Guest-Stimulated Nonplanar Porphyrins in Flexible Metal-Organic Frameworks.

Nonplanar porphyrins with out-of-plane distortions play crucial roles in many biological functions and chemical applications. The artificial construction of nonplanar porphyrins usually involves organic synthesis and modification, which is a highly comprehensive approach. However, incorporating porphyrins into guest-stimulated flexible systems allows to manipulate the porphyrin distortion through simple ad/desorption of guest molecules.

Preparation, characterization, and electrochemical sensing performance of a novel pristine Cd-MOF and its composite with carbon nanotubes.

A novel Cd(II)-organic framework (Cd-MOF) {[Cd(isba)(bbtz)(HO)]·HO} (1) and its composite with CNTs (Cd-MOF@CNTs), [Hisba = 2-iodo-4-sulfobenzoicacid; bbtz = 1, 4-bis(1,2,4-triazolyl-1-methyl)benzene], were synthesized successfully under ambient conditions. The Cd-MOF is a 2D (4, 4) topological framework, further extending into a two-fold interpenetrated 3D supramolecular network hydrogen bonding. The activation energy for proton transfer in the composite Cd-MOF@CNT/Nafion membrane is lower than that in pristine Cd-MOF/Nafion, leading to its more temperature-insensitive proton conductivity.

Band gap, sorption properties and fluorescence sensing behaviour of a novel 1D→2D cathenane-like cobalt(II)-organic framework.

A novel hydrolytic stable Co-organic framework, namely poly[[bis(2-amino-4-sulfonatobenzoato-κO)tetraaquatris{μ-1,4-bis[(imidazol-1-yl)methyl]benzene-κN:N}dicobalt(II)] tetrahydrate], {[Co(CHNOS)(CHN)(HO)]·2HO}, (1), based on multifunctional 2-amino-5-sulfobenzoic acid (Hasba) and the auxiliary flexible ligand 1,4-bis[(imidazol-1-yl)methyl]benzene (bix), was prepared using the solution evaporation method. The purity of (1) was confirmed by elemental analysis and powder X-ray diffraction (PXRD) analysis. Complex (1) shows a novel 1D→2D interpenetrating network, which is further extended into a 3D supramolecular framework with channels occupied by the lattice water molecules.

Preparation, characterization and luminescence-sensing properties of two Zn MOFs with mixed 5-amino-2,4,6-tribromoisophthalic acid and bipyridyl-type ligands.

The bromo-substituted aromatic dicarboxylic acid 5-amino-2,4,6-tribromoisophthalic acid (HATBIP), in the presence of the N-donor flexible bipyridyl-type ligands 1,3-bis(pyridin-4-yl)propane (bpp) and N,N'-bis(pyridin-4-ylmethyl)oxalamide (4-bpme) and Zn ions, was used as an O-donor ligand to assemble two novel luminescent metal-organic frameworks (MOFs), namely poly[[(μ-5-amino-2,4,6-tribromoisophthalato-κO:O)[μ-1,3-bis(pyridin-4-yl)propane-κN:N']zinc(II)] dimethylformamide monosolvate], {[Zn(CHBrNO)(CHN)]·CHNO}, (1), and poly[[(μ-5-amino-2,4,6-tribromoisophthalato-κO:O)diaqua[μ-N,N'-bis(pyridin-4-ylmethyl)oxalamide-κN:N']zinc(II)] monohydrate], {[Zn(CHBrNO)(CHNO)(HO)]·HO}, (2), using the solution evaporation method. Both (1) and (2) were characterized by FT-IR spectroscopy, elemental analysis (EA), solid-state diffuse-reflectance UV-Vis spectroscopy, and powder and single-crystal X-ray diffraction analysis. Complex (1) shows a two-dimensional (2D) corrugated layer simplified as a 2D (4,4) topological network.

Synthesis and characterization of two one-dimensional Cd coordination polymers (CPs) with 5-amino-2,4,6-tribromoisophthalic acid and flexible N-donor bipyridyl ligands.

The bromo-substituted aromatic dicarboxylic acid 5-amino-2,4,6-tribromoisophthalic acid (HATBIP) was used to assemble with Cd ions in the presence of the N-donor flexible bipyridyl ligands 3,3'-(diazene-1,2-diyl)dipyridine (mzpy) and 1,3-bis(pyridin-3-ylmethyl)urea (3bpmu), leading to the formation of two chain coordination polymers by adopting solution methods, namely, catena-poly[[[triaqua(5-amino-2,4,6-tribromoisophthalato-κO)cadmium(II)]-μ-3,3'-(diazene-1,2-diyl)dipyridine-κN:N] dihydrate], {[Cd(CHBrNO)(CHN)(HO)]·2HO} or {[Cd(ATBIP)(mzpy)(HO)]·2HO}, (1), and catena-poly[[[tetraaquacadmium(II)]-μ-1,3-bis(pyridin-3-ylmethyl)urea-κN:N-[diaquabis(5-amino-2,4,6-tribromoisophthalato-κO)cadmium(II)]-μ-1,3-bis(pyridin-3-ylmethyl)urea-κN:N] octahydrate], {[Cd(CHBrNO)(CHNO)(HO)]·4HO} or {[Cd(ATBIP)(3bpmu)(HO)]·4HO}, (2). Both complexes were characterized by FT-IR spectroscopic analysis, thermogravimetric analysis (TGA), solid-state diffuse reflectance UV-Vis spectroscopic analysis, and single-crystal and powder X-ray diffraction analysis (PXRD). The mzpy and 3bpmu ligands bridge the Cd metal centres in (1) and (2) into one-dimensional chains, and the ATBIP ligands show a monodentate coordination to the Cd centres in both coordination polymers.

Two new Co coordination polymers with multifunctional 5-amino-2,4,6-tribromoisophthalic acid and flexible isomeric bis(imidazole) ligands: preparation, crystal structure and characterization.

Two new Co coordination polymers (CPs), namely, catena-poly[[[(5-amino-2,4,6-tribromobenzene-1,3-dicarboxylato-κO)aquacobalt(II)]-bis[μ-1,3-bis(imidazol-1-ylmethyl)benzene-κN:N']] 4.75-hydrate], {[Co(CHBrNO)(CHN)(HO)]·4.75HO}, (1), and poly[(μ-5-amino-2,4,6-tribromobenzene-1,3-dicarboxylato-κO:O)[μ-1,2-bis(imidazol-1-ylmethyl)benzene-κN:N']cobalt(II)], [Co(CHBrNO)(CHN)], (2), have been synthesized successfully by the assembly of multifunctional 5-amino-2,4,6-tribromoisophthalic acid (HATBIP) and Co ions in the presence of the flexible isomeric bis(imidazole) ligands 1,3-bis(imidazol-1-ylmethyl)benzene (mbix) and 1,2-bis(imidazol-1-ylmethyl)benzene (obix).

A new copper(II) supramolecular coordination polymer and a dinuclear compound with multifunctional 2-amino-5-sulfobenzoic acid and flexible N-donor ligands: synthesis, structure and characterization.

Multifunctional 2-amino-5-sulfobenzoic acid (Hafsb) can exhibit a variety of roles during the construction of supramolecular coordination polymers. The pendant carboxylic acid, sulfonic acid and amino groups could not only play a role in directing bonding but could also have the potential to act as hydrogen-bond donors and acceptors, resulting in extended high-dimensional supramolecular networks. Two new Cu coordination compounds, namely catena-poly[[[diaquacopper(II)]-μ-1,6-bis(1H-1,2,4-triazol-1-yl)hexane-κN:N] bis(3-amino-4-carboxybenzenesulfonate) dihydrate], {[Cu(CHN)(HO)](CHNOS)·2HO} or {[Cu(bth)(HO)](Hafsb)·2HO}, (1), and bis(μ-2-amino-5-sulfonatobenzoato-κO:O)bis{μ-1,2-bis[(1H-imidazol-1-yl)methyl]benzene-κN:N}bis[aquacopper(II)] trihydrate, [Cu(CHNOS)(CHN)(HO)]·3HO or [Cu(afsb)(obix)(HO)]·3HO, (2), have been obtained through the assembly between Hafsb and the Cu ion in the presence of the flexible N-donor ligands 1,6-bis(1H-1,2,4-triazol-1-yl)hexane (bth) and 1,2-bis[(1H-1,2,4-triazol-1-yl)methyl]benzene (obix), respectively.

Preparation and characterization of two new Cu supramolecular coordination polymers incorporating sulfobenzoate and flexible heterocyclic ligands.

The assembly of Cu with the multifunctional ligand 2-amino-4-sulfobenzoic acid (Hasba) in the presence of the auxiliary flexible ligands 1,4-bis(triazol-1-ylmethyl)benzene (bbtz) and 1,4-bis(imidazol-1-ylmethyl)benzene (bix) under ambient conditions resulted in two new supramolecular coordination polymers, namely poly[[(3-amino-4-carboxybenzenesulfonato-κO)aquabis[μ-1,4-bis(triazol-1-ylmethyl)benzene-κN:N]copper(II)] 3-amino-4-carboxybenzenesulfonate tetrahydrate], {[Cu(CHNOS)(CHN)(HO)](CHNOS)·4HO}, (1), and poly[[bis(μ-2-amino-4-sulfonatobenzoato-κO:N,O)tetraaqua[μ-1,4-bis(triazol-1-ylmethyl)benzene-κN:N]dicopper(II)] tetrahydrate], {[Cu(CHNOS)(CHN)(HO)]·4HO}, (2). Single-crystal X-ray structure diffraction analysis of (1) reveals that the bbtz ligand acts as a bridge, linking adjacent Cu ions into a two-dimensional cationic (4,4) topological network, in which the coordinated 3-amino-4-carboxybenzenesulfonate (Hasba) anion uses its sulfonate group to bind with the Cu ion in a monodentate fashion and the carboxylate group remains protonated. The lattice Hasba anion resides in the two-dimensional layer and balances the charge.

Synthesis and characterization of a cadmium(II)-organic supramolecular coordination compound based on the multifunctional 2-amino-5-sulfobenzoic acid ligand.

Much attention has been paid by chemists to the construction of supramolecular coordination compounds based on the multifunctional ligand 5-sulfosalicylic acid (HSSA) due to the structural and biological interest of these compounds. However, no coordination compounds have been reported for the multifunctional amino-substituted sulfobenzoate ligand 2-amino-5-sulfobenzoic acid (Hasba). We expected that Hasba could be a suitable building block for the assembly of supramolecular networks due to its interesting structural characteristics.

Synthesis, structure and characterization of two new metal-organic coordination polymers based on the ligand 5-iodobenzene-1,3-dicarboxylate.

Two new coordination polymers (CPs) formed from 5-iodobenzene-1,3-dicarboxylic acid (H2iip) in the presence of the flexible 1,4-bis(1H-imidazol-1-yl)butane (bimb) auxiliary ligand, namely poly[[μ2-1,4-bis(1H-imidazol-1-yl)butane-κ(2)N(3):N(3')](μ3-5-iodobenzene-1,3-dicarboxylato-κ(4)O(1),O(1'):O(3):O(3'))cobalt(II)], [Co(C8H3IO4)(C10H14N4)]n or [Co(iip)(bimb)]n, (1), and poly[[[μ2-1,4-bis(1H-imidazol-1-yl)butane-κ(2)N(3):N(3')](μ2-5-iodobenzene-1,3-dicarboxylato-κ(2)O(1):O(3))zinc(II)] trihydrate], {[Zn(C8H3IO4)(C10H14N4)]·3H2O}n or {[Zn(iip)(bimb)]·3H2O}n, (2), were synthesized and characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), solid-state UV-Vis spectroscopy, single-crystal X-ray diffraction analysis and powder X-ray diffraction analysis (PXRD). The iip(2-) ligand in (1) adopts the (κ(1),κ(1)-μ2)(κ(1), κ(1)-μ1)-μ3 coordination mode, linking adjacent secondary building units into a ladder-like chain. These chains are further connected by the flexible bimb ligand in a trans-trans-trans conformation.

Synthesis, structure and characterization of two copper(II) supramolecular coordination polymers based on a multifunctional ligand 2-amino-4-sulfobenzoic acid.

Copper(II) coordination polymers have attracted considerable interest due to their catalytic, adsorption, luminescence and magnetic properties. The reactions of copper(II) with 2-amino-4-sulfobenzoic acid (H(2)asba) in the presence/absence of the auxiliary chelating ligand 1,10-phenanthroline (phen) under ambient conditions yielded two supramolecular coordination polymers, namely (3-amino-4-carboxybenzene-1-sulfonato-κO(1))bis(1,10-phenanthroline-κ(2)N,N')copper(II) 3-amino-4-carboxybenzene-1-sulfonate monohydrate, [Cu(C7H6N2O5S)(C12H8N2)2](C7H6N2O5S)·H2O, (1), and catena-poly[[diaquacopper(II)]-μ-3-amino-4-carboxylatobenzene-1-sulfonato-κ(2)O(4):O(4')], [Cu(C7H6N2O5S)(H2O)2]n, (2). The products were characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), solid-state UV-Vis spectroscopy and single-crystal X-ray diffraction analysis, as well as by variable-temperature powder X-ray diffraction analysis (VT-PXRD).

Synthesis, structure and properties of a new three-dimensional interpenetrated metal-organic framework with 3,3'-azodibenzoic acid (H2azdc) and 1,4-bis(1H-imidazol-1-yl)butane (bimb): {[Cd(azdc)(bimb)2]·H2O}n.

A new three-dimensional interpenetrated Cd(II)-organic framework based on 3,3'-azodibenzoic acid [3,3'-(diazenediyl)dibenzoic acid, H2azdc] and the auxiliary flexible ligand 1,4-bis(1H-imidazol-1-yl)butane (bimb), namely poly[[bis[μ2-1,4-bis(1H-imidazol-1-yl)butane-κ(2)N(3):N(3')][μ2-3,3'-(diazenediyl)dibenzoato-κ(2)O:O']cadmium(II)] monohydrate], {[Cd(C14H8N2O4)(C10H14N2)2]·H2O}n, (1), was obtained by a typical solution reaction in mixed solvents (water and N,N'-dimethylformamide). Each Cd(II) centre is six-coordinated by two O atoms of bis-monodentate bridging carboxylate groups from two azdc(2-) ligands and by four N atoms from four bimb ligands, forming an octahedral coordination environment. The Cd(II) ions are connected by the bimb ligands, resulting in two-dimensional (4,4) layers, which are further pillared by the azdc(2-) ligands, affording a threefold interpenetrated three-dimensional α-Po topological framework with the Schläfli symbol 4(12)6(3).

Synthesis, characterization and properties of a family of lead(II)-organic frameworks based on a multi-functional ligand 2-amino-4-sulfobenzoic acid exhibiting auxiliary ligand-dependent dehydration-rehydration behaviours.

A systematic investigation is reported of the use of the multi-functional ligand 2-amino-4-sulfobenzoate (asba(2-)) to construct lead(II)-organic frameworks in the presence and absence of N-donor auxiliary ligands phen, bipy and bix [phen = 1,10-phenanthroline, bipy = 2,2'-bipyridine and bix = 1,4-(methylene-benzene)bisimidazole]. Under ambient, aqueous conditions the assembly of asba(2-) with Pb(II) and phen or bipy leads to two iso-structural 2D double-layer frameworks, {[Pb2(asba)2(phen)2(H2O)]·2H2O}n (1) and {[Pb2(asba)2(bipy)2(H2O)]·2H2O}n (2). [Pb2(asba)2(bix)2(H2O)2]n (3) is obtained in the presence of the auxiliary ligand bix and possesses a 3D network built up from 2D Pb(II)-asba(2-)-bridged double-layer pillared by bix.

Preparation, structural diversity and characterization of a family of Cd(II)-organic frameworks.

Two Cd(II)-organic frameworks based on 5-iodoisophthalate (IIP(2-)), {[Cd(IIP)(bte)(H2O)]·H2O}n (1) and [Cd(IIP)(bpp)(H2O)]n (2), were obtained either at an ambient temperature or under solvothermal conditions at 120 °C in the presence of 1,4-bis(1,2,4-triazol-1-yl)ethane (bte) and 1,3-bis(4-pyridyl)propane (bpp) as auxiliary ligands, respectively. 1 is a novel discrete single-walled Cd(II)-organic tube (SWCOT) which further extends into a 3D supramolecular interdigitated microporous columnar architecture supported by C-I···I halogen bonds and hydrogen bonds, while 2 exhibits an interesting two-fold interpenetrated 3D diamond network architecture. When the auxiliary ligands bte or bpp were replaced by a longer spacer ligand with more flexibility, 1,4-bis(triazol-1-ylmethyl)benzene (bbtz), the unique discrete single-walled Cd(II)-organic nanotube (SWCONT), {[Cd(IIP)(bbtz)(H2O)]·H2O}n (3), which further extends into a 3D supramolecular microporous framework supported by face-to-face π···π stacking interactions and hydrogen bonds, was generated at room temperature.

Poly[[bis-(μ-3-amino-5-carb-oxy-benzoato-κ(2)N:O(1))diaqua-zinc] dihydrate].

The Zn(II) atom in the title polymeric compound, {[Zn(C(8)H(6)NO(4))(2)(H(2)O)(2)]·2H(2)O}(n), lies on a center of inversion and is coordinated by two amine N atoms and two carboxyl-ate O atoms from two 3-amino-5-carb-oxy-benzoate anions along with two water mol-ecules in a distorted octa-hedral geometry. The bridging nature of the anion generates a layer motif parallel to (100). Hydrogen bonds of the N-H⋯O and O-H⋯O types exist in the structure.

1-{[4'-(1H-1,2,4-Triazol-2-ium-1-ylmeth-yl)biphenyl-4-yl]meth-yl}-1H-1,2,4-triazol-2-ium bis-(3-carb-oxy-5-iodo-benzoate)-5-iodo-benzene-3,5-dicarb-oxy-lic acid-water (1/2/2).

The neutral carb-oxy-lic acid mol-ecule and the carboxyl-ate anion in the title compound, C(18)H(18)N(6) (2+)·2C(8)H(4)IO(4) (-)·2C(8)H(5)IO(4)·2H(2)O, are both nearly planar (r.m.s.

Poly[[diaqua-(1,10-phenanthroline-κN,N')(μ(3)-4-sulfonato-benzene-1,2-dicarboxyl-ato-κO:O,O:O)dysprosium(III)] dihydrate].

The 4-sulfophthalate trianion in the polymeric title complex, {[Dy(C(8)H(3)O(7)S)(C(12)H(8)N(2))(H(2)O)(2)]·2H(2)O}(n), bridges three water/phenanthroline-coordinated Dy(III) atoms to form a three-dimensional network architecture. The metal atom is further chelated by a carboxyl-ate group and is covalently bonded to a monodentate carboxyl-ate group and to a monodentate sulfonate group in a distorted square-anti-prismatic geometry. The coordinating and the solvent water mol-ecules are hydrogen bonded to the network.

Poly[[diaqua-(1,10-phenanthroline-κN,N')(μ(3)-4-sulfonato-benzene-1,2-di-car-boxyl-ato-κO:O,O:O)erbium(III)] dihydrate].

The 4-sulfophthalate trianion in the polymeric complex, {[Er(C(8)H(3)O(7)S)(C(12)H(8)N(2))(H(2)O)(2)]·2H(2)O}(n), bridges three water/phenanthroline-coordinated Er(III) ions to form a three-dimensional network architecture. The metal atom is further chelated by a carboxyl-ate group and is covalently bonded to a monodentate carboxyl-ate group as well as to a monodentate sulfonate group in a distorted square anti-prismatic geometry. The coordinating water molecules and the lattice water molecules, one of which is disordered over two positions [major component 65 (3)%], are hydrogen bonded to the network.

5-Amino-2,4,6-triiodo-isophthalic acid-4,4'-bipyridine N,N'-dioxide-water (1/1/1).

The aromatic rings of the N,N'-dioxide molecule in the title compound, C(8)H(4)NI(3)O(4)·C(10)H(8)N(2)O(2)·H(2)O, are twisted by 14.0 (2)°. The -CO(2)H substituents of the 5-amino-2,4,6-triiodo-isophthalic acid are twisted by 83.

(5-Amino-isophthalato-κN)triaqua-(1,10-phenanthroline-κN,N')nickel(II) trihydrate.

The Ni(II) atom in the title compound, [Ni(C(8)H(5)NO(4))(C(12)H(8)N(2))(H(2)O)(3)]·3H(2)O, is six-coordinated in an NiN(3)O(3) octa-hedral geometry. The triply water-coordinated Ni(II) atom is chelated by the phenantroline ligand and is additionally coordinated by the amino group of the 5-amino-isophtalate anion. The anion, the coordinated and the uncoordinated water mol-ecules inter-act through an extensive O-H⋯O and N-H⋯O hydrogen-bonding network, generating a three-dimensional cage-like network.

4-(4-Pyrid-yl)pyridinium 3-amino-5-carb-oxy-2,4,6-triiodo-benzoate-5-amino-2,4,6-triiodo-isophthalic acid (1/1).

In the title ammonium carboxyl-ate-carb-oxy-lic acid co-cystal, C(10)H(9)N(2) (+)·C(8)H(3)I(3)NO(4) (-.)C(8)H(4)I(3)NO(4), the carboxyl-ate anion and carb-oxy-lic acid mol-ecule are linked by O-H⋯O and N-H⋯O hydrogen bonds to form a chain running along the c axis of the monoclinic unit cell. The chains are linked by pyridinum and pyridine N-H⋯O hydrogen bonds, generating a layer motif.

catena-Poly[[tetra-aqua-[μ(2)-1,4-bis-(1,2,4-triazol-1-yl)butane-κN:N]cadmium(II)] sulfate].

In the polymeric title compound, {[Cd(C(8)H(12)N(6))(H(2)O)(4)]SO(4)}(n), the Cd(II) atom is located on an inversion center and coordinated by four water mol-ecules and two 1,4-bis-(1,2,4-triazol-yl)butane ligands in a distorted CdO(4)N(2) octa-hedral geometry. The 1,4-bis-(1,2,4-triazol-yl)butane ligand is centrosymmetric, the mid-point of the central C-C bond being located on an inversion center. It links adjacent water-coordinated metal atoms into polymeric chains running along the c axis.

2,2'-Biimidazolium 5-amino-2,4,6-tri-bromo-isophthalate.

In the cation of the title salt, C(6)H(8)N(4) (2+)·C(8)H(2)Br(3)NO(4) (2-), the dihedral angle between the two five-membered rings is 2.1 (3)°. In the anion, the mean planes of the carboxyl units are twisted from the benzene ring by 84.

Tetra-kis(1H-imidazole-κN)(2-phenyl-propanedioato-κO,O)nickel(II).

In the title complex, [Ni(C(9)H(6)O(4))(C(3)H(4)N(2))(4)], the Ni(II) ion is O,O'-chelated by the phenyl-malonato ligand and coordinated by four imidazole ligands in a slightly distorted octa-hedral geometry. In the crystal structure, symmetry-related mol-ecules are linked by N-H⋯O hydrogen bonds, generating a three-dimensional network.

(5-Amino-isophthalato-κN)triaqua-(1,10-phenanthroline-κN,N')cobalt(II) trihydrate.

The Co(II) atom in the title compound, [Co(C(8)H(5)NO(4))(C(12)H(8)N(2))(H(2)O)(3)]·3H(2)O, is six-coordinated in a CoN(3)O(3) octa-hedral geometry; the water-coordinated Co(II) atom is chelated by the N-heterocycle. An inter-molecular N-H⋯O hydrogen bond occurs. The carboxyl-ate entity coordinates through the amino group.