Divalent Copper Coordination Polymers Research Articles

Dipyridylamide Donor Disposition and Isophthalate Substituent Steric Effect on the Dimensionality and Topology of Divalent Copper Coordination Polymers

AbstractDivalent copper coordination polymers containing an isophthalate ligand and a dipyridylamide ligand show different dimensionalities and topologies depending on pyridyl nitrogen donor disposition and the steric bulk of the substituent on the dicarboxylate aromatic ring. According to single‐crystal X‐ray diffraction, [Cu(ip)(3‐pna)]n (1, ip = isophthalate, 3‐pna = 3‐pyridylnicotinamide) shows a (4, 4) layered grid structure based on {Cu2(OCO)2} dimeric units. {[Cu(ip)(3‐pina)]·H2O}n (2, 3‐pina = 3‐pyridylisonicotinamide) exhibits similar dimeric units, but in contrast to 1 these are connected into a non‐interpenetrated 3D 658 cds network. Both [Cu(mip)(3‐pina)]n (3, mip = 5‐methylisophthalate) and [Cu(meoip)(3‐pina)]n (4, mip = 5‐methoxyisophthalate) display dimer‐based 41263 pcu networks in contrast to 2. Use of 5‐hydroxyisophthalate (H2hip) as a precursor afforded a mixture of {[Cu2(hip)2(3‐pina)4]·9.5H2O}n (5) and [Cu(hip)(3‐pina)]n (6). Compound 5 shows a 2D interdigitated structure with [Cu(hip)]n coordination polymer layers featuring {Cu2(OCO)2} dimeric units and pendant 3‐pina ligands, while 6 also showed a dimer‐based 41263 pcu network. Use of the very sterically bulky 5‐tert‐butylisophthalate (tbip) ligand afforded the 1D chain coordination polymer {[Cu(tbip)(3‐pina)2(H2O)]·H2O}n (7), which contains isolated copper ions in contrast to 1–6, and has a curious “butterfly“ resemblance. Very weak antiferromagnetic coupling is seen within the {Cu2(OCO)2} dimeric units in 1. Thermal decomposition behavior is also discussed.

Control of water molecule aggregations in copper 1,4-cyclohexanedicarboxylate coordination polymers containing pyridyl–piperazine type ligands

A series of layered divalent copper coordination polymers containing 1,4-cyclohexanedicarboxylate and long-spanning pyridyl–piperazine type ligands exhibits greatly different co-crystallized water molecule aggregations depending on the specific ligands used. Both [Cu(t-14cdc)(4-bpmp)]n (1, t-14cdc=trans-1,4-cyclohexanedicarboxylate, 4-bpmp=bis(4-pyridylmethyl)piperazine) and {[Cu(t-14cdc)(4-bpfp)(H2O)2]·6H2O}n (2, 4-bpfp=bis(4-pyridylformyl)piperazine) possess 2D (4,4) coordination polymer grids. However 1 lacks any co-crystallized water and has pinched grid apertures, while 2 manifests infinite water tapes with T6(2)4(2) classification and rectangular grid apertures. {[Cu2(c-14cdc)2(4-bpmp)]·2H2O}n (3, c-14cdc=cis-1,4-cyclohexanedicarboxylate) has [Cu2(c-14cdc)]2 ribbons with paddlewheel dimeric units linked into 2D slabs by 4-bpmp tethers, along with isolated water molecule pairs. In contrast, {[Cu2(c-14cdc)2(4-bpfp)]·10H2O}n (4) shows a very similar underlying coordination polymer topology but entrains unique decameric water molecule clusters. The minor product {[Cu2(c-14cdcH)2(t-1,4-cdc)(4-bpfp)2(H2O)2]·2H2O}n (5) was isolated along with 4; this compound underwent some in situ cis to trans cyclohexane-dicarboxylate ligand isomerization and exhibits a ladder polymer motif.

Divalent copper trans-1,4-cyclohexanedicarboxylate coordination polymers with isomeric dipyridylamide ligands: new pillared and self-penetrated binodal networks

Hydrothermal synthesis has afforded a pair of divalent copper coordination polymers containing trans-1,4-cyclohexanedicarboxylate (t-14cdc) and one of two isomeric dipyridylamides, 3-pyridylnicotinamide (3-pna) or 3-pyridylisonicotinamide (3-pina). Both of these materials feature unprecedented 3-D topologies. [Cu(t-14cdc)(3-pna)]n (1) manifests [Cu(t-14cdc)]n 4·82 layers featuring embedded anti–syn axial–equatorial bridged [Cu(OCO)]n chain motifs, pillared by anti-conformation 3-pna ligands into a new yet very simple binodal 3,5-connected (4·6·8)(4·66·83) network topology. {[Cu2(t-14cdc)2(3-pina)2(H2O)]·5H2O}n (2) shows two different copper/t14cdc chain motifs with isolated copper ions and {Cu2O2} dimeric units, respectively. These are linked together by 3-pina ligands to afford a new self-penetrated 4,6-connected binodal net with (4·64·8)2(42·612·8) topology. Variable temperature magnetic susceptibility experiments reveal very weak ferromagnetism (g = 2.01(1), J = 0.04(1) cm−1) along the [Cu(OCO)]n chains in 1 and weak antiferromagnetism (g = 1.906(3), J = −3.4(3) cm−1) within the {Cu2O2} dimeric units in 2. Thermal properties are also presented.

Two- and Three-Dimensional Copper 5-Sulfoisophthalate Coordination Polymers with Conformationally Flexible Dipyridyl-Piperazine Type Co-Ligands

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)]·H2O}n (5), which manifests {Cu4(OH)2} “butterfly” clusters linked into a unique three-dimensional (3-D) 3,3,8-connected trinodal lattice with (3.42)(426)(3244536977829) topology. The copper clusters in 3 and 5 exhibit antiferromagnetic coupling.

Topological diversity in copper aromatic meta-dicarboxylate coordination polymers with bis(pyridylformyl)piperazine coligands

Hydrothermal synthesis has afforded divalent copper coordination polymers containing bis(4-pyridylformyl)piperazine (4-bpfp) tethers and aromatic meta-dicarboxylate ligands. {[Cu(ip)(4-bpfp)]·2H 2O} n ( 1, ip = isophthalate) possesses a (4, 4) rectangular grid structure with an unusual ABCD stacking pattern along a 4 1 screw axis. Sterically bulky substituents in the 5-position of the isophthalate ligands reduced the coordination polymer dimensionality, with [Cu 2(tBuip) 2(4-bpfp)(H 2O) 2] n ( 2, tBuip = 5- tert-butylisophthalate) and {[Cu(MeOip)(HMeOip) 2(4-bpfp)]·3H 2O} n ( 3, MeOip = 5-methoxyisophthalate) displaying 1D polymeric ladder and chain motifs, respectively. Compound 3 possesses a rare twofold interpenetrated binodal supramolecular hms net with (6 3)(6 98) topology. Longer meta-disposed acetate pendant arms induced a doubly interpenetrated 3D primitive cubic topology in {[Cu 2(1,3-phda) 2(H 2O) 2(4-bpfp)]} n ( 4, 1,3-phda = 1,3-phenylenediacetate), which possesses antiferromagnetically coupled {Cu 2O 2} kernels ( J = −6.14(8) cm −1).

Two- and three-dimensional aliphatic dicarboxylate copper coordination polymers with bis(3-pyridylmethyl)piperazine tethers

Divalent copper coordination polymers containing aliphatic dicarboxylate and bis(3-pyridylmethyl)piperazine (3-bpmp) tethering ligands exhibit different topologies depending on the length of the polymethylene chain and stoichiometric ratio. {[Cu(succinate)(3-bpmp)]·8H 2O} n ( 1) and {[Cu(adipate)(3-bpmp)(H 2O)]·10H 2O} n ( 4) both display (4,4) rhomboid grids, although the latter shows significant undulations to accommodate the additional girth of the dicarboxylate tethers. [Cu 2(succinate) 2(3-bpmp) 0.5(H 2O)] n ( 2) and [Cu 2(glutarate) 2(3-bpmp)] n ( 3) possess {Cu 2(OCO) 3} partial paddlewheel and {Cu 2(OCO) 4} complete paddlewheel carboxylate bridged dimeric units, respectively. However, 2 has a (6,3) brick-layered structure with a rare binodal moganite ( mog) supramolecular topology, while 3 possesses a non-interpenetrated primitive cubic network. Intriguing co-crystallized water tapes are seen in 1 and 4. Thermal dehydration and decomposition behavior of 1– 4 is also presented.

Isomer dependent self-penetrated topologies and cluster subunits in copper phenylenediacetate coordination polymers with flexible dipyridyl ligands

Divalent copper coordination polymers containing flexible dipyridylpropane (dpp) and phenylenediacetate (phda) ligands display different metal cluster subunits and self-penetrated three-dimensional (3-D) topologies, depending on the disposition of the pendant arms within the anionic components. [Cu2(1,3-phda)2(dpp)]n (1) possesses dinuclear {Cu2(OCO)4} paddlewheel subunits linked into a 6-connected self-penetrated rob lattice with 48668 topology. {[Cu4(1,4-phda)3(OH)2(dpp)2]·2H2O}n (2) manifests non-cubane tetrameric {Cu4(OH)2}6+ kernels, connected into an 8-connected self-penetrated ilc lattice with 4245.63 topology. Antiferromagnetic coupling within the metal cluster subunits is observed in both 1 and 2.

Synthesis and Magnetic Properties of Dual-Ligand Divalent Copper Coordination Polymers with Rhomboid Layer, Archimedean Grid, and Self-Penetrated Network Topologies

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...

Diverse dimensionalities and structures in copper coordination polymers incorporating substituted aliphatic dicarboxylate ligands and 4,4′-bipyridine

Abstract Hydrothermal synthesis has afforded a series of divalent copper coordination polymers with substituted glutarate ligands and the rigid rod tether 4,4′-bipyridine (bpy): {[Cu(Hdmg)2(bpy)]·H2O}n (1, dmg = 3,3-dimethylglutarate), {[Cu2(dmg)(bpy)2](ClO4)]n (2), [Cu2(emg)2(bpy)]n (3, emg = 3-ethyl, 3-methylglutarate) and [Cu2(cda)2(bpy)]n (4, cda = 1,1-cyclopentanediacetate). All materials were characterized by single-crystal X-ray diffraction. Compound 1 manifests μ2-oxygen bridged [Cu2(Hdmg)4] “X”-patterns connected into a ribbon motif by bpy linkers. On the other hand, 2 possesses mixed-valence [CuICuIICuIICuI] tetrameric clusters bridged by dmg ligands and pillared into an 8-connected body-centered cubic (bcu) cationic lattice by bpy linkers. Compounds 3 and 4 are structurally very similar, displaying chain motifs with {Cu2(CO2)4} paddlewheels connected by dicarboxylates, in turn conjoined into (4,4)-grid coordination polymer layers by bpy tethers. Variable temperature magnetic data indicate the presence of very strong antiferromagnetic coupling within the {Cu2(CO2)4} paddlewheels in the latter two complexes, with g = 2.30(2) and J = −352(3) cm−1 for 3 and g = 2.35(2) and J = −352(5) cm−1 for 4. Significant structural contrasts are evident when compared to previously reported divalent copper/4,4′-bipyridine coordination polymers with unsubstituted or 2-methyl substituted glutarate ligands.

Copper benzenedicarboxylate coordination polymers incorporating a long-spanning neutral co-ligand: Effect of anion inclusion and carboxylate pendant-arm length on topology and magnetism

Three divalent copper coordination polymers containing aromatic dicarboxylate ligands and the long-spanning tethering imine bis(4-pyridylmethyl)piperazine (bpmp) have been prepared and structurally characterized. The length of the dicarboxylate pendant arms, carboxylate binding mode, and the inclusion of anionic components play a synergistic role in structure direction in this system. {[Cu(ip)(bpmp)(H 2O)]·5H 2O} n (ip = isophthalate, 1) displays neutral (4,4) rectangular coordination polymer grids that stack in an ABCD repeat pattern. Use of the longer pendant arm dicarboxylate 1,3-phenylenediacetate (phda) resulted in {[Cu 2(phda) 2(bpmp)]·H 2O} n ( 2), a 3-D network coordination polymer with primitive cubic topology that features strongly antiferromagnetically coupled ( J = −331(1) cm −1) {Cu 2(CO 2) 4} paddlewheel units. In the presence of excess nitrate ions, {[Cu(phda)(Hbpmp)](NO 3)·3H 2O} n ( 3) was isolated instead of 2; 3 manifests cationic 2-D coordination polymer layers built from weakly antiferromagnetically coupled ( J = −2.43(1) cm −1) {Cu 2O 2} dimers linked through phda and protonated bpmp ligands. The striking difference in magnetic properties is ascribed to the equatorial–equatorial versus axial–equatorial bridging of copper coordination spheres in 2 and 3, respectively.

Synthesis, structure and magnetic properties of a pair of copper dicarboxylate/dipyridylamine coordination polymers with a non-interpenetrated CdSO 4 topology

Hydrothermal synthesis has afforded a pair of divalent copper coordination polymers containing the kinked and hydrogen-bonding capable imine 4,4′-dipyridylamine (dpa) and aromatic dicarboxylates, {[Cu(iph)(dpa)]·0.5H 2O} n ( 1, iph = isophthalate) and [Cu(tdc)(dpa)] n ( 2, tdc = 2,5-thiophenedicarboxylate). Compounds 1 and 2 contain orthogonally disposed parallel sets of 1-D [Cu(iph)] n and [Cu(tdc)] n chains, respectively, containing dicarboxylate-bridged dinuclear {CuOCO} 2 units. The chain motifs are joined by tethering dpa ligands to construct uncommon non-interpenetrated 3-D CdSO 4 lattices (6 58 topology) in both cases. Variable temperature magnetic studies show the presence of weak antiferromagnetic coupling within the {CuOCO} 2 dimers in both complexes, with J = −2.66(3) and −1.68(5) cm −1 for 1 and 2, respectively.

One- and two-dimensional divalent copper coordination polymers based on kinked organodiimine and long flexible aliphatic dicarboxylate ligands

Hydrothermal synthesis under acidic conditions has afforded a pair of divalent copper coordination polymers containing the kinked dipodal tethering organodiimine 4,4′-dipyridylamine (dpa) and flexible long-chain aliphatic dicarboxylate ligands. The new materials were characterized by single crystal X-ray structure determination, infrared spectroscopy, and thermogravimetric analysis. [CuCl(suberate) 0.5(dpa)] ( 1) manifests 1-D ladder-like motifs aggregated into 3-D through hydrogen bonding and copper-mediated supramolecular interactions. Extension of the aliphatic chain within the dicarboxylate ligand by one methylene unit resulted in {[Cu(azelate)(dpa)(H 2O)] · 3H 2O} ( 2), a (4,4) rhomboid grid 2-D coordination polymer encapsulating acyclic water molecule trimers.