2-fold Interpenetration Research Articles

Tunable gas adsorption properties of porous coordination polymers by modification of macrocyclic metallic tectons

By using the semi-rigid ligand tetrakis[4-(carboxyphenyl)oxamethyl]methane acid (H4TCM) and various macrocyclic metallic tectons, eight new Ni(II) coordination polymers, namely, [(NiL1)2(TCM)]·17H2O (1), [(NiL2)2(TCM)]·17H2O (2), [(NiL3)2(TCM)]·18H2O (3), [(NiL4)2(TCM)]·4DMF·10H2O (4), [(NiL5)2(TCM)]·4DMF·9H2O (5), [(NiL6)2(TCM)]·20H2O (6), [(NiL7)2(TCM)]·18H2O (7), [(NiL8)2(TCM)]·4H2O (8) (L1 = 1,8-dimethyl-1,3,6,8,10,13-hexaaza-cyclotetradecane, L2 = 1,3,6,9,11,14-hexaaza-tricyclooctadecane, L3 = 1,3,6,10,12,15-hexaaza-tricycloeicosane, L4 = 1,3,6,8,11,14-hexaaza-tricyclooctadecane, L5 = 4-methyl-1,3,6,8,11,14-hexaaza-tricyclooctadecane, L6 = 1,3,6,8,12,15-hexaaza-tricycloeicosane, L7 = 11-methyl-1,4,8,10,13,15-hexaaza-tricycloicosane and L8 = 3,10-diisobutyl-1,3,5,8,10,12-hexaaza-cyclotetradecane), were synthesized and structurally characterized. Single crystal X-ray analyses reveal that compounds 1–8 exhibit a similar diamondoid (dia) topology network. Regulated by macrocyclic metallic tectons, compounds 1–3 feature a three-dimensional (3D) framework with 7-fold interpenetration, giving rise to a 1D porous channel with size of ca. 1 nm. Compounds 4–7 possess a 3D network with 2D porous channels (porous size ca. 0.5 nm) and 4-fold interpenetration. Compound 8 shows a 3D dense packing arrangement with 2-fold interpenetration. The porosity of compounds 1–7 was confirmed by N2 gas adsorption measurements at 77 K. Furthermore, due to functional groups exposed on the porous surface, activated compound 3 exhibits selective adsorption of CO2 over N2. The results show the crystal structure, stability and gas adsorption can be tuned by the modification of macrocyclic metallic tectons.

Luminescent Coordination Polymers for Highly Sensitive Detection of Nitrobenzene

Three new luminescent coordination polymers (CPs), [Ag2(bpp)(Hsba)]·H2O (1), [Cd(bpp)(Hsba)·H2O] (2), and [Pb(bpp)3(H2sba)2] (3) (bpp = 1,3-bis(4-pyridyl)propane, H3sba = 2,4-dichloro-5-sulfamoylbenzoic acid), have been designed and synthesized by hydrothermal methods. Compound 1 exhibits left- and right-handed helical chains. Compound 2 shows a 2-fold parallel interpenetration sql net with 44·62 topology. Compound 3 displays a supramolecular wavelike chain. These three title CPs are used as fluorescence sensors for highly selective and sensitive detection of nitrobenzene in a wide linear detection range.

Tuning the Dimensionality of Interpenetration in a Pair of Framework-Catenation Isomers To Achieve Selective Adsorption of CO2 and Fluorescent Sensing of Metal Ions.

A pair of framework-catenation isomers (UPC-19 and UPC-20) based on an anthracene-functionality dicarboxylate ligand were synthesized and characterized for the first time through tuning of the dimensionality of interpenetration. The interpenetration dimensionality significantly influences the properties including the porosity, gas-uptake capacity, and fluorescent sensing ability: UPC-19 with 5-fold interpenetration is nonporous, whereas the 3-fold interpenetration form of UPC-20 is porous and exhibits selective adsorption of CO2 and fluorescent sensing of Cu(2+) and Fe(3+) through fluorescence quenching.

Three complexes of manganese(II) based on a new semirigid tetracarboxylate and N-containing ligands: Synthesis, crystal structures and magnetic properties

Three manganese(II) coordination polymers, namely [Mn(L)0.5(bipy)0.5(H2O)]n (1), [Mn2(L)(1,4-bimb)(H2O)2]n (2) and [Mn(L)0.5(4,4′-bibp)0.5(H2O)2]n (3), where H4L=5,5′-([1,1′-biphenyl]-4,4′-diylbis(oxy))diisophthalic acid, bipy=4,4′-bipyridine, 1,4-bimb=1,4-bis(imidazol-1-ylmethyl) benzene and 4,4′-bibp=4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl, have been successfully constructed using the hydrothermal method. To understand these compounds completely, single crystal X-ray diffraction, IR, powder X-ray diffraction (PXRD) and thermogravimetric studies have been carried out. Complexes 1 and 2 possess three-dimensional (3D) pillared-layer frameworks, and 2-fold and 3-fold interpenetration take place in 1 and 2, respectively. In complex 3, 2D layers are linked by hydrogen bonds, resulting in a 3D supramolecular architecture. Meanwhile, the magnetic behaviors of complexes 1 and 2 have been investigated and weak antiferromagnetic interactions between two Mn(II) centres within the polymers have been revealed.

A series of entangled coordination polymers assembled by a V-shaped bisimidazole ligand and various dicarboxylic acids: synthesis, characterization and luminescence properties

Based on a V-shaped bisimidazole ligand and various dicarboxylic acids, nine entangled coordination polymers, namely, [Zn(o-bdc)(bips)]·2H2O (1), [Zn2(cdc)2(bips)2]·2H2O (2), [Zn2(bpedc)2(bips)2] (3), [Zn(odc)(bips)]·H2O (4), [Zn2(sdc)2(bips)2]·5H2O (5), [Co2(sdc)2(bips)2(H2O)]·2H2O (6), [Cd2(bpdc)2(bips)2]·3H2O (7), [Cd2(2,6-ndc)2(bips)2(H2O)2]·2H2O (8) and [Cd(1,4-ndc)(bips)]·DMF·H2O (9) (bips = bis(4-imidazol-ylphenyl)sulfone, o-H2bdc = o-phenyldicarboxylic acid, H2cdc = 1,4-cyclohexanedicarboxylic acid, H2bpedc = 4,4′-stibenedicarboxylic acid, H2odc = 4,4′-oxybisbenzoic acid, H2sdc = 4,4′-sulfonyldibenzoic acid, H2bpdc = biphenyl-4,4′-dicarboxylic acid, 1,4-H2ndc = naphthalene-1,4-dicarboxylic acid, 2,6-H2ndc = naphthalene-1,4-dicarboxylic acid), have been synthesized and structurally characterized. Compound 1 exhibits a 2D → 2D polycatenane of 3-fold interpenetrated sql layers. Compound 2 shows a 2D → 3D polycatenane of 3-fold interpenetrated sql layers. Compound 3 displays a 2D → 3D polycatenane of 5-fold interpenetrated sql layers. Compound 4 exhibits a 2-fold interpenetration of CdSO4 networks. Compound 5 presents a 2D → 3D polycatenane by three-fold interpenetrated {42·63·8}2 layers. Compound 6 features an unusual 2D → 2D polycatenane framework assembled by the entanglement of sql layers containing 2-membered loops. Compound 7 exhibits a 1D → 3D polycatenane by the 3-fold interpenetration of 3-connected ribbons. Compound 8 displays a 3-fold interpenetration of SrAl2 networks. Compound 9 exhibits a 4-fold interpenetration of dia networks in a [2 + 2] mode. Their luminescence properties were also measured.

Novel mode of 2-fold interpenetration observed in a primitive cubic network of formula [Ni(1,2-bis(4-pyridyl)acetylene)2(Cr2O7)]n.

A primitive cubic (pcu) network of formula [Ni(1,2-bis(4-pyridyl)acetylene)2(Cr2O7)]n, , has been synthesised and found to exhibit a novel type of inclined 2-fold interpenetration and an isosteric heat of adsorption (Q(st)) of 30.5 kJ mol(-1) towards CO2 at zero loading. Q(st) is relatively high in the broad context but less than that observed in related hybrid ultramicroporous materials, a feature that can be understood after studying pore structure and molecular simulations of CO2 adsorption.

A novel 3-fold interpenetration metal–organic framework with tunable luminescence and selective adsorption of CO2 properties

A novel acylamide metal–organic framework (MOF) with 3-fold interpenetration has been synthesized, which shows high selective adsorption behaviors of CO2 and tunable luminescence properties dependent on excitation wavelengths.

Effect of Dicarboxylate Ligands on the Construction of Cd(II) Complexes Based on a Flexible Bis-Triazole Ligand

In this work, two dicarboxylate ligands, 4,4′-oxybis(benzoic acid) (H2oba) and 4,4′-biphenyldicarboxylic acid (H2bpdc) were employed as coligands to perform a comparison on the structures of Cd(II)-btmx complexes (btmx = 1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene) motifs. Two new complexes, {[Cd(btmx)(oba)]·H2O}n (1) and [Cd(btmx)(bpdc)]n (2), have been synthesized and characterized. Structural analyses show that 1 shows a 1D double-chain, while 2 displays an undulating 2D 44-sql network with 2-fold interpenetration. The structural differences of the two complexes suggest that the dicarboxylate ligands have great impact on the formation of such coordination architectures. Furthermore, the photoluminescence properties of 1 and 2 have also been investigated.

The various architectures and properties of a series of coordination polymers tuned by the central metals and auxiliary N-donor ligands

Five new coordination polymers, namely, [Zn(HL)(bib)]n·2nH2O (1), [Zn2(L)(μ3-OH)(H2O)]n·2nH2O (2), [Cd1.5(L) (H2O)2]n·0.5nH2O (3), [Cd1.5(L) (CH3CN)]n·0.5nH2O (4) and [Cd1.5(L)(bib)(H2O)2]n·nH2O (5), (H3L = biphenyl-2,4′,5-tricarboxylic acid, bib = 4,4′-bis(imidazol-1-yl)phenyl) have been synthesized under solvothermal conditions. Complexes 1–5 have been characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analysis. Complex 1 shows a 2D (4,4) network and further forms a 3D supramolecular framework by π–π interactions. Complex 2 is a 3D framework based on infinite rod-shaped chains. Complex 3 exhibits a 3D framework with a (3,4,5)-connected {42·6}2{42·84}{43·6·86}2 topology. Complex 4 features a 3D network with a (4,4,6)-connected {44·62}3{46·67·82}2 topology. 5 displays a 3D 2-fold interpenetrating (4,4,4)-connected framework with a point symbol of {4·64·10}2{4·64·8}2{62·84}. Moreover, the thermal stabilities and photoluminescence properties of 1–5 have been investigated.

Syntheses, characterization and luminescence properties of five entangled coordination polymers based on bis(4-imidazolphenoxy)methane and various dicarboxylic acids

Five novel entangled coordination polymers, namely, [Cd(sdc)(bipm)(H2O)]·DMF (1), [Cd2(bdc)2(bipm)2(DMF)2] (2), [Cd2(ndc)2(bipm)2]·2H2O (3), [Cd(bdc)(bipm)] (4) and [Cd2(bpdc)2(bipm)2] (5) [bipm = bis(4-imidazolphenoxy)methane, H2sdc = 4,4′-sulfonyldibenzoic acid, H2bdc = 1,4-benzenedicarboxylic acid , H2bpdc = biphenyl-4,4′-dicarboxylic acid, and H2ndc = naphthalene-2,6-dicarboxylic acid], have been synthesized and structurally characterized. Compound 1 exhibits a 2-fold interpenetration of (4,4)-connected sql network. Compound 2 displays an inclined catenation of (6,3)-connected hcb network. Compound 3 features an unusual twofold interpenetrating polyrotaxane motif composed of two interlocked sets of identical pcu nets. Compounds 4 and 5 both show 3D polycatenane motifs generated by the 2D → 2D parallel → 3D parallel interpenetration of (4,4)-connected sql network. But in 4, one net is interpenetrated by five others, while in 5, unusually, one net is interpenetrated by eight others. The thermal stabilities and photochemical properties of these compounds have also been studied.

A novel acylamide MOF showing self-catenated hxg-d-4-Fddd nets with 3-fold interpenetration and highly selective adsorption of CO2 over N2, CH4, and CO

Reported here is a novel acylamide MOF, Zn(L) (tdca)·1.5 DMF(1), obtained by a mixed ligand approach, where N4,N4′-di(pyridin-4-yl)-[1,1′-biphenyl]-4,4′- dicarboxamide(L) and thiophene-2,5-dicarboxylic acid (tdca) are used. The 3D framework can be represented as a rare 4-connected self-catenated hxg-d-4-Fddd net with a 65.8 topological symbol. Notably, the MOF shows high CO2 adsorption selectivity over CH4, CO, and N2 gases.

Hydrothermal syntheses, crystal structures and magnetic properties of five interpenetrated coordination networks: Effect of reaction conditions

Five new coordination networks, namely [Cu3(bimb)3(BTC)2] (1), [M(H2O)2(bimb)(SUC)] [M=CoII (2), MnII (3) and NiII (4)] and [Co(bimb)0.5(BDC)] (5) (bimb=1,4-bis(imidazol-1-yl)-butane, H3BTC=1,3,5-benzenetricarboxylic acid, H2SUC=succinic acid and H2BDC=1,4-benzenedicarboxylic acid) have been synthesized hydrothermally and structurally characterized by elemental analysis, IR spectra and X-ray diffraction analyses. Complex 1 exhibits a binodal 3,4-tfz net with 3-fold interpenetration. Complexes 2–4 are isostructural, all showing 3-fold interpenetrated dia structures. Complex 5 is a 3-fold interpenetrated 3D network structure of the pcu topology that is built from tetra-carboxylate dinuclear Co2 units with a paddle-wheel structure. We examined all the related known structures containing the same mixed ligands and found that the reaction conditions play an important role in the final structure. Furthermore, the magnetic property of 5 has also been investigated.

Construction of Zn(II) microporous metal–organic frameworks based on 1,1′-ethynebenzene-3,3′,5,5′-tetracarboxylate

Three novel microporous zinc MOFs, [Zn3(EBTC)2]∙2(CH3)2NH2∙0.5DMSO∙3H2O (1), [Zn(EBTC)0.5(BPY)]∙2DMSO∙0.5DMF∙2H2O (2) and [Zn2(EBTC)(BPP)2]∙3DMSO∙2DMF∙5H2O (3) (EBTC=1,1′-ethynebenzene-3,3′,5,5′-tetracarboxylate, BPY=4,4′-bipyridine, BPP=1,3-bi(4-pyridyl)propane), have been synthesized under solvothermal conditions. The versatile coordination modes of EBTC are the key to such diverse MOFs. The results of X-ray single diffraction analyses indicate that 3D microporous MOF 1 with fla topology possesses 2D [Zn3(EBTC)2]∞ layer built from 1D double-chain-like motif containing trinuclear [Zn3(COO)8]2− SBUs, in which the two phenyls of EBTC are almost perpendicularly arranged. Compound 2 is a 3D layer-pillar structure with Zn(II) ions bridged by planar EBTC to generate 2D [Zn(EBTC)0.5]∞ sheet, and the 2D sheets are further pillared by rigid BPY to form a 3D porous framework with fsc topology. Complex 3 exhibits a 3D 2-fold interpenetrating framework with (4.64.8)2(42.64) topology, in which the flexible BPP links the 1D [Zn2(EBTC)]∞ ladder to form a 2D [Zn2(EBTC)(BPP)2]∞ structure with large 1D channels, which leads the flexible 2D framework to 2-fold interpenetration and forms a 3D porous network. Complexes 1 and 3 exhibit good luminescent properties around the blue-violet region.

Synthesis, Characterization and Photoluminescence of Lanthanide Metal‐organic Frameworks, Constructed from Triangular 4,4′,4″‐s‐triazine‐1,3,5‐triyl‐p‐aminobenzoate Ligands

AbstractEight isomorphous metal‐organic frameworks: [Ln2(TATAB)2(H2O)(DMA)6]·5H2O (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Er (6), Tm (7), Yb (8)); TATAB = 4,4′,4″‐s‐triazine‐1,3,5‐triyl‐p‐aminobenzoate, DMA = N,N‐dimethylacetamide), were synthesized by the self‐assembly of lanthanide ions, TATAB, DMA and H2O. Single‐crystal X‐ray crystallography reveals they are three dimensional frameworks with 2‐fold interpenetration. Solid‐state photoluminescence studies indicate ligand‐to‐metal energy transfer is more efficient for compounds 2 and 4 which exhibit intense characteristic lanthanide emissions at room temperature.

Two different Zn(II) interpenetrating networks derived from different dicarboxylate ligands mixed with a flexible imidazole-based ligand

Two interpenetrating networks based on 1,4-bis(2-methylimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (bmimx), namely, {[Zn2(bmimx)2(cba)2]·2.5H2O}n (1) and {[Zn(bmimx)(suc)]·2H2O}n (2) (H2cba=4,4′-carbonyldibenzoic acid, H2suc=succinic acid) have been prepared at hydrothermal condition by varying the dicarboxylate ligands. Single-crystal X-ray diffraction indicates that complex 1 shows a 4-connected dmp net with 3-fold interpenetration which contains 1D (Zn−cba)n right- and left-handed helical chains; complex 2 shows a dia topology with 4-fold interpenetration. The results indicate that the spacers of dicarboxylate coligands have an important effect on the interpenetrating characters and ultimate frameworks. Moreover, the photoluminescence properties of the two complexes were studied in the solid state at room temperature.

Network flexibility: control of gate opening in an isostructural series of Ag-MOFs by linker substitution.

An isostructural series of 15 structurally flexible microporous silver metal-organic frameworks (MOFs) is presented. The compounds with a dinuclear silver core as secondary building unit (Ag2N4) can be obtained under solvothermal conditions from substituted triazolyl benzoate linkers and AgNO3 or Ag2SO4; they exhibit 2-fold network interpenetration with lvt topology. Besides the crystal structures, the calculated pore size distributions of the microporous MOFs are reported. Simultaneous thermal analyses confirm the stability of the compounds up to 250 °C. Interconnected pores result in a three-dimensional pore structure. Although the porosity of the novel coordination polymers is in the range of only 20-36%, this series can be regarded as a model system for investigation of network flexibility, since the pore diameters and volumes can be gradually adjusted by the substituents of the 3-(1,2,4-triazol-4-yl)-5-benzamidobenzoates. The pore volumes of selected materials are experimentally determined by nitrogen adsorption at 77 K and carbon dioxide adsorption at room temperature. On the basis of the flexible behavior of the linkers a reversible framework transformation of the 2-fold interpenetrated network is observed. The resulting adsorption isotherms with one or two hysteresis loops are interpreted by a gate-opening process. Due to external stimuli, namely, the adsorptive pressure, the materials undergo a phase transition confirming the structural flexibility of the porous coordination polymer.

Silver(I)/Bipyrazole/Dicarboxylate Interpenetrated Coordination Networks: Spontaneous Chiral Resolution, Modulation of Topologies, Water Clusters, and Photoluminescences

Seven novel silver(I) coordination networks with mixed flexible 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (bpz) and C3–C9 aliphatic dicarboxylic acids, [Ag2(bpz)4(mal)·7H2O]n (1L and 1R), [Ag2(bpz)3(suc)]n (2), [Ag4(bpz)5(glu)2]n (3), [Ag4(bpz)5(adip)2]n (4), [Ag4(bpz)7(pim)2·12H2O]n (5), [Ag2(bpz)4(sub)·7H2O]n (6), and [Ag2(bpz)3(aze)·3.5H2O]n (7) (H2mal = malonic acid, H2suc = succinic acid, H2glu = glutaric acid, H2adip = adipic acid, H2pim = pimelic acid, H2sub = suberic acid, H2aze = azelaic acid), have been synthesized and structurally characterized by single-crystal X-ray diffraction analyses and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). Single crystal X-ray diffraction analysis reveals that 1 crystallized into a pair of enantiomerically pure 3D 3-fold interpenetrated chiral SrSi2 networks (point symbol {103}) through spontaneous resolution in the absence of any chiral source. Complex 2 is a 3D 2-fold interpenetrated 3-connected uninodal dia-f network (point symbol {4·142}) without consideration of Ag···Ag interaction. Complexes 3 and 4 are similar 2D + 2D → 2D 63-hcb layer featuring 3-fold parallel interpenetration. Complex 5 is a 3D 3-fold interpenetrated 3,4-connected 3,4T1 network (point symbol {4·6·8}{4·62·83}). Complexes 6 and 7 are similar 2D + 2D → 2D fes layers (point symbol {4·82}) featuring 3-fold parallel interpenetration. In 1–7, structural diversity ranging from 2D hcb and fes layers to 3D chiral SrSi2, achiral dia-f, and 3,4T1 networks is modulated by dicarboxylates with alkyl chains of different lengths. Interestingly, a well-resolved octanuclear water cluster built from a chairlike (H2O)6 cluster and two water molecules dangling on two corners of it and a unusual seesaw-like pentanuclear water cluster is observed in the voids of 5 and 7, respectively. Furthermore, the solid-state photoluminescence properties of the 1–7 were investigated at 298 and 77 K.

Highly Selective Sorption of Small Hydrocarbons and Photocatalytic Properties of Three Metal–Organic Frameworks Based on Tris(4-(1H-imidazol-1-yl)phenyl)amine Ligand

By employing a tris(4-(1H-imidazol-1-yl)phenyl)amine (Tipa) ligand, three new metal-organic frameworks, [Zn2(Tipa)(4,4'-bpdc)1.5(H2O)(NO3)]·2(DMF)·H2O (1; 4,4'-bpdc = 4,4'-biphenyldicarboxylate, DMF = N,N-dimenthylformamide), [Cd(Tipa)Cl2]·2(DMF)·H2O (2), and [Co(Tipa)Cl2(H2O)]·DMF·H2O (3), have been synthesized solvothermally. Compound 1 features a three-dimensional (3D) pillared-layer structure with low band gap and interesting photocatalytic properties. Compound 2 is a 2-fold interpenetrating (3,6)-connected porous framework, and it shows highly selective adsorption of C2H2, CO2, and C2H4 over CH4. Compound 3 with honeycomb-like layers exhibits unusual 2D + 2D→ 3D polycatenation (2D = two-dimensional). The luminescent properties for these compounds were also investigated.

Reversible Structural Flexibility and Sensing Properties of a Zn(II) Metal–Organic Framework: Phase Transformation between Interpenetrating 3D Net and 2D Sheet

A three-dimensional Zn(II) framework, [Zn4O(L)3(DMF)2]·0.5DMF·H2O (1; H2L = 3,3′-dimethoxybiphenyl-4,4′-dicarboxylic acid) was prepared under a solvothermal reaction in DMF. The structure reveals that the 3-fold interpenetration is stabilized in the framework with a distinct secondary building unit of the formula [Zn4O(R-CO2)6(DMF)2], slightly different from that of MOF-5. Phase transformations in 1 occur reversibly via two pathways of solvent exchange/resolvation and activation/resolvation, which is indicative of the presence of extensive structural flexibility. Nitrobenzene among tested solvents is selectively detected by 1, and the sensing event was operating repeatedly. The three-dimensional framework of 1 with 3-fold interpenetration is uniquely converted to the two-dimensional Cu phase with no interpenetration, reflecting a drastic dimensionality variation.

A New 3D Metal-organic Framework Based on the Four-connecting Cobalt(II) Node Showing Unusual dmp Topology with 3-Fold Interpenetration

topology, InterpenetrationThe synthesis of polymeric coordination networks ormetal–organic frameworks (MOF s) has evoked an enormousamount of recent interest for their intriguing and diversearchitectures and for their potential as functional materialswith specific properties, such as luminescence, magnetism,absorption, catalysis, ion-exchange,