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Four copper dimethylmalonate (dmmal) phases containing long-spanning dipyridyl coligands have been prepared and structurally characterized by single-crystal X-ray diffraction. {[Cu2(dmmal)2(edin)(H2O)2]·3H2O}n (1, edin = N,N′-(ethane-1,2-diyl)diisonicotinamide) and {[Cu2(dmmal)2(bdin)(H2O)2]·2H2O}n (2, bdin = N,N′-(butane-1,4-diyl)diisonicotinamide) both show (6,3) herringbone layers constructed from the edin pillaring of [Cu(H2O)(dmmal)]n chain motifs, that feature embedded equatorial-equatorial bridged {Cu(OCO)}n chains. [Cu2(dmmal)2(bpmp)]n (3, bpmp = bis(4-pyridylmethyl)piperazine) shows a decorated (4,4) grid topology built from bpmp pillared [Cu2(dmmal)2]n ribbon motifs, that feature embedded {Cu2(OCO)4} paddlewheel dimeric units. [Cu2(dmmal)2(bpfp)]n (4, bpfp = bis(4-pyridylformyl)piperazine) shows a 5-connected non-interpenetrated 3D 4466 sqp topology, formed from the bpfp pillaring of rectangular equatorial-equatorial bridged [Cu2(dmmal)2]n layers. Variable temperature magnetic studies were carried out on 1, 2 and 4, indicating predominant ferromagnetic superexchange within their equatorial-equatorial {Cu(OCO)}n chain motifs.

Four new divalent zinc coordination polymers containing a dianionic cyclohexyldicarboxylate and the long-spanning pillaring dipyridyl ligand bis(4-pyridylmethyl)piperazine (bpmp) have been prepared and structurally characterized via single-crystal X-ray diffraction. Significant structural and topological diversity across the series is evident. {[Zn2(cis-12cdc)2(bpmp)]·6H2O}n (1, cis-12cdc = cis-1,2-cyclohexanedicarboxylate) shows a coordination polymer layer motif with embedded paddlewheel {Zn2(OCO)4} dinuclear units and T6(4)4(4) classification water tapes. Using cis-1,2-cyclohex-4-enedicarboxylate (cis-12chedc) afforded [Zn2(cis-12chedc)2(bpmp)(H2O)2]n (2), which manifests a simple yet unusual (6)(648.10) topology. [Zn2(cis-13cdc)2(bpmp)]n (3, cis-13cdc = cis-1,3-cyclohexanedicarboxylate) displays sawtooth (4,4) coordination polymer layers, while [Zn2(trans-14cdc)2(bpmp)]n (4, trans-14cdc = trans-1,4-cyclohexanedicarboxylate) shows a 3D system of coordination polymer networks with 3-fold interpenetrated 41263 pcu topology. The layered phases 1–3 showed capability for the detection of small quantities of nitrobenzene in ethanol suspension.

Hydrothermal reaction of copper nitrate, 1,2-phenylenediacetic acid (pdaH2), and flexible dipyridylamide ligands afforded four new coordination polymers with diverse structural topologies, as characterized by single crystal X-ray diffraction. {[Cu(pda)(hdn)(H2O)2]·2H2O}n (1, hdn = N,N′-(hexane-1,6-diyl)dinicotinamide) shows 1D ribbon motifs. In contrast, [Cu(pda)(hdin)]n (2, hdin = N,N′-(hexane-1,6-diyl)diisonicotinamide) presents a rare example of a five-fold interpenetrated 4-connected 658 cds 3D topology. [Cu(pda)(bdn)]n (3, bdn = N,N′-(butane-1,4-diyl)dinicotinamide) displays an unprecedented 3,5-connected binodal (63)(6783) 3D topology with embedded {Cu(OCO)}n axial-equatorial bridged chain motifs. {[Cu(pda)(bpfp)(H2O)]·4H2O}n (4, bpfp = N,N′-(bis-4-pyridylformyl)piperazine) shows rectangular (4,4) grid submotifs. All four materials were assayed as heterogeneous catalysts for the degradation of Congo Red (CR) in aqueous suspension under ultraviolet irradiation; only compound 3 catalyzed the degradation. Thermal properties of 1–4 are also discussed herein.

Hydrothermal reaction of cadmium nitrate, 2,5-thiophenedicarboxylic acid (H2tdc) and one of the conformationally flexible dipyridylamide ligands N,N′-(heptane-1,7-diyl)dinicotinamide (hedn), N,N′-(hexane-1,6-diyl)diisonicotinamide (hdin), N,N′-(hexane-1,6-diyl)dinicotinamide (hdn), N,N′-(propane-1,3-diyl)dinicotinamide (pdn), N,N′-(propane-1,3-diyl)diisonicotinamide (pdin) produced five new coordination polymers which were structurally characterized by single-crystal X-ray diffraction. {[Cd(tdc)(hedn)(H2O)]·3H2O}n (1) manifests looped (4,4) grid motifs with two-fold parallel interpenetration. {[Cd(tdc)(hdin)(H2O)]·H2O}n (2) shows stacked (4,4) grid motifs. {[Cd2(tdc)2(hdn)(H2O)4]·H2O}n (3) exhibits herringbone (6,3) grid motifs. In contrast to the 2D topologies seen in 1–3, {[Cd2(tdc)2(pdn)(H2O)2]·4H2O}n (4) displays a 3D self-penetrated net with 6482 nbo topology and [Cd(tdc)(pdin)]n (5) shows a 1D ribbon structure constructed from staple-conformation pdin ligands and {Cd2O2} dimer-containing [Cd(tdc)]n chains. Thermal decomposition and nitrobenzene detection properties of these five new materials are discussed.

Three new divalent cobalt coordination polymers containing anionic cyclohexyldicarboxylate and neutral 3-pyridylnicotinamide (3-pna) tethering ligands have been prepared and structurally characterized via single-crystal X-ray diffraction. These phases show a diversity of layered topologies and differences in cobalt atom aggregation. [Co(cis-12chedc)(3-pna)(H2O)]n (1, cis-12chedc = 4-cyclohexene-cis-1,2-dicarboxylate) shows a standard (4,4) grid topology with magnetically isolated cobalt atoms. [Co(cis-13cdc)(3-pna)]n (2, cis-13cdc = cis-cyclohexane-1,3-dicarboxylate) shows a 2D 3,5-connected net with a previously unreported (3.52)(3253647) topology featuring “infinite” anti–syn bridged {Co(OCO)}n chain motifs pillared by 3-pna ligands. [Co(cis-14cdc)(3-pna)]n (3, cis-14cdc = cis-cyclohexane-1,4-dicarboxylate) shows a 2D 6-connected triangular net with (3,6) topology built from {Co2(OCO)2} dimeric units linked by cis-14cdc and 3-pna tethers. Magnetic susceptibility studies of compound 2 revealed a decrease in χmT product upon cooling, ascribed to antiferromagnetic coupling along the {Co(OCO)}n chain motifs concomitant with Kramers doublet formation (g = 2.24(3), D = 12.8(8) cm−1, J = –0.46(6) cm−1). For compound 3, Kramers doublet formation was also observed, but with ferromagnetic superexchange within its {Co2(OCO)2} dimeric units (g = 2.27(1), D = 24(1) cm−1, J = 0.35(2) cm−1). Thermal decomposition behavior of the three new phases is also discussed.

In the title compound, {[Cu(C14H8O4)(C11H10N4O)(H2O)]·1.25H2O} n , the CuII cations are coordinated in a square-pyramidal fashion by trans carboxylate O-atom donors from two diphenate (dip) ligands, trans pyridyl N-atom donors from two bis(4-pyridyl)urea (bpu) ligands, and a ligated water molecule in the apical position. [Cu(H2O)(dip)(bpu)] n coordination polymer layer motifs are oriented parallel to (\overline{1}02). These layer motifs display a standard (4,4) rectangular grid topology and stack in an AAA pattern along the a-axis direction to form the full three-dimensional crystal structure of the title compound, mediated by N—H...O and O—H...O hydrogen bonding patterns involving the water molecules of crystallization.

We performed comparative profiling of four specialized metabolites in the lichen Evernia prunastri, collected at three different geographic locations, California and Maine, USA, and Yoshkar Ola, Mari El, Russia. Among the compounds produced at high concentrations that were identified in all three specimens, evernic acid, usnic acid, lecanoric acid and chloroatranorin, evernic acid was the most abundant. Two depsidones, salazinic acid and physodic acid, were detected in the Yoshkar-Ola collection only. The crystalline structure of evernic acid (2-hydroxy-4-[(2-hydroxy-4-methoxy-6-methylbenzoyl)oxy]-6-methylbenzoate) (hmb) revealed two crystallographically and conformationally distinct hmb anions, along with two monovalent sodium atoms. One hmb moiety contained an exotetradentate binding mode to sodium, whereas the other exhibited an exohexadentate binding mode to sodium. Embedded edge-sharing {Na2 O8 }n sodium-oxygen chains connected the hmb anions into the full three-dimensional crystal structure of the title compound. The crystal used for single-crystal X-ray diffraction exhibited non-merohedral twinning. The data suggest the importance of the acetyl-polymalonyl pathway products to processes of maintaining integrity of the lichen holobiont community.

Hydrothermal reaction of cobalt nitrate, 2-carboxycinnamic acid (H2cca), and a long-spanning dipyridyl-type ligand resulted in three coordination polymers that were characterized by single crystal X-ray diffraction and manifested different structural topologies and interpenetration schemes. {[Co(cca)(4-bpmp)(H2O)2]·4H2O}n (1, 4-bpmp = bis(4-pyridylmethyl)piperazine) shows a 2-fold interpenetrated 4-connected 66 dia network. Use of the dipyridylamide bis(4-pyridylformyl)piperazine (4-bpfp) produced a crystalline mixture of the major product 3D 6-connected 41263 pcu network coordination polymer {[Co(cca)(4-bpfp)]·2H2O}n (2) and the minor product 1D chain coordination polymer [Co(dibf)2(4-bpfp)(H2O)2]n (3, dibf = 3-dihydro-3-oxo-1-isobenzofuranacetate). The in situ rearrangement of 2-carboxycinnamic acid in the presence of 4-bpfp produced the anionic lactone dibf in 3. Thermal decomposition behavior of the new major product phases was probed.

Hydrothermal reaction of a metal nitrate, a methyl-substituted aliphatic dicarboxylic acid, and the hydrogen-bonding capable 4,4′-dipyridylamine (dpa) ligand afforded four crystalline coordination polymers whose dimensionality, topology, and interpenetration scheme depends on the aliphatic tether length, methyl group position, and coordination geometry at the metal. The four new phases were structurally characterized via single-crystal X-ray diffraction. [Zn(22dmg)(dpa)]n (1, 22dmg = 2,2-dimethylglutarate) displays a system of mutually inclined interpenetrated (4,4) grid coordination polymer layers. [Zn(33dmg)(dpa)]n (2, 33dmg = 3,3-dimethylglutarate), in contrast to 1, displays a stacked arrangement of pairs of (4,4) grid coordination polymer layers, without any interpenetration. [Zn(3mad)(dpa)]n (3, 3mad = 3-methyladipate) possesses a system of four-fold interpenetrated 66 dia topology coordination polymer networks. [Cd(33dmg)(dpa)]n (4) displays a 2-fold interpenetrated 41263 pcu 3D topology, based on pillaring of dimer-based [Cd2(33dmg)2]n layers by pairs of dpa ligands. Luminescent behavior in 1–4 is attributed to intra-ligand molecular orbital transitions within the dpa aromatic pyridyl rings. The new phases were also surveyed for the ability to detect nitroaromatics in ethanol suspension, with 4 providing optimum response for nitrobenzene detection. Thermal decomposition behavior is also discussed herein.

Hydrothermal reaction of zinc nitrate, diphenic acid (H2dip), and one of the dipyridylamide ligands N,N′-(hexane-1,6-diyl)diisonicotinamide (hdin), N,N′-(pentane-1,5-diyl)diisonicotinamide (pedin), N,N′-(butane-1,4-diyl)diisonicotinamide (bdin), or N,N′-(ethane--1,2-diyl)diisonicotinamide (edin) resulted in coordination polymers whose dimensionalities depend on the aliphatic tether length within the coligand and the amount of base used in the synthesis. The five new phases were characterized by single crystal X-ray diffraction. {[Zn(dip)(hdin)]·2.5H2O}n (1) and {[Zn(dip)(pedin)]·2.5H2O}n (2) both possess undulating 2D coordination polymer layers with [Zn(dip)]n chains spanned by looped dipyridylamine ligands into a 2,4-connected self-penetrated (6)(648.10) topology. [Zn(dipH)2(bdin)]n (3) manifests a 1-D zig-zag chain topology, while {[Zn3(dip)3(bdin)3]·13H2O}n (4) and {[Zn(dip)(edin)]·3H2O}n (5) manifest helical substructures linked into a rare two-fold interpenetrated 6482 nbo topology. Thermal and luminescent properties were also probed; compounds 1–5 showed ability to detect nitrobenzene in ethanol suspension with the 3D derivatives 4 and 5 manifesting the best “turn-off” luminescence quenching behavior.

Crystals of {[Cu5(oba)4(bpmp)3(H2O)2]·10H2O}n (1, oba = oxybisbenzoate, bpmp = bis(4-pyridylmethyl)piperazine) were prepared by hydrothermal methods. A single-crystal structure determination showed the presence of [Cu5(oba)4(H2O)2]n ribbons with {Cu2(OCO)4} paddlewheel dimers connected to isolated divalent copper atoms and isolated monovalent copper atoms. These ribbon motifs are pillared into the full complicated 3D coordination polymer net of 1 by long-spanning bpmp tethers. Compound 1 presents the unique example of a self-penetrated 3,4,4-connected (83)2(6.8.104)(64.8.10) topology. Decameric water molecule clusters entrained within the net play an important stabilization role.

Hydrothermal reaction of nickel nitrate, an adamantane-based dicarboxylic acid, and a hydrogen-bonding capable dipyridyl ligand generated six coordination polymers that were isolated and subsequently structurally characterized by single-crystal X-ray diffraction. {[Ni(adc)(ebin)(H2O)]·2H2O}n (1, adc = 1,3-adamantanedicarboxylate, ebin = N,N′-ethylenediaminebis(isonicotinamide)) shows ABAB stacked (4,4) coordination polymer grids. In contrast, [Ni(ada)(ebin)]n (2, ada = 1,3-adamantanediacetate) manifests a very rare self-penetrated layer with a 3,5-connected (426)(42678) topology. {[Ni(adc)(pbin)]·2H2O}n (3, pbin = N,N′-propyleneenediaminebis(isonicotinamide)) shows a dimer-based 41263 pcu network, while {[Ni5(ada)5(pbin)5(H2O)5]·8H2O}n (4) manifests looped layers with (4)(4.85) topology. {[Ni2(adc)(adcH)2(dpa)2]·H2O}n (5, dpa = 4,4′-dipyridylamine) possesses [Ni2(adc)(adcH)2] linear fragments connected into an uncommon 3-connected 103 srs network. Concomitantly formed along with 5, {[Ni(adc)(dpa)]·6.5H2O}n (6) is a stacked (4,4) grid phase but with a direct AAA stacking pattern. Embedded {Ni2(OCO)2} dimeric units in 2 and 3 exhibit antiferromagnetic coupling (J = −10.5(1) cm−1 (2), J = −2.38(7) cm−1 (3)). Thermal decomposition behavior of 1–6 was also investigated.

Hydrothermal reaction of copper nitrate, sodium 5-sulfoisophthalate (sip), and a long-spanning hydrogen-bonding capable dipyridylamide ligand afforded four coordination polymers whose dimensionality depends critically on the dipyridylamide tether length. The four new phases were structurally characterized via single-crystal X-ray diffraction. {[Cu 8 (sip) 4 (pbn) 3 (nic)(μ 3 -OH) 2 (μ 2 -OH)(μ 2 -H 2 O)(H 2 O) 4 ]·5H 2 O} n ( 1 , pbn = 1,3-propanediaminebis(nicotinamide), nic = nicotinate) manifests an intriguing 2D slab structure featuring trimeric copper clusters containing bridging hydroxide ions and water molecules along with substantial crystallographic disorder. {[Cu 3 (sip) 2 (pbin) 4 (H 2 O) 4 ]·14H 2 O} n ( 2 , pbin = 1,3-propanediaminebis(isonicotinamide)) shows 1D chain motifs with curled conformation dipyridylamide ligands. {[Cu 4 (μ 3 -OH) 2 (sip) 2 (hbin)]·2H 2 O} n ( 3 , hbin = 1,6-hexanediaminebis(isonicotinamide)) features [Cu 4 (μ-OH) 2 (sip) 2 ] butterfly clusters connected into a 3D 3,8-connected network with (4.6 2 ) 2 (4 2 6 18 7 4 8 4 ) topology. {[Cu(Hsip)(hbn)(H 2 O)]·2H 2 O} n ( 4 , hbn = 1,6-hexanediaminebis(nicotinamide)) exhibits a sawtooth (4,4) grid topology. Variable temperature magnetic susceptibility studies on 1 and 3 revealed antiferromagnetic behavior ( g = 2.079(6), J = −5.7(2) cm −1 for 1 , g = 2.14(2), J 1 = −19(1) cm −1 , J 2 = −35(2) cm −1 for 3 ). Thermal decomposition behavior of 1 – 4 is also discussed.

Hydrothermal reaction of either cobalt or cadmium nitrate, D-camphoric acid (H2cam), and conformationally flexible dipyridylamide ligands produced five coordination networks which were structurally characterized by single-crystal X-ray diffraction. {[Co2(DL-cam)2(bdn)]·2H2O}n (1, bdn = N,N′-(butane-1,4-diyl)dinicotinamide) possesses {Co2(OCO)4} paddlewheel dimer-based [Co2(DL-cam)2] grid layers pillared by bdn ligands into a 6-connected 41263pcu network. In contrast, the cadmium analog {[Cd2(D-cam)2(bdn)2]·5H2O}n (2) shows {Cd2(OCO)2} dimer-based [Cd2(D-cam)2] layers tethered by bdn ligands into an 8-connected 42464bcu network. {[Co2(D-cam)2(pdn)]·2H2O}n (3, pdn = N,N′-(propane-1,3-diyl)dinicotinamide) manifests a self-penetrated 446810 mab network in contrast to 1, and retains chirality. {[Cd2(D-cam)2(pdn)]·H2O}n (4) manifests {Cd2(OCO)4} paddlewheel dimer-based [Cd2(D-cam)2] grids, connected by exotridentate pbn ligands into a unique 3,7-connected 3D network with (3·52)(324456687) topology derived from a rare non-self-penetrated 4966acs topology sublattice. {[Co2(DL-cam)2(pedn)]·2H2O}n (5, pedn = N,N′-(pentane-1,5-diyl)dinicotinamide) shows a hybrid structure of discrete slabs of 3D pcu network with interleaved 2D hxl (3,6) layers at random intervals, instead of the self-penetrated mab network seen in 3. The specific coordination environments and dipyridylamide lengths result in control of topology and self-penetration in this series of coordination networks. The cadmium complexes 2 and 4 were assayed for luminescent and nitrobenzene detection properties. Thermal properties of 1–5 are also discussed.

Hydrothermal reaction of zinc or cadmium nitrate, a 5-position substituted isophthalic acid, and the long-spanning dipyridylamide ligand N,N′-(hexane-1,6-diyl)dinicotinamide (hdn) resulted in coordination polymers whose dimensionalities depend on the nature of the ring substituent and the metal coordination environment. The six new phases were characterized by single crystal X-ray diffraction. {[Zn2(hip)2(H2O)2(hdn)]·2H2O}n (1, hip = 5-hydroxyisophthalate) shows a 1D ladder topology with [Zn(hip)(H2O)]n uprights spanned by disordered hdn rungs. {[Zn2(nip)2(hdn)2]·2H2O}n (2, nip = 5-nitroisophthalate) displays a 1D ribbon motif with [Zn(nip)]n chains pillared by looped pairs of hdn ligands. [Zn3(tbip)2(nic)2]n (3, tbip = 5-tert-butylisophthalate, nic = nicotinate) shows trimeric [Zn3(OCO)2] clusters connected into a 3D 8-connected 42464 bcu net by tbip and in situ generated nic ligands. {[Cd2(ip)2(H2O)4(hdn)]·2H2O}n (4, ip = isophthalate) and {[Cd2(tbip)2(H2O)4(hdn)]·H2O}n (5) both show a ladder topology similar to that in 1. {[Cd(mip)(hdn)]·H2O}n (6, mip = 5-methylisophthalate) manifests a 2D (4,4) grid topology based on linked dimeric [Cd2(OCO)2] units. Luminescent properties were probed; compounds 4 and 6 showed good ability to detect nitrobenzene in ethanol suspension.

Hydrothermal reaction of cadmium or cobalt nitrate, oxybis(benzoic acid) (obaH2), and a hydrogen-bonding capable dipyridylamide ligand afforded four crystalline coordination polymers whose dimensionality depends critically on the coordination environment or dipyridylamide length. The four new phases were structurally characterized via single-crystal X-ray diffraction. {[Cd(obaH)2(3-pina)2]·2(3-pina)·2H2O}n (1, 3-pina = 3-pyridylisonicotinamide) shows 1D chain motifs, while {[Co(oba)(3-pina)]·H2O}n (2) displays closely interdigitated 2D (4,4) grid layer motifs. The longer-spanning dipyridylamide ligand N,N′-(hexane-1,6-diyl)diisonicotinamide (hdin) afforded coordination polymers with more interesting self-penetrated or entangled 3D networks. [Cd(oba)(hdin)]n (3) manifests a unique 4,6-connected 3D self-penetrated network with {426272}(42687283} topology. [Co2(oba)2(hdin)]n (4) exhibits a {Co2(OCO)4} paddlewheel-dimer based 6-connected 3-fold interpenetrated jsm net with 510648 topology. Luminescent behavior in 1 and 3 is attributed to intra-ligand molecular orbital transitions. The new d10 phases were also surveyed for the ability to detect nitrobenzene in ethanol suspension. Thermal decomposition behavior is also discussed herein.

Zinc and cadmium diphenate (dip, biphenyl-2,2′-dicarboxylate) coordination polymers containing conformationally flexible dipyridylamide ligands show diverse chain and layer topologies as determined by single-crystal X-ray diffraction. [Cd(dipH)2(bdin)]n (1) [bdin = N,N′-(butane-1,3-diyl)diisonicotinamide] shows a simple 1D zigzag chain structure. {[Cd(dip)(pdin)(H2O)]·1.25H2O}n (2) [pdin = N,N′-(propane-1,3-diyl)diisonicotinamide] shows bilayer slabs formed by interleaving of (4,4) rectangular grid layers. {[Zn2(dip)2(3-pna)2]·3H2O}n (3) (3-pna = 3-pyridylnicotinamide) manifests a rare 4-connected 1D ribbon topology. {[Cd(dip)(4-ppbp)]·2H2O}n (4) [4-ppbp = propane-1,3-diylbis(piperidine-4,1-diyl)bis(pyridin-4-ylmethanone)] shows a 3,5-connected layer with (426)(42678) 3,5L2 topology. {[Zn4(dip)4(H2O)2(4-ppbp)2]·12H2O}n (5) exhibits 2D 3,6-connected layers with (43)2(466683) kgd topology featuring embedded R(8)A(2) classification 10-membered water clusters. Compounds 1, 4, and 5 undergo violet or blue-violet fluorescence upon ultraviolet irradiation. Thermal decomposition behavior of the new phases is also discussed.

Hydrothermal reaction of divalent metal nitrates, pyromellitic acid (pymH 4 ), and either 1,6-hexanediaminebis(nicotinamide) (hbn) or 1,6-hexanediaminebis(isonicotinamide) (hbin) afforded crystalline coordination polymers whose dimensionality depends synergistically on the dipyridylamide nitrogen donor disposition and metal coordination environment. These new phases were structurally characterized via single-crystal X-ray diffraction. [Cd(pymH 2 )(hbn)(H 2 O) 2 ] n ( 1 ) and [Co(pymH 2 )(hbn)(H 2 O) 2 ] n ( 2 ) display isostructural (4,4) grid topologies with [M(pymH 2 )(H 2 O) 2 ] n chains pillared by hbn ligands. {[Cu 2 (pym)(hbn)(H 2 O) 2 ]·2H 2 O} n ( 3 ) manifests a 3D 3,4-connected network with a rare (8 3 ) 2 (8 6 ) topology built from the hbn pillaring of [Cu 2 (pym)(H 2 O)] n layer motifs. {[Zn 2 (pym)(hbin) 2 (H 2 O)]·H 2 O} n ( 4 ) shows a 1D ribbon motif based on [Zn 2 (OCCCCO) 2 ] 14-membered circuits. {[Ni 2 (pym)(hbin)(H 2 O) 4 ]·3H 2 O} n ( 5 ) exhibits 3,4-connected layer motifs with rare {4.6 2 } 2 {4 2 6 2 8 2 } topology. Luminescent behavior in 1 and 4 is ascribed to intra-ligand molecular orbital transitions. These phases were also surveyed for the ability to detect nitrobenzene in ethanol suspension. Thermal decomposition behavior of 1 – 5 is also discussed herein.

In the title compound, [Zn(C9H6O4)] n , the ZnII cations are coordinated in a tetrahedral fashion by carboxylate O-atom donors belonging to four 4-(carboxymethyl) benzoate (4-cmb) ligands. Each 4-cmb ligand binds to four ZnII cations in an exotetradentate fashion to create a non-interpenetrated [Zn(4-cmb)] n three-dimensional coordination polymer network with a new non-diamondoid 66 topology. The crystal studied was refined as an inversion twin.

In the title compound, [Cd(C10H8O4)(H2O)2)] n , the CdII cation is coordinated in a distorted trigonal–prismatic fashion. 3-(4-Carboxyphenyl)propionate (cpp) ligands connect the CdII cations into zigzag [Cd(cpp)(H2O)2)] n coordination polymer chains, which are oriented parallel to [101]. The chains aggregate into supramolecular layers oriented parallel to (10\overline{1}) by means of O—H...O hydrogen bonding between bound water molecules and ligating cpp carboxylate O atoms. The layers stack in an ABAB pattern along [100] via other O—H...O hydrogen-bonding mechanisms also involving the bound water molecules. The crystal studied was an inversion twin.

Hydrothermal reaction of a metal nitrate, 2,5-furandicarboxylic acid (H2fdc), and the long-spanning dipyridylamide ligand bis(4-pyridylformyl)piperazine (bpfp) produced three coordination polymers which were structurally characterized by single-crystal X-ray diffraction. {[Cd2(fdc)2(bpfp)(H2O)4]·10H2O}n (1) possesses 1D 3-connected coordination polymer ladders co-crystallized with decameric water molecule clusters. {[Cu(fdc)(bpfp)(H2O)2]·2H2O}n (2) exhibits (4,4) grid coordination polymer layers stacked in an unusual parallel ABCD pattern. {[Ni(fdc)(bpfp)(H2O)2]·4H2O}n (3) also manifests (4,4) grid coordination polymer layers, but these engage in 2D + 2D → 3D mutually inclined interpenetration. Hydrothermal reaction of metal nitrates, 2,5-thiophenedicarboxylic acid (H2tdc), bpfp afforded {[Zn(tdc)(bpfp)(H2O)]·2H2O}n (4), {[Cd(tdc)(bpfp)(H2O)]·2H2O}n (5), {[Ni2(tdc)2(bpfp)2(H2O)4]·3H2O}n (6), and {[Cu(tdc)(bpfp)(H2O)2]·3H2O}n (7). Compounds 4 and 5 exhibit (4,4) sawtooth coordination polymer layer motifs that engage in relatively uncommon 2D + 2D → 3D parallel interpenetration. Compounds 6 and 7 both showed 2D + 2D → 3D mutually inclined interpenetration of parallel sets of (4,4) grid layer motifs, but with different orientations of the heterocycles within their respective metal/tdc chain submotifs. Thermal properties of all new materials were also investigated. The luminescent cadmium and zinc derivatives 1, 4, and 5 were assayed as potential detectors for nitrobenzene in methanol suspension.

Hydrothermal reaction of metal nitrates, 2,5-furandicarboxylic acid (H2fdc) and the conformationally flexible dipyridylamide ligand 3-pyridylnicotinamide (3-pna) afforded three new coordination polymers which were structurally characterized by single-crystal X-ray diffraction. {[Cd2(fdc)2(3-pna)(H2O)4]·6H2O}n (1) exhibits a 1D ladder structural motif with tethering anti-conformation 3-pna ligands acting as the rungs. {[Ni(fdc)(3-pna)2(H2O)]·2.5H2O}n (2) displays a (4,4) rhomboid grid structure that resembles a rarer (3,6) triangular grid if supramolecular interactions provided by pendant syn-conformation 3-pna ligands are considered. [Co(fdc)(3-pna)(H2O)]n (3) manifests {Co2(OCO)2} anti-syn dimer-based 3-connected 4.82 layers pillared into a novel 3D 3,5-connected self-penetrated (4.6.8)(4.658310) topology network by anti-conformation 3-pna ligands. The specific metal coordination environments, fdc binding mode, and 3-pna conformation act synergistically to enforce structure direction in this system. Thermal decomposition properties of these three new materials are also discussed.

Zinc nitrate, 2,4-pyridinedicarboxylic acid (2,4-pdcH2), and a hydrogen-bonding capable dipyridylamide ligand were combined in aqueous solution and subjected to hydrothermal reaction conditions. Three new crystalline coordination complexes were generated; their dimensionality depends crucially on the dipyridylamide length and geometric disposition of the pyridyl nitrogen donors. The three new phases were structurally characterized via single-crystal X-ray diffraction. {[H23-pina][Zn(2,4-pdc)2(H2O)2]·H2O} (1, 3-pina = 3-pyridylisonicotinamide) is a salt with protonated dipyridylamide cations and coordination complex anions. {[Zn2(2,4-pdc)2(H2O)4(3-pna)]·3H2O}n (2, 3-pna = 3-pyridylnicotinamide) shows a system of two-fold interpenetrated ruffled (6,3) coordination polymer layers. {[Zn(2,4-pdc)(H2O)2(3-pmna)]n (3, 3-pmna = 3-pyridylmethylnicotinamide) manifests a simple 1D chain topology. Luminescence was observed for two of the zinc complexes; this behavior is attributed to π–π* or π–n molecular orbital transitions. Thermal decomposition properties of the new phases are also probed.

Divalent metal coordination polymers containing the rigid 2,5-thiophenedicarboxylate (tdc) ligand and the conformationally flexible dipyridylamide ligand bis(4-pyridylformyl)homopiperazine (bpfh) show different layer topologies and chirality. As determined by single-crystal X-ray diffraction, {[Cd(tdc)(bpfh)(H2O)]·3H2O}n (1) shows a twofold parallel interpenetrated centrosymmetric (4,4) layered grid structure. {[Zn(tdc)(bpfh)]·H2O}n (2) exhibits a similar system of twofold interpenetrated (4,4) grid-like layers, but in contrast to 1, it crystallizes in an acentric space group. {[Ni2(tdc)2(bpfh)2(H2O)]·2H2O}n (3) possesses {Ni2(μ-H2O)(OCO)2} dimeric units connected into a doubled layer motif by the full span of the tdc and bpfh ligands. Weak antiferromagnetic coupling is observed within the dimeric units in 3 [g = 2.172(6) and J = –0.79(1) cm–1]. Compounds 1 and 2 undergo blue-violet fluorescence upon ultraviolet irradiation; the cadmium derivative 1 shows potential as a sensor for the solution-phase detection of nitrobenzene although coordination polymer exfoliation likely occurs. Thermal decomposition behavior of the three new phases is also discussed.

Hydrothermal reaction of the requisite metal nitrate, potassium terephthalate (K 2 tere) and the dipyridylamide 3-pyridylisonicotinamide (3-pina) afforded a pair of crystalline coordination polymers whose dimensionality and topology depends critically on the metal coordination environment. The two new crystalline phases were structurally characterized via single-crystal X-ray diffraction. {[Zn(tere)(3-pina) 2 ]·2H 2 O} n ( 1 ) manifests a 1-D zig-zag ribbon motif with monodentate 3-pina ligands. [Cd(tere)(3-pina) 2 ] n ( 2 ) displays a self-penetrated 3-D network with 4 4 6 10 8 mab topology. Thermal and luminescent properties of these two new materials are also presented. Both 1 and 2 show capability as sensors for nitroaromatic compounds via luminescence quenching, with better absorption for nitrobenzene than the more sterically bulky analyte m -nitrophenol.

Hydrothermal reaction of metal nitrates, 2,5-thiophenedicarboxylic acid (H2tdc) and the conformationally flexible and very long spanning dipyridylamide ligand propane-1,3-diylbis(piperidine-4,1-diyl)bis(pyridin-4-ylmethanone) (4-ppbp) produced three new coordination polymers which were structurally characterized by single-crystal X-ray diffraction. [Cu(tdc)(4-ppbp)(H2O)]·2H2O}n (1) manifests a slab topology with pairs of interleaved (4,4) layer motifs. [Co(tdc)(4-ppbp)(H2O)]n (2) shows a 2,4-connected 1-D tubular structure that engages in very rare 1D + 1D → 2D parallel polycatenation. [Ni(tdc)(4-ppbp)2(H2O)]n (3) possesses a unique system of 2D + 2D → 2D interpenetrated 2,6-connected layers, derived from the edge-crossed SP 2-periodic (4,4)IIb net, when O–H⋯N hydrogen bonding patterns are taken into account. The conformational flexibility of the 4-ppbp ligand affords the requisite loops for the unique polycatenation patterns in 2 and 3. Thermal decomposition properties of these three new materials are discussed.

Hydrothermal reaction of nickel nitrate, adipic acid, and a dipyridylamide ligand produced two coordination polymers which were structurally characterized by single-crystal X-ray diffraction. {[Ni2(adipate)2(3-pna)2(H2O)]·H2O}n (1, 3-pna = 3-pyridylnicotinamide) possesses carboxylate bridged {Ni(μ2-H2O)(OCO)2} dimeric units connected into (6,3) graphitic 2D layer motifs. Use of the isomeric 3-pyridylisonicotinamide (3-pina) afforded {[Ni2(adipate)2(3-pina)2(H2O)]·2H2O}n (2), which manifested similar {Ni(μ2-H2O)(OCO)2} dimeric units. Crystallographic disorder within the adipate ligands in 2 produced a 3D coordination polymer net that is a hybrid of a non-interpenetrated 3D 6-connected primitive cubic α-Po 41263pcu net and 2D 7-connected slab motifs with a pillared (3,6) triangular net 3641253 topology. Magnetic analysis for 1 revealed weak antiferromagnetic coupling (J = −0.36(1) cm−1 with g = 2.077(1)), while 2 exhibited weak ferromagnetic coupling (J = +0.51(2) cm−1 with g = 2.034(7)).

Hydrothermal reaction of copper nitrate, 3,4-pyridinedicarboxylic acid (34pdcH2), and a variety of ditopic dipyridyl ligands afforded six new coordination polymer solids with diverse 2D and 3D topologies as characterized via single-crystal X-ray diffraction. {[Cu(34pdc)(dpa)]·H2O}n (1, dpa = 4,4′-dipyridylamine) reveals a 3,5-connected layered net with a (426)(42678) topology. [Cu(34pdc)(3pina)]n (2, 3pina = 3-pyridylisonicotinamide) manifests a 2-fold interpenetrated 3,5-connected 3D net with (426)(426583) topology. [Cu2(34pdc)2(bbn)(H2O)2]·7H2O}n (3, bbn = bis(butane-1,4-diyl)nicotinamide) shows a 3D trinodal network with {(63)2(6.102)(64102)} topology, with looped pairs of bbn ligands acting as single connectors. [Cu4(34pdc)4(bbin)(H2O)4]·8H2O}n (4, bbin = bis(butane-1,4-diyl)isonicotinamide) displays a quite complicated 3D multinodal network with {(63)2(628)(6282102)(668310)} topology. [Cu2(34pdc)2(pebn)(H2O)]·8H2O}n (5, pebn = bis(pentane-1,5-diyl)nicotinamide) shows a 3,4,4-connected 2D network with {(63)2(6472)(6.74.11)} topology, along with entrapped chair-centered 14-water molecule clusters. [Cu4(34pdc)4(hbn)(H2O)4]·3H2O}n (6, hbn = bis(hexane-1,6-diyl)nicotinamide) showed the same {(63)2(6.102)(64102)} topology as 3, but with single dipyridylamide ligands instead of looped pairs. Thermal decomposition of these six new materials are also probed, along with their catalytic behavior for the aqueous degradation of Congo Red dye in the presence of ultraviolet radiation and hydrogen peroxide.

Crystals of [Cu4(OH)2(sip)2(bpu)(H2O)4]n (1, sip = 5-sulfoisophthalate, bpu = bis(4-pyridyl)urea) were prepared by hydrothermal methods. A single-crystal structure determination showed the presence of [Cu4(OH)2(sip)2(H2O)4] kgd layer motifs bearing “butterfly” {Cu4(OH)2} tetranuclear cluster units. These are linked by sulfonate oxygen atoms and the bpu tethers into a self-penetrated 4,10-connected binodal network with an unprecedented (46)2(41251661275) topology. Variable temperature magnetic susceptibility data showed antiferromagnetic interactions within the tetrameric “butterfly” cluster units (g = 2.094(9), J1 = –8.2(3) cm−1, and J2 = –14.3(6) cm−1). Compound 1 also demonstrated utility as a heterogeneous catalyst for the UV-mediated degradation of Congo Red dye in the presence of hydrogen peroxide oxidant.

Hydrothermal reaction of zinc or cadmium nitrate, 4-(carboxylatomethyl)benzoic acid (cmbH2), and bis-(4-pyridyl)urea (bpu) generated a pair of coordination polymers that were isolated and subsequently structurally characterized by single-crystal X-ray diffraction. {[Zn2(cmb)2(bpu)2]·2H2O}n (1) shows a 2D + 2D → 3D parallel polycatenated pattern of sawtooth (4,4) coordination polymer grids. In contrast, {[Cd3(cmb)3(bpu)2(H2O)4]·3H2O}n (2) manifests [Cd3(cmb)3(H2O)4]n slab motifs threaded and linked by bpu ligands into an unprecedented self-penetrated 3,3,4,4-connected 3D network with (6·7·8)(627)(627·83)(7383) topology. Thermal decomposition of the new phases is discussed. Both 1 and 2 underwent visible light luminescence upon ultraviolet irradiation, and acted as luminescent “turn-off” sensors for nitrobenzene absorption in ethanol suspension.

Hydrothermal reaction of cobalt nitrate, a cyclohexyldicarboxylic acid, and the long-spanning dipyridyl coligand bis(4-pyridylmethyl)piperazine (bpmp) produced four structurally diverse coordination polymers which were characterized by single-crystal X-ray diffraction. [Co(cis-12chedc)(bpmp)]n (1, cis-12chedc = cyclohex-4-ene-1,2-cis-dicarboxylate) possesses a 3D pcu network based on embedded {Co2(OCO)2} dimeric units. {[Co(cis-13cdc)(bpmp)(H2O)]·2H2O}n (2, cis-13cdc = cyclohexane-1,3-cis-dicarboxylate) exhibits (4,4) sawtooth coordination polymer layers polycatenated in a 2D + 2D → 3D parallel fashion. {[Co2(cis-14cdc)2(bpmp)]·2H2O}n (3, cis-14cdc = cyclohexane-1,4-cis-dicarboxylate) also shows (4,4) grid layer structures, but without any interpenetration. {Co2(OCO)4} paddlewheel dimers are seen in chain-like substructures in 3. The minor phase [Co(cis-14cdc)(bpmp)(H2O)2]n (4) was isolated along with 3 and manifests a non-interpenetrated 658 cds topology 3D network. Thermal properties of 1–3 were also investigated. Variable temperature magnetic susceptibility studies showed dimer-based antiferromagnetic behavior for 1 and 3.

Hydrothermal reaction of cobalt nitrate, d -camphoric acid, and flexible dipyridylamide ligands afforded a series of coordination polymers with diverse structural topologies, as characterized by single crystal X-ray diffraction.{[Co2( dl -cam)2(edn)]·2H2O}n (1, edn = N,N′-(ethane-1,2-diyl)dinicotinamide) shows a 3D 41263 pcu net built from straight-pillaring of {Co2(OCO)4} paddlewheel dimer-based [Co2( dl -cam)2]n layer motifs. In contrast, [Co( d -cam)(edin)]n (2, edin = N,N′-(ethane-1,2-diyl)diisonicotinamide) manifests a two-fold parallel interpenetrated looped layer topology. {[Co2( dl -cam)2(bdin)]·2H2O}n (3, bdin = N,N′-(butane-1,4-diyl)diisonicotinamide) displays a very rare 3D 446108 roa self-penetrated net built from cross-pillaring of {Co2(OCO)4} paddlewheel dimer-based [Co2( dl -cam)2]n layer motifs, as does {[Co2( dl -cam)2(pedin)]·2H2O}n (4, pedin = N,N′-(pentane-1,5-diyl)diisonicotinamide). [Co( d -cam)(hdin)]n (5, hdin = N,N′-(hexane-1,6-diyl)diisonicotinamide) shows a simple stacked system of sawtooth (4,4) grid motifs. Thermal properties are discussed herein.

In the title compound, [Ni(C4H5NO4)(C10H9N3)(H2O)] n , the NiII cations are octahedrally coordinated by an N atom donor and two O donor atoms belonging to a tridentate iminodiacetate (ida) ligand in a fac fashion, an O atom donor from an aqua ligand, and cis-disposed pyridyl N donor atoms from two 4,4′-dipyridylamine (dpa) ligands. The dpa ligands are disordered over two sets of sites in a 0.594 (7):0.406 (7) ratio. Through the bridging dpa ligands, [Ni(ida)(dpa)(H2O)] n zigzag coordination polymer chains are formed that are oriented along the b-axis direction. These chain motifs are anchored into the three-dimensional supramolecular crystal structure of the title compound by means of O—H...O and N—H...O hydrogen-bonding pathways.

In the title compound, [CuNa2(C9H4O6)2(H2O)4] n , the CuII cations are square-planar coordinated by carboxylate O-atom donors from four different hydrogen benzene-1,2,4-tricarboxylate (btcH) ligands, thereby forming [Cu(btcH)2] n 2n− coordination polymer ribbons. These are connected by octahedrally coordinated and hydrated NaI cations within Na2(μ-H2O)2 clusters to construct the full [Na2(H2O)4Cu(btcH)2] n three-dimensional coordination polymer.

Three new manganese(II) complexes, namely [Mn(NCS)2(L)2(CH3OH)2]·2CH3OH (1), [Mn(NCS)2(L)2(C2H5OH)2]·2C2H5OH (2) and [Mn(NCS)2(μ-L)2]n (3) (L = 4-acetylpyridine nicotinoylhydrazone) have been synthesized and characterized by elemental analysis, IR spectra, single-crystal and powder X-ray diffraction analysis. In order to investigate the effect of solvent, methanol, ethanol and acetonitrile have been used in the synthesis of complexes 1–3, respectively. When using methanol as solvent, complex 1 was obtained. Complex 2 was synthesized under the similar synthetic conditions of complex 1 using ethanol instead of methanol as a solvent. To further examine the effect of solvent on the structure, we used CH3CN as a solvent instead of the ethanol. Unlike the complexes 1 and 2, complex 3 was formed with 1D chain structure. The energetic features of the noncovalent interactions observed in the solid state of compounds 1 and 2 have been studied by means of DFT calculations.

Slow diffusion of an ethanolic solution of 4,4′-bipyridine (bpy) into an aqueous solution of copper dimethylmalonate (dmmal) afforded two different coordination polymer complexes as time elapsed. These were structurally characterized via single-crystal X-ray diffraction. A small amount of light blue crystals of {[Cu2(dmmal)2(bpy)1.5(H2O)]·2H2O}n (1) were initially deposited at the solution interface. Compound 1 displays a 3,4-connected 2D layer with an unprecedented (426)(42638) topology comprising alternating rows of hexagonal and rectangular circuits. These crystals dissolved as the reaction continued, with dark blue crystals of {[Cu3(dmmal)3(bpy)3(H2O)4]·H2O}n (2) forming at the bottom of the reaction vessel. Compound 2 manifests a 4-connected self-penetrated 658 cds topology. Thermal properties of 2 are also reported.

The dimensionality and structure of divalent zinc coordination polymers containing the dipyridylamide ligand 3-pyridylnicotinamide (3-pna) can be adjusted by varying the 5-position substituent on an isopthalate moiety. Two new coordination polymer solids were obtained by hydrothermal self-assembly and structurally characterized via single-crystal X-ray diffraction. Using the unsubstituted isophthalate (ip) ligand, [Zn(ip)(3-pna)]n (1) was obtained. This material exhibits {Zn2(OCO)2} dimer-based [Zn(ip)]n chains linked into (426)(42678) 3,5L2 topology layers by anti conformation 3-pna ligands. By employing 5-methylisophthalate (mip), the coordination polymer {[Zn(mip)(3-pna)]·2H2O}n (2) was obtained; these feature syn conformation 3-pna ligands. Compound 2 shows a rarely encountered 4-connected 1-D ribbon motif with 33425 topology, encapsulating infinite single-file water molecule chains within incipient tubular channels. Thermal and luminescent properties of these materials are also discussed.

Hydrothermal reaction of the requisite metal nitrate, carboxycinnamic acid (H2cca), and the long-spanning dipyridylamide bis(4-pyridylformyl)piperazine (4-bpfp) generate crystalline coordination polymers whose topology depends critically on the metal coordination geometric preference. These two new phases were structurally characterized by single-crystal X-ray diffraction. {[Cu(cca)(4-bpfp)]·2.5H2O}n (1) manifests a non-interpenetrated 6-connected pcu net based on chain motifs featuring carboxylate-bridged {Cu2(OCO)2} dinuclear units, with embedded D(5) water molecule chains. {[Ni(cca)(4-bpfp)(H2O)2]·3H2O}n (2) displays an acentric twofold interpenetrated 4-connected 66 dia network topology with entrapped R(4)A(1) water molecule rings. Variable temperature magnetic studies performed on 1 revealed very weak antiferromagnetic coupling within its dinuclear units. Thermal properties of these two new materials are also discussed.

Hydrothermal reactions of nickel or cobalt nitrate with the dipyridylamide ligand bis(4-pyridylformyl)piperazine (4-bpfp) and either 5-methoxyisophthalate (H2omeip) or 5-methylisophthalate (H2mip) afforded a series of coordination polymers that were structurally characterized by single-crystal X-ray diffraction. Different synthetic conditions afforded the 1D chain phase {[Ni(Homeip)2(H2omeip)(bpfp)]·2H2O}n (1) or the mutually inclined interpenetrated (4, 4) grid system in {[Ni(omeip)(bpfp)(H2O)]·2H2O}n (2). The analogous cobalt phase {[Co(omeip)(bpfp)]·3H2O}n (3) lacks bound water molecules, which enforces a non-interpenetrated (4, 4) grid structure based on {Co2(OCO)2} dinuclear clusters. Similar clusters are seen in {[Co(mip)(bpfp)(H2O)2]·3.5H2O}n (4), which manifests a 1D ribbon structural motif. Its nickel congener {[Ni(Hmip)2(bpfp)(H2O)2]·2H2mip}n (5) also shows a 1D chain motif. A variable temperature magnetic susceptibility study indicates antiferromagnetic coupling within the dimeric units in 3 and 4 concomitant with single ion effects. Additionally, thermal degradation properties of these new materials are described.

A pair of three-dimensional divalent copper pyromellitate (1,2,4,5-benzene-tetracarboxylate, pyro) coordination polymers containing 4,4′-dipyridylamine (dpa) was hydrothermally prepared and structurally characterized by single-crystal X-ray diffraction. The higher-temperature phase ([H{sub 2}dpa][Cu{sub 3}(pyro){sub 2}(H{sub 2}O){sub 3}]·2.5H{sub 2}O){sub n} (1) displays an acentric 3-D 4,4,6-connected anionic network with (4{sup 4}5.6)(5{sup 4}8{sup 2})(4{sup 4}5{sup 4}6{sup 3}7{sup 4}) topology, featuring (Cu{sub 2}(OCO){sub 4}) paddlewheel dimers and isolated copper ions. Charge-balancing H{sub 2}dpa cations are embedded in incipient voids. Prepared at lower temperature, ([Cu{sub 3}(pyro){sub 2}(dpa){sub 2}(dpaH){sub 2}]·3H{sub 2}O){sub n} (2) manifests a 3-D 4,4,4-connected neutral network with uncommon (4{sup 2}6{sup 4}){sub 4}(6{sup 4}8{sup 2}) frl topology based on (Cu{sub 3}(OCO){sub 2}) linear trimers. Antiferromagnetic coupling (J=–82(5) cm{sup –1}) was observed within the (Cu{sub 2}(OCO){sub 4}) dimeric units in 1, while weak ferromagnetic coupling (J=1.0(4) cm{sup –1}) was evident for the (Cu{sub 3}(OCO){sub 2}) linear trimers in 2. Thermal degradation behavior of these new materials is also presented. - Graphical abstract: Two copper pyromellitate coordination polymers containing 4,4′-dipyridylamine were prepared. The higher-temperature phase ([H{sub 2}dpa][Cu{sub 3}(pyro){sub 2}(H{sub 2}O){sub 3}]∙2.5H{sub 2}O){sub n} displays an acentric 3-D trinodal anionic network with (4{sup 4}5.6)(5{sup 4}8{sup 2})(4{sup 4}5{sup 4}6{sup 3}7{sup 4}) topology, featuring antiferromagnetically coupled (Cu{sub 2}(OCO){sub 4}) paddlewheel dimers andmore » isolated copper ions. - Highlights: • Copper pyromellitate (pyro) coordination polymers with 4,4′-dipyridylamine (dpa). • Higher-temperature phase 1 has 3-D anionic trinodal network with H{sub 2}dpa cations. • Lower-temperature phase 2 has rare 3-D frl network. • Dimers and chains in 1 show antiferromagnetism, trimers in 2 show ferromagnetism.« less

Hydrothermal treatment of zinc nitrate, a 5-substituted isophthalic acid, and 4-pyridylisonicotinamide (4-pina) resulted in crystalline coordination polymers that incorporated different fragments formed by in situ hydrolysis of the 4-pina precursor. These materials were characterized by single crystal X-ray diffraction. In the case of {[4-ampyrH]2[Zn(hip)2]·H2O}n (1, 4-ampyrH = 4-aminopyridinium, hip = 5-hydroxyisophthalate), anionic [Zn(hip)2]n2n− (4,4) grid layers co-crystallize with protonated 4-ampyr cations. Using 5-nitroisophthalic acid (H2nip), [Zn7(isonic)4(OH)6(nip)2]n (2, isonic = isonicotinate) was formed. This material manifests [Zn7(OH)6]n cationic inorganic chain motifs linked by isonic and nip ligands into a non-interpenetrated 3-D coordination polymer network with pcu topology. Luminescent behavior is attributed to intra-ligand molecular orbital transitions.

Hydrothermal reaction of copper nitrate and aromatic dicarboxylate precursors with the conformationally flexible and very long-spanning dipyridylamide ligand propane-1,3-diylbis(piperidine-4,1-diyl)bis(pyridin-4-ylmethanone) (4-ppbp) has generated three coordination polymers and a threaded-loop supramolecular complex. {[Cu(tere)(4-ppbp)(H2O)]·1.5H2O}n (1, tere = terephthalate) and {[Cu(iph)(4-ppbp)(H2O)]·2H2O}n (2, iph = isophthalate) both display slab motifs built from interdigitated (4,4) grid layers. {[Cu2(phda)(phdaH)2(4-ppbp)2]·6H2O}n (3, phda = 1,4-phenylenediacetate) possesses a 4-connected 658 cds network with self-penetration of 8-membered circuits. {[Cu2(phtH)2(4-ppbp)2(H2O)4](NO3)2·H2O}n (4, pht = phthalate) manifests ring-like dinuclear coordination complex cations with anionic phtH ligands projecting into supramolecular tubes with an inner diameter of approximately 12 A. Dehydration and thermal degradation properties of these new materials are discussed. We also report the crystal structure of the recrystallized dipyridylamide, 4-ppbp·2H2O.

Hydrothermal reaction of cobalt or nickel nitrate with 5-tert-butylisophthalic acid (H2tbip) and bis(4-pyridylformyl)piperazine (bpfp) under varying synthetic conditions afforded four coordination polymers that were subsequently structurally characterized via single-crystal X-ray diffraction. {[Co(Htbip)2(H2O)2(bpfp)]·H2O}n (1), prepared with a lower concentration of added base, exhibits a 1D sawtooth chain structure. {[Co2(tbip)2(H2O)4(bpfp)]·2H2O}n (2), prepared under higher base conditions, and its analog {[Ni2(tbip)2(H2O)4(bpfp)]·2H2O}n (3), show isostructural 1D ladder topologies. {[Ni(tbip)(H2O)2(bpfp)]·2.25H2O}n (4), prepared using a higher concentration of reactants than for 3, manifests an extremely rare 658 4T10 4-connected self-penetrated topology and represents the first metal dicarboxylate coordination polymer to possess this network. Thermal decomposition behavior of these materials is also discussed.

Hydrothermal reaction of copper nitrate and 3-pyridylmethylnicotinamide (3-pmna) with aromatic dicarboxylates has afforded a series of coordination polymers that were structurally characterized via single-crystal X-ray crystallography. [Cu(tere)(3-pmna)] n ( 1 , tere = terephthalate) displays a 3,5-connected 3-D binodal net with uncommon (6 3 )(6 9 8) gra topology. {[Cu(iph)(3-pmna)(H 2 O)]·3H 2 O} n ( 2 , iph=isophthalate) possesses an extremely rare 4-connected 3-D self-penetrated net with 8 6 tcb topology. [Cu 2 (nip) 2 (3-pmna) 2 ] n ( 3 , nip = 5-nitroisophthalate) manifests a doubled chain 1-D structure, while increased steric bulk in [Cu(tbip)(3-pmna)] n ( 4 , tbip = 5-tert-butylisophthalate) results in a 1-D single chain motif. A significant dependence of the dimensionality and topology of these materials on the part of the carboxylate donor disposition and ring substituent was thus revealed. Thermal properties of these new materials were also investigated.

Hydrothermal reaction of zinc nitrate, aliphatic dicarboxylic acids, and the long-spanning hydrogen-bonding capable tethering ligand bis(4-pyridylmethyl)piperazine (4-bpmp) has produced seven coordination polymer solids that were characterized via single-crystal X-ray crystallography. [Zn(suc)(4-bpmp)(H2O)2]n (1, suc = succinate) shows 2D + 2D → 3D mutually inclined interpenetrated parallel coordination polymer layers with (4,4) grid topology. {[Zn2(dms)2(4-bpmp)]·2H2O}n (2, dms = 2,2-dimethylsuccinate) exhibits 1-D [Zn2(dms)2]n ribbons featuring {Zn2(OCO)2} dimeric units pillared into 2-D by 4-bpmp ligands. {[Zn(glu)(4-bpmp)]·6H2O}n (3, glu = glutarate) manifests a 3-fold interpenetrated 3-D 66 diamondoid topology with embedded C(10)A(4) water chains. [Zn(22dmg)(4-bpmp)]n (4, 22dmg = 2,2-dimethylglutarate) and [Zn(33dmg)(4-bpmp)]n (5, 33dmg = 3,3-dimethylglutarate) both display stacked zig–zag (4,4) grid layered topologies, and do not entrain any co-crystallized water molecules. Reduction of the steric hindrance by using 3-methylglutarate (3mg) afforded {[Zn(3mg)(4-bpmp)]·3H2O}n (6), which also displays a (4,4) grid topology, but with embedded R(4)A(2) water molecule hexamers connecting to three different layer motifs. [Zn(adp)(4-bpmp)]n (7, adp = adipate) possesses a system of 5-fold interpenetrated diamondoid nets. Thermal and luminescent properties of these materials are discussed herein.

Crystals of [Cu(ox)(dpa)(H2O)]n (1, ox = oxalate, dpa = 4,4′-dipyridylamine) were prepared by hydrothermal reaction of potassium copper oxalate and dpa. Single-crystal X-ray diffraction showed the formation of orthogonally oriented sets of 1D [Cu(ox)(dpa)(H2O)]n chains that interlock in a 1D + 1D ➔ 2D manner to form woven “warp-and-woof” supramolecular layers. Thermogravimetric analysis indicated that the structure of 1 remained stable to about 175 °C.

Hydrothermal reaction of divalent copper salts, aliphatic dicarboxylic acids, and 3-pyridylmethylnicotinamide (3-pmna) has afforded a series of coordination polymer solids that were characterized via single-crystal X-ray crystallography. A significant dependence of the dimensionality and topology of these materials on the part of aliphatic chain length and substituent was revealed. Both [Cu2(suc)2(3-pmna)]n (1, suc = succinate) and its substituted congener {[Cu2(dms)2(3-pmna)]·4H2O}n (2, dms = 2,2-dimethylsuccinate) manifest {Cu2(OCO)4} paddlewheel dimers, connected into chain motifs that are further linked by 3-pmna ligands into 2-D (4,4) grid networks. The enhanced steric bulk of the dms ligands in 2 impart larger interlamellar regions occupied by disordered water molecules. {[Cu2(glu)2(3-pmna)]·H2O}n (3, glu = glutarate) has similar dimer-containing [Cu2(glu)2]n chain motifs, but retains a 1-D dimensionality due to bridging by syn-conformation 3-pmna ligands. [Cu(2-mglu)(3-pmna)]n (4, 2-mglu = 2-methylglutarate) features anti-syn {CuOCO}n chain patterns and a 3,5-connected (3.52)(3253647) 2-D topology. {[Cu2(adp)2(3-pmna)2]·H2O}n (5, adp = adipate) exhibits 2-D [Cu2(adp)2]n layers, linked by anti-conformation 3-pmna ligands into a very rare 3-D 3,5-connected hms net with (63)(698) topology. A minor 1-D chain product {[Cu2(adp)2(3-pmna)]·0.25H2O}n (6) was also isolated at higher temperature. Variable temperature magnetic susceptibility data for 5 indicates the presence of very weak antiferromagnetic coupling along its anti-syn bridged {CuOCO}n chains. Thermal properties of these new materials are also investigated.

Hydrothermal synthesis has yielded four divalent metal coordination polymers containing both bis(4-pyridylformyl)piperazine (4-bpfp) and pyromellitate (pyro, 1,2,4,5-benzenetetracarboxylate) ligands, which were structurally characterized by single-crystal X-ray diffraction. Various topologies were obtained depending on specific metal used and level of base in the reaction mixture. {[Cd(pyroH2)(4-bpfp)]·2H2O}n (1) displays an uncommon 3-D binodal fsc network, while {[Zn2(pyro)(4-bpfp)(H2O)8]·4H2O}n (2) and {[Co2(pyro)(4-bpfp)(H2O)8]·4H2O}n (3) manifest aggregated 1-D coordination polymer chains. A decrease in amount of added base from that used in the preparation of 3 resulted in the generation of {[Co(pyroH2)(4-bpfp)]·2H2O}n (4), which has the same 3-D fsc topology as 1. The closed shell complexes 1 and 2 emit blue-violet and blue light, respectively, upon ultraviolet irradiation. Dehydration and decomposition behavior of these four new materials is also presented.