Dipyridylamide Ligands Research Articles

Synthesis, crystal structures and vapor adsorption properties of mercury(II) coordination polymers derived from two dipyridylamide ligands

AbstractTwo complexes, [HgL1Cl2]n (1) and [Hg2(L2)2Cl4]n (2), have been synthesized and characterized from two dipyridylamide ligands (L1 and L2) with mercury(II) chloride, respectively. The two complexes exist as 1D coordination polymers but exhibit different architectures with slightly adjusted 3‐ and 4‐position of nitrogen atom in the pyridyl rings from the two ligands. In complex 1, the mercury(II) center is four‐coordinated with distorted tetrahedral geometry in 1D‐chain structures. In complex 2, the mercury(II) center is five‐coordinated with distorted square pyramidal geometry in the 1D‐looped structures. The thermal stabilities and vapor adsorption properties of the two complexes were investigated as well.

Copper 3,4-pyridinedicarboxylate mixed ligand coordination polymers with diverse topologies and aqueous Congo Red degradation catalytic properties

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.

Nitroaromatic‐detecting Layered Cadmium Cyclohexyldicarboxylate Coordination Polymers with Long‐Spanning Dipyridyl Pillaring Ligands

Three new divalent cadmium coordination polymers containing cyclohexyldicarboxylate and pillaring dipyridylamide ligands have been prepared and structurally characterized via single‐crystal X‐ray diffraction. All three compounds exhibited layered structures, but with different topologies and interpenetration schemes. [Cd2(12chedc)2(ebin)(H2O)2]n (1) [12chedc = 1,2‐cyclohex‐4‐ene‐dicarboxylate, ebin = ethylenediamine(bis)isonicotinamide] displays a 2D 3,4‐connected net with (426)(42638) topology, also known as the V2O5 structural type. {[Cd(13cdc)(ebin)]·H2O}n (2) (13cdc = cis‐1,3‐cyclohexanedicarboxylate) showed a rare 2D + 2D → 3D parallel polycatenated system of looped layer networks. {[Cd(13cdc)(hbn)]·H2O}n (3) [hbn = hexanediamine(bis)nicotinamide] manifests a (426)(42678) network, also known as the 3,5L2 net. All three materials were assayed as fluorescent “turn‐off” sensors for the detection of nitrobenzene in solution. Thermal decomposition behavior of the new phases is also discussed.

Structural diversity in cobalt camphorate coordination polymers with flexible dipyridylamide ligands including looped layers and self-penetrated topologies

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 41263pcu 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.

Structural diversity and dye degradation capability of copper 1,2-phenylenediacetate coordination polymers with flexible dipyridylamide ligands

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.

Nitrobenzene-detection cadmium thiophenedicarboxylate coordination polymers with flexible dipyridylamide ligands and diverse topologies

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 6482nbo 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.

Divergent topologies in luminescent and nitrobenzene-detecting zinc diphenate coordination polymers with flexible dipyridylamide ligands

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 6482nbo 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.

Control of chirality and catenation in cobalt and cadmium camphorate coordination complexes

Five cobalt or cadmium camphorate coordination polymers with various flexible-tether dipyridylamide ligands were structurally characterized. {[Co2(d-cam)2(pdn)]·2H2O}n (3, pdn = N,N′-(propane-1,3-diyl)dinicotinamide) has a self-penetrated 446810 mab network. {[Cd2(d-cam)2(pdn)]·H2O}n (4) shows a new 3,7-connected 3D network. The cadmium complexes were assayed for luminescent and nitrobenzene detection properties.

Auxiliary dipyridylamide ligand control of dimensionality in copper 5-sulfoisophthalate coordination polymers

Abstract 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.

Front Cover: Zinc and Cadmium Diphenate Coordination Polymers with Conformationally Flexible Dipyridylamide Ligands (Z. Anorg. Allg. Chem. 17/2017)

Front Cover: Zinc and Cadmium Diphenate Coordination Polymers with Conformationally Flexible Dipyridylamide Ligands (Z. Anorg. Allg. Chem. 17/2017)

Divergent topologies in luminescent zinc and cadmium substituted isophthalate coordination polymers constructed from long-spanning dipyridylamide ligand precursors

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 42464bcu 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.

Zinc and Cadmium Diphenate Coordination Polymers with Conformationally Flexible Dipyridylamide Ligands

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.

Cadmium and cobalt oxybis(benzoate) coordination polymers with diverse topologies depending on dipyridylamide ligands including a new self-penetrated network

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.

Luminescent cadmium 1,3-adamantanedicarboxylate coordination polymers with diverse topologies depending on dipyridylamide ligands

Hydrothermal reaction of cadmium nitrate, 1,3-adamantanedicarboxylic acid (adcH2), and a hydrogen-bonding capable dipyridylamide ligand afforded five crystalline coordination polymers whose dimensionality depends on the dipyridylamide length and nitrogen donor disposition. The five new phases were structurally characterized via single-crystal X-ray diffraction. [Cd(adc)(4-pmina)]n (1, 4-pmina=4-pyridylmethylisonicotinamide) displays a (4,4) grid topology with [Cd(adc)]n chains pillared by the dipodal dipyridylamide ligands. {[Cd(adc)(4-pmna)(H2O)]·4H2O}n (2, 4-pmna=4-pyridylmethylnicotinamide) displays a similar layered topology, but with octameric water molecule clusters residing in the interlamellar regions. {[Cd(adc)(3-pna)(H2O)]·6H2O}n (3, 3-pna=3-pyridylnicotinamide) possesses 1-D ribbon submotifs due to the syn-conformation and shorter tether length of the dipyridylamide ligands. Compound 3 entrains intriguing “infinite” water molecule tapes comprised of 4- and 5-membered rings. {[Cd2(adc)2(3-pina)2]·H2O}n (4, 3-pina=3-pyridylisonicotinamide) manifests a 4-connected 3D 658cds topology. The minor coordination polymer chain product {[Cd(adc)(3-pyram)2(H2O)]·2H2O}n (5) was isolated along with 4 (3-pyram=3-pyridylamine). Luminescent behavior in 1–4 is attributed to intra-ligand molecular orbital transitions. The new phases were also surveyed for the ability to detect nitrobenzene in ethanol suspension. Thermal decomposition behavior is also discussed herein.

Substituent dependent layer topologies in copper isophthalate coordination polymers containing long-spanning dipyridylamide ligands

Hydrothermal reaction of copper nitrate, a 5-position substituted isophthalic acid, and the long-spanning dipyridylamide ligand 1,6-hexanediaminebis(nicotinamide) (hbn) resulted in two new coordination polymers whose layer topologies and interpenetration mechanisms depend critically on the nature of the substituent. The new phases were structurally characterized by single crystal X-ray diffraction. {[Cu(meoip)(hbn)]·H2O}n (1, meoip = 5-methoxyisophthalate) exhibits [Cu(meoip)]n chain motifs with embedded {Cu2(OCO)2} dinuclear units, pillared by pairs of hbn ligands into a decorated (4,4) grid topology. {[Cu3(sip)2(hbn)3(H2O)4]·11.5H2O}n (2, sip = 5-sulfoisophthalate) displays neutral [Cu3(sip)2(H2O)4] fragments connected by hbn ligands into 3,4-connected layer motifs with a {4.62}2{426282} topology, derived from the standard (4,4) grid with regular removal of some pillars. The layer motifs in 2 engage in 2D + 2D → 3D parallel interpenetration, with entrained co-crystallized water molecule tapes. Thermal decomposition behavior of the new phases is also discussed.

Synthesis and Characterization of Copper Complexes with CuICuI, Cu1.5Cu1.5m and CuIICuII Core Structures Supported by a Flexible Dipyridylamide Ligand.

A series of copper complexes supported by a simple dipyridylamide ligand (H2pcp) were isolated and characterized. Treatment of H2pcp with NaH and copper(I) salts led to the formation of [Cu2(2pcp)2] (1a) and {Na[(Cu2(2pcp)2)2]PF6}n (1b). The X-ray crystal structures of both complexes feature CuICuI cores with close Cu···Cu interactions. Electrochemical studies of 1a showed a reversible one-electron oxidation wave in CH2Cl2. On the basis of the work on 1a, we began studying the mixed-valence copper species supported by this ligand. The reaction of H2pcp with Cu(OAc)2 and CuCl in different stoichiometries yielded [Cu2(2pcp)2Cl] (2) and [Cu3(2pcp)2Cl2] (3). X-ray crystallography and spectroscopic characterization suggested delocalized Cu1.5Cu1.5 core structures of both compounds. These results further inspired us to explore the coordination properties of H2pcp toward CuII ions. The complexes [HNEt3][Cu2(2pcp)3(ClO4)](ClO4) (4a), [Cu2(2pcp)3(NO3)] (4b), and [Cu2(2pcp)3(H2O)]BF4 (4c) featuring dinuclear CuIICuII cores were prepared and characterized by X-ray crystallography and spectroscopic methods. Structural analysis of these complexes implied that the accommodation of CuICuI, Cu1.5Cu1.5, and CuIICuII is attributed to the structural flexibility of the ligand H2pcp. Complexes 1a, 2, 3, and 4a were examined by X-ray photoelectron spectroscopy, which confirmed the oxidation state assignments. Computational studies were also performed to provide insight into the electronic structures of these complexes.

Effect of solvents and metal ions on the structural diversity of coordination polymers based on a dipyridylamide ligand: Construction, fluorescent and photocatalytic properties

Five new NiII/CdII/CoII coordination polymers (CPs), namely [Ni(3-pna)(mip)]·H2O (1), [Ni(3-pna)(mip)(H2O)]·4H2O (2), [Cd2(3-pna)(mip)2(H2O)]·2H2O (3), [Cd(3-pna)(mip)]2·3H2O (4) and [Co(3-pna)(mip)]·H2O (5) [3-pna=3-pyridylnicotinamide, H2mip=5-methylisophthalic acid], have been hydrothermally or solvothermally synthesized. These complexes were characterized by IR spectroscopy, thermal analysis and single-crystal X-ray diffraction. Complexes 1–5, based on the same dipyridylamide (3-pna) and dicarboxylate (mip) ligands but using different solvent systems and metal ions, exhibit various structures. Complexes 1 and 5 feature isostructural 2D networks, which are very similar to that of 4. Their structures contain [M2(COO)2-(3-pna)2]n (M=Ni, Cd or Co) ladder-like double chains. Complex 2 displays a 2D 4-connected grid structure consisting of 1D [Ni-3-pna]n and [Ni-mip]n chains. Complex 3 presents a new 3D framework constructed from Cd4(COO)4 subunits and μ2-bridging 3-pna ligands. The versatile structures reveal the remarkable impact of the solvent systems on the architectures. Furthermore, the fluorescent behaviors of 3–4 and the photocatalytic properties of 1–5 under UV irradiation have been studied.

Nitrobenzene-detecting 2D and 3D cadmium phenylenediamine coordination polymers with N,N′-ethylenediaminebis(isonicotinamide) auxiliary ligands

Hydrothermal reaction of cadmium nitrate, either 1,2-phenylenediacetic acid (12phdaH2) or 1,3-phenylenediacetic acid (13phdaH2), and the long-spanning dipyridylamide ligand N,N′-ethylenediaminebis(isonicotinamide) (ebin) produced a pair of new coordination polymers which were structurally characterized by single-crystal X-ray diffraction. {[Cd(12phda)(ebin)(H2O)]·H2O}n (1) exhibits 2D non-interpenetrated (4,4) grid coordination polymer layers stacked in an alternating ABAB pattern. In contrast, {[Cd(13phda)(ebin)(H2O)]·H2O}n (2) exhibits a very uncommon 3D 4-fold interpenetrated 658 cds topology. Compounds 1 and 2 showed potential as detectors for nitrobenzene in ethanol suspension, with more efficacious adsorption by the layered phase 1. Thermal properties of both new materials were also investigated.

Divergent topologies in divalent metal furandicarboxylate or thiophenedicarboxylate coordination polymers with bis(4-pyridylformyl)piperazine coligands

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.

Structure and Antiferromagnetism of Trinuclear Heterometallic Strings Containing MnII–MII–MnII Frameworks (M = Ni, Pd, Pt)

The syntheses, crystal structures, and magnetic properties of three trinuclear, symmetric, heterometal string complexes stabilized by four dipyridylamide (dpa) ligands were explored. MnNiMn(dpa)4Cl2 (1), MnPdMn(dpa)4Cl2 (2), and MnPtMn(dpa)4Cl2 (3) were found to exhibit an approximate D4 symmetry and a linear metal framework helically wrapped by four syn–syn‐type ligands. The center metal ions bond with the amide part of dpa– in a square‐planar environment, and the outer Mn ions bond with Cl– and the pyridyl part of dpa– in a square‐pyramidal environment. The magnetic susceptibilities of these three compounds showed antiferromagnetic interactions (2J = –13.7 cm–1 for 1, –29.7 cm–1 for 2, and –66.2 cm–1 for 3 in the Heisenberg exchange framework) between the MnII magnetic centers. The value of 2J increased with increasing atomic number of the central metal ion. The antiferromagnetic properties were further confirmed by electron paramagnetic resonance spectroscopy studies in variable‐temperature measurements.