hydrogen-bonding capable tethering organodiimines 4,4′-dipyridylamine (dpa) or bis(4-pyridylmethyl)piperazine (bpmp) have been prepared and structurally characterized. [Cd(glutarate)(dpa)]n (1) manifests a doubly interpenetrated decorated α-Po (pcu, 41263 topology) lattice, with octahedral coordination at cadmium. Compound 1 undergoes blue-violet luminescence upon UV irradiation. Use of the longer tethering organodiimine resulted in the formation of {[Cd(glutarate)(bpmp)(H2O)]·6H2O}n (2), which displays non-interpenetrated (4,4)-rhomboid grid coordination polymer layers. In contrast to 1, the cadmium ions in 2 adopt a pentagonal bipyramidal coordination geometry, with aqua ligands allowing construction of a hexagonal boron nitride (bnn, 4466 topology) supramolecular framework through interlayer hydrogen bonding. Unprecedented one-dimensional water molecule tapes with 2T5(2)7(2) classification occupy large ellipsoid channels coursing through the...

Hydrothermal synthesis has afforded a family of divalent metal coordination polymers incorporating both the isophthalate dianion (ip) and the flexible organodiimine N,N′-bis(4-pyridylmethyl)piperazine (bpmp). The compounds of type {[M(ip)(bpmp)]·H2O} (M = Co, 1; M = Cd, 2) are isomorphous, possessing puckered two dimensional (2D) rectangular grid layers built from the linkage of [M2(ip)2] double chains through bpmp tethers. In contrast, the nickel congener {[Ni(ip)(bpmp)(H2O)]·H2O} (3) displays a corrugated, interpenetrated 2D structure. {[Zn(ip)(bpmp)]·H2O} (4) adopts a 5-fold interpenetrated three-dimensional diamondoid topology due to the tetrahedral coordination at Zn. Analysis of the variable temperature magnetic susceptibility of 1 indicated the presence of ferromagnetic coupling and zero-field splitting effects within the dinuclear subunits along with possible long-range ferromagnetic interactions transmitted through the ip ligands. The d10 derivatives 2 and 4 exhibited blue-violet luminescence upo...

Hydrothermal synthesis has afforded a series of zinc-containing coordination polymers incorporating the kinked organodiimine 4,4′-dipyridylamine (dpa) and phenylenediacetate (phda) isomers. {[Zn(1,4-phda)(dpa)]·H2O}∞ (1) manifests a two-dimensional (2D) corrugated layer morphology. While both {[Zn(1,2-phda)(dpa)]·2H2O}∞ (2) and [Zn(1,3-phda)(dpa)]∞ (3) contain three-dimensional 4-fold interpenetrated coordination polymer networks, 2 possesses the SrAl2 structure type (sra, 42638 topology) but the acentric material 3 adopts the diamond structure type (dia, 66 topology). The varying morphologies thus reveal a significant structure-directing effect of the position of the acetate groups during self-assembly of these coordination polymers. Hydrogen-bonding mechanisms imparted by the central amine group of the dpa ligand provide ancillary supramolecular structure-directing effects in all three cases. All three materials undergo blue–violet luminescence upon irradiation with ultraviolet light.

Hydrothermal synthesis has afforded a family of five divalent metal succinate (suc) coordination polymers incorporating the kinked dipodal organodiimine 4,4‘-dipyridylamine (dpa), which were structurally characterized by single-crystal X-ray diffraction and thermogravimetric analysis. [Co(suc)(dpa)2] (1) manifests chiral helical one-dimensional (1-D) chains formed from the linkage of neighboring Co atoms through bischelating bisbridging succinate moieties, with pendant dpa ligands. {[Ni(dpa)2(suc)0.5]Cl} (2) possesses a rare self-interpenetrated 5-connected cationic framework with a unique 610 topology, constructed from the junction of quadruply interpenetrated adamantoid [Ni(dpa)2]2n+ networks via bischelating μ2-succinate ligands. {[Cu(suc)(dpa)]·0.5H2O} (3) exhibits a doubly interpenetrated CdSO4 net (658 topology) containing both 1-D double braided cationic helical [Cu(dpa)]2+ ribbons and orthogonally situated zigzag [Cu(suc)] chains. The quadruply interpenetrated three-dimensional (3-D) network struc...

The one-dimensional (1-D) coordination polymers [Cu(2,4‘-bpy)4SO4]·6H2O (1), [Cu(4-phpyr)4SO4]·5H2O (2), [Cu(2,4‘-bpy)4SiF6]·4.5 H2O (3), and [Cu(4-phpyr)4SiF6]·4.5H2O (4) (2,4‘-bpy = 2,4‘-bipyridine, 4-phpyr = 4-phenylpyridine) have been prepared in aqueous solution and characterized via single-crystal X-ray diffraction. The crystal structures of 1−4 manifest zigzag 1-D chains constructed from interdigitated “X-shaped” CuL42+ cations and the relevant counteranions while entraining hydrogen-bonded supramolecular water substructures that serve to connect the 1-D coordination polymer subunits into pseudo three-dimensional (3-D) structures. In 1, 1-D aqueous tapes comprised of water molecule tetramers and individual water molecules are evident. Discrete zero-dimensional (0-D) water clusters are observed in 2, while discrete water molecule chains are manifested in 3 and 4. The markedly different morphologies of the respective aqueous substructures within this family of coordination polymers are dictated by th...

The coordination polymer {[Cu2(glu)2(bpmp)]·4H2O}n (1, glu = glutarate, bpmp = N,N′-bis(4-pyridyl)piperazine) was prepared via solution-phase methods. Single-crystal X-ray diffraction revealed the presence of [Cu2(glu)2]n layers containing “paddle-wheel” dinuclear units. These layers are connected by tethering bpmp ligands into a self-penetrated three-dimensional covalent network with 6-connected 446108 topology. Variable-temperature magnetic studies indicated the presence of very strong antiferromagnetic coupling (J = −283(8) cm−1) within the {Cu2} dinuclear units of 1. Incipient channels within the self-penetrated framework are occupied by ”infinite” C(4) water molecule chains.