Sulfonyldibenzoic Acid Research Articles

New coordination polymers based on a V-shaped ligand and lanthanides: Structural description and symmetry-luminescence correlation using europium as a probe

We have synthesized new luminescent coordination polymers using 4,4׳-sulfonyldibenzoic acid (H2SDA) and several lanthanide ions by open crystallization in DMF. Three different 1-D structures were obtained, as determined by single-crystal X-ray diffraction: [La(η2-NO3)(μ-SDA)(DMF)3]n (1), [Sm(η2-NO3)(μ-SDA)(DMF)2·2DMF]n (3), [Ln(η2-NO3)(μ-SDA)(DMF)2·DMF]n (Ln = Eu (4), Dy (5), Ho (6), Er (7), Tm (8) and Lu (9)). A 2-D structure, [Er2(η2-SDA)3(DMF)(H2O)3·2DMF]n (10), was also obtained. The measured photophysical properties of these compounds seem to be interesting for applications (high lifetime, narrow line width and high degree of color purity). In addition, emission spectra, spontaneous emission coefficients (Arad and Anrad), and intensity parameters (Ω2 and Ω4), from spectroscopic data of Eu3+, were used to evaluate crystal stabilities. Differences in the spectra acquired before and after DMF removal clearly reflected the changes taking place in the ion environment.

A family of entangled coordination polymers constructed from a flexible bisimidazole ligand and versatile polycarboxylic acids: Syntheses, structures and properties

A family of entangled coordination polymers, namely, [Cd(cba)(ibpi)] (1), [Cd(sdc)(ibpi)]·H2O (2), [Cd2(bpdc)2(ibpi)2] (3), [Ni2(sdc)2(ibpi)2(H2O)2]·H2O (4), [Cd2(tdc)2(ibpi)]·H2O (5), [Cd(Hbtc)(ibpi)] (6), [Co2(tdc)2(ibpi)2·H2O]·2H2O (7) and [Cd2(cdc)2(ibpi)2]·2H2O (8). [ibpi=1-(4-(4-(1H-imidazol-1-yl)benzyloxy)phenyl)-1H-imidazole, H2cba=4,4′-carbonyldibenzoic acid, H2sdc=4,4′-sulfonyldibenzoic acid, H2bpdc=biphenyl-4,4′-dicarboxylic acid, H2cdc=1,4-cyclohexanedicarboxylic acid, H2tdc=thiophene-2,5-dicarboxyl acid, and H3btc=1,3,5-benzenetricarboxylic acid], have been synthesized and structurally characterized. Compound 1 exhibits a 2-fold parallel interpenetration of sql networks. Compound 2 presents a 3-fold parallel interpenetration of sql networks. Compound 3 features a parallel polycatenation of 3-fold interpenetrated sql networks. Compound 4 shows a unique type of inclined interpenetration of sql networks. Compound 5 displays a 3-fold interpenetration of pcu network. Compound 6 exhibits a uninodal self-catenating mab network. Compound 7 shows an 8-connected self-catenating framework of 8T10 topology with the point symbol (420·68). Compound 8 presents a unique 8-connected 8T21 self-catenating framework with the point symbol (424·64). The thermal stabilities and photochemical properties of compounds 1, 2, 3, 5, 6and8 have also been studied.

ChemInform Abstract: Synthesis of Heterofunctional 3,3′‐Sulfonyldibenzoic Acid Derivatives.

A method for the preparation of previously difficult to access heterofunctional 3,3'-sulfonyldibenzoic acid derivatives containing amino-, alkylamino-, hydroxy-, and alkoxy substituents at the vicinal position relative to the sulfonyl group has been elaborated. The interaction of methyl 4-nitro-10,10-dioxophenoxathiine-2,8-dicarboxylate with amines and O-nucleophiles was shown to proceed under mild conditions, resulting in oxathiine ring opening, and the nucleophilic substitution occurred exclusively at position 4а of phenoxathiine.

Switchable Room-Temperature Ferroelectric Behavior, Selective Sorption and Solvent-Exchange Studies of [H3 O][Co2 (dat)(sdba)2 ]⋅H2 sdba⋅5 H2 O.

A newly synthesized compound, [H3 O][Co2 (dat)(sdba)2 ]⋅H2 sdba⋅5 H2 O (I, dat=3,5-diamino-1,2,4-triazole; H2 sdba=4,4'-sulfonyldibenzoic acid), has Co2 "paddlewheel" units connected by sdba ligands to form one-dimensional chains, which are connected by dat to form an anionic three-dimensional structure with cds topology. The one-dimensional channels in the structure contain water molecules, hydronium ions and H2 sdba. The water molecules could be reversibly exchanged with D2 O, CH3 OH and C2 H5 OH molecules; these exchanges were performed in a single-crystal-to-single-crystal manner. Gas sorption studies on the dehydrated compound showed the selective adsorption of CO2 over methane at 195 K. Nonlinear optical measurements indicated that I exhibits a second harmonic generation signal that is approximately one-third that of urea. Studies of polarization versus electric field demonstrated compound I as a potential room-temperature ferroelectric material with a saturation polarization of 0.23 μC cm-2 and remnant polarization of 0.14 μC cm-2 . The dehydrated compound exhibited a simple paraelectric behavior.

Two new luminescent Cd(II)/Zn(II) metal–organic frameworks for exceptionally selective detection of picric acid explosives

Two new coordination polymers, {[Cd(BIDPT)(oba)]·0.5H2O}n (1) and {[Zn(BIDPT)(4,4′-sdb)]·2.25H2O}n (2) (BIDPT=4,4′-bis(imidazol-l-yl)diphenyl thioether, H2oba=4,4′-oxydibenzoic acid, 4,4′-H2sdb=4,4′-sulfonyldibenzoic acid), have been solvothermally synthesized and characterized. Both 1 and 2 show 2-fold interpenetrating 3D frameworks with {65∙8} cds and {66} dia topology, respectively. These two coordination polymers show strong luminescence and their luminescence could be quenched by a series of nitro explosives. Importantly, they exhibit very highly sensitive and selective detection of picric acid compared to other nitro explosives.

Synthesis of heterofunctional 3,3'-sulfonyldibenzoic acid derivatives

A method for the preparation of previously difficult to access heterofunctional 3,3'-sulfonyldibenzoic acid derivatives containing amino-, alkylamino-, hydroxy-, and alkoxy substituents at the vicinal position relative to the sulfonyl group has been elaborated. The interaction of methyl 4-nitro-10,10-dioxophenoxathiine-2,8-dicarboxylate with amines and O-nucleophiles was shown to proceed under mild conditions, resulting in oxathiine ring opening, and the nucleophilic substitution occurred exclusively at position 4а of phenoxathiine.

1D lead(II) coordination chains with carboxylate containing ligands. A rare example of polyrotaxane 1D → 1D interpenetrated coordination polymer

The structural determination of two interesting lead(II) coordination polymers, namely [Pb(ind)2(H2O)]n (1) and [Pb2(dbsf)2(bipy)]n (2) (Hind=indane-2-carboxylic acid, H2dbsf=4,4′-sulfonyldibenzoic acid, and bipy 4,4′-bipyridine), reveals in the second an unexpected polyrotaxane 1D→1D interpenetrated coordination polymer thanks to the hemidirected coordination geometry of the metal and the rings formed by the dicarboxybiphenyl sulfone ligands along the 1D chain.

Diverse structures of metal-organic frameworks via a side chain adjustment: interpenetration and gas adsorption.

Three new coordination polymers have been synthesized based on three linear pyridine ligands with different side chains and one flexible V-shaped dicarboxylate co-ligand: {[Co(L1)0.5(sdb)]}n (1), {[Co(L2)0.5(sdb)]·1.5H2O}n (2) and {[Co(L3)0.5(sdb)]·2DMF}n (3) (L1 = E,E-2,5-dioctyloxy-1,4-bis-[2-pyridin-vinyl]-benzene; L2 = E,E-2,5-dibutoxy-1,4-bis-[2-pyridin-vinyl]-benzene; L3 = E,E-2,5-dimethoxy-1,4-bis-[2-pyridin-vinyl]-benzene; H2sdb = 4,4'-sulfonyldibenzoic acid). Complexes 1-3 are 4-connected sql nets with a point symbol of {44·62}. The interpenetration forms and porosity of frameworks have been well controlled by side chain prolongation. A larger steric hindrance for the pendant -OnOct and -OnBut groups leads to a larger repulsive force between the layers and effective construction of inclined polycatenations. A smaller steric hindrance for the pendant -Me group leads to the formation of a parallel stacked network. Therefore, compounds 1 and 2 feature 3D structures with inclined polycatenation (2D + 2D → 3D); compound 3 exhibits a non-interpenetrated 2D + 2D → 2D parallel stacked network. These complexes have been characterized by single crystal X-ray diffraction, infrared spectroscopy, thermogravimetry, elemental analysis, and powder X-ray diffraction measurements. In addition, the gas adsorption properties of the compounds have also been explored.

Synthesis and characterization of an unprecedented 3D lanthanide coordination polymer assembled by cubane-like clusters and a flexible V-shaped dicarboxylate ligand

A lanthanide coordination polymer based on H2sfdb ligand, namely [Tb4(sdbc)4(phen)2(μ3-OH)4]n∙1.5nH2O (1) (H2sfdb=4,4′-sulfonyldibenzoic acid, phen =1,10-phenanthroline) has been hydrothermal synthesized and characterized. Compound 1 exhibits an unprecedented three-dimensional framework that comprised new cubane-like hydroxo clusters [Tb4(μ3-OH)4]8+ as the nodes and flexible (sfdb)2− ligands as the linkers. In 1, (sfdb)2− ligands display completely different four kinds of coordination modes. Interestingly, not only the carboxylate groups but also one oxygen atom of sulfonyl group of (sfdb)2− ligand are coordinated with TbIII ions in 1, which is first found in the compounds based on H2sfdb ligand. The luminescence experiments show that TbIII compound exhibits the typical TbIII-centered luminescence.

Сrystal structure and magnetic property of a new two-dimensional coordination polymer constructed by 1,4-bis(1,2,4-triazol-1-ylmethyl)-benzene and 4,4′-sulfonyldibenzoic acid

A two-dimensional Ni(II) complex {[Ni(BTX)(SDBA)(H2O)]•0.29H2O}n (1) (BTX = 1,4-bis(1,2,4-triazol-1-ylmethyl)-benzene, H2SDBA = 4,4′-sulfonyldibenzoic acid) is synthesized and characterized using single crystal X-ray diffraction, IR spectroscopy, and elemental analysis. The single crystal X-ray diffraction analysis reveals that complex 1 is a two-dimensional polymer containing 28-membered rings based on the rhomboid subunit [Ni2(C14H8O6S)2] with a Ni–Ni separation of 12.923 A. The thermal stability and magnetic property of the title complex are briefly investigated.

Thermal, spectroscopic and luminescence investigations of lanthanide(III) coordination polymers based on V-shaped 4,4′-sulfonyldibenzoic acid

The complexes of lanthanide ions with V-shaped 4,4′-sulfonyldibenzoic acid (Hssdb) of the formula Ln2sdb3·nH2O, where Ln=La(III), Nd(III), Eu(III), Tb(III), Dy(III), Yb(III) and n=2–6 have been prepared by the hydrothermal method. The complexes were examined by elemental analysis, infrared spectroscopy (ATR-FTIR), X-ray diffraction pattern measurements and different methods of thermal analysis (TG-DSC and TG-FTIR). The luminescence properties of Eu(III) and Tb(III) complexes have been also investigated. The complexes crystallize in the triclinic (La, Nd and Eu) or monoclinic (Tb, Dy, Yb) crystal systems. Additionally, pentahydrate complexes of Dy(III) and Tb(III) are isostructural. 4,4′-sulfonyldibenzoate ligand coordinates lanthanide ions through both carboxylate groups. Heating of the complexes resulted in dehydration and formation of stable Ln2sdb3 compounds. Combustion of the organic ligand leads to the formation of intermediate stable lanthanide oxysulfate Ln2O2SO4 which further decompose into the suitable oxides. In nitrogen atmosphere, investigated complexes release: water, carbon oxides, disulphur oxide and benzene molecules. The Eu(III) and Tb(III) complexes exhibit characteristic red and green luminescence.

Crystal growth, differential gas adsorption, high thermal stability, and reversible coordination of two new barium-organic frameworks, Ba(SBA)(DMF)4 and Ba2(BTEC)(H2O)

Single crystals of two barium-organic framework materials, Ba(SBA)(DMF)4 (CAUMOF-15) and Ba2(BTEC)(H2O) (CAUMOF-16), have been grown through solvothermal reactions (H2SBA=4,4′-sulfonyldibenzoic acid and H4BTEC=1,2,4,5-benzenetetracarboxylic acid). The crystal structures of the reported frameworks have been determined by single-crystal X-ray diffraction. The materials have been fully characterized by powder X-ray diffraction (PXRD), elemental analyses, Infrared (IR) spectroscopy, and thermogravimetric analyses (TGA). CAUMOF-15 reveals a three-dimensional open-framework that comprises of an inorganic motif with one-dimensional chains and the SBA linkers. CAUMOF-16 shows another three-dimensional backbone consisting of layers of edge-shared BaO9 and BaO10 polyhedra, and BTEC pillars. Both of the 3D frameworks exhibit relatively high thermal stabilities. The PXRD and IR spectral data confirm that CAUMOF-15 and CAUMOF-16 reveal reversible coordinations of the respective solvent molecules, DMF and H2O. Gas adsorption properties towards nitrogen, hydrogen, and carbon dioxide have been also investigated.

Coordination complexes based on V-shaped ligand and rare earth(III) ions: lanthanide contraction effect induced structural changes

A series of metal-organic frameworks, {Ln2(SDB)3(H2O)5}n [Ln = Eu(1), Gd(2), Tb(3), Dy(4)], {[Ln2(SDB)3(H2O)4]·H2O}n [Ln = Ho(5), Er(6), Tm(7), Y(8)] and {[Lu2(SDB)3·(H2O)3]·4H2O}n (9) (H2SDB = 4,4’-sulfonyldibenzoic acid), have been synthesized under hydrothermal conditions by using the V-shaped ligand H2SDB. The structures of the complexes have been determined by single-crystal X-ray diffraction and further characterized using IR spectroscopy, powder X-ray diffraction, and thermogravimetric analysis. The single crystal X-ray structures show that 1–4 are isostructural featuring a 2-D weaving structure based on two chain structures containing binuclear units and organic linkers. The structures of 5–8 are analogous to those of 1–4 except that they contain coordinated solvent. Complex 9 forms a 1-D structure containing binuclear units connected by organic linkers. This series affords an opportunity to study the effect of lanthanide contraction, demonstrating that the average C–S–C bond angle in coordinated H2SDB decreases as the atomic number increases. The luminescence of 1 and 3 are also reported.

Synthesis, structure, and magnetic property of a 3D supramolecular Gd(III) coordination polymer with 4,4′-sulfonyldibenzoic acid ligands

A new coordination polymer [Gd(Sfdb)(NO3)(DMF)2] · 2H2O (Sfdb = 4,4′-sulfonyldibenzoic acid) has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction (CIF file CCDC no. 1023460). The X-ray diffraction analysis shows that I (C20H24N3O12SGd) crystallizes in the monoclinic crystal system, which reveals that I is a 3D supramolecular framework assembled by the intermolecular hydrogen bonds. Moreover, the magnetic studies of I showed that there exist antiferromagnetic interactions between the Gd(III) centres. The unit cell parameters for I: a = 33.453(3), b = 10.5469(10), c = 18.7895(18) A, β = 123.7670(10)°, V = 5511.0(9) A3, Z = 8.

Two 2-fold interpenetrated polythreading networks assembled by 4,4′-sulfonyldibenzoic acid and N-donor ligand

Self-assembly of NiII/CoII with 4,4′-sulfonyldibenzoic acid (H2E1) and 1,4-bis(1,2,4-triazole-1-ylmethyl)benzene (pbtx) has produced 3-D interpenetrated polythreading networks with non-trivial linkages, [{Ni(pbtx)(E1)(H2O)}·H2O]n (1) and [{Co(pbtx)(E1)(H2O)}·H2O]n (2), respectively. Single-crystal X-ray diffraction analyses revealed that 1 and 2 are isomorphous and isostructural. Complexes 1 and 2 possess a 2-D grid layer consisting of metal ions bridged by pbtx ligands and entirely deprotonated E12− ligands, which led to the formation of 2-fold interpenetrated polythreading networks. The interpenetrated networks were further bridged by C–H⋯O and O–H⋯O hydrogen bonds to generate their 3-D frameworks. Further characterizations including elemental analysis, FT-IR, XPRD, and Thermogravimetric analysis have been studied.

Four new Mn(II) inorganic-organic hybrid frameworks with diverse inorganic magnetic chain's sequences: syntheses, structures, magnetic, NLO, and dielectric properties.

Four new inorganic-organic hybrid manganese frameworks, formulated as [Mn(Am-Hip)2]·3H2O (1), [Mn2(ip)2(H2O)]·CH3OH (2), [Mn2(OH-ip)2(DMF)]·DMF (3), and (Me2NH2)[Mn4(sdba)4(Hsdba)(H2O)]·3H2O·2DMF (4) (Am-H2ip = 5-aminoisophthalic acid, H2ip = isophthalic acid, OH-H2ip = 5-hydroxyisophthalic acid, and H2sdba = 4,4'-sulfonyldibenzoic acid), have been prepared by solvothermal reactions of Mn(II) ions with different polycarboxylate acids in the presence of LiNO3 or NH4NO3. Single-crystal X-ray diffraction studies reveal that the frameworks of 1-4 contain diverse Mn(II)-oxygen inorganic magnetic chain's sequences, -J1J1J1J1- for 1, -J1J2J1J2- for 2, -J1J1J2J2- for 3, and -J1J2J3J3- for 4. The sequence in 4 has never been seen for the magnetic chain compounds and is a new type of magnetic alternating sequence. Magnetic investigations indicate that these compounds all show weak antiferromagnetic couplings between the adjacent Mn(II) ions. Magnetostructural analyses based on the data of 1-4 and other related Mn(II) chain compounds imply that the magnitude of the magnetic coupling has some relationship with the Mn-O-Mn angle of the μ2-O bridge and the average Mn-O-C-O torsion angle of the carboxylate bridges. Compounds 2 and 4 crystallize in chiral and acentric space groups, and they both exhibit powder second harmonic generation (SHG) efficiencies approximately 0.6 and 0.9 times, respectively, that of the standard potassium dihydrogen phosphate (KDP) powder. In addition, the dielectric properties of 2 and 4 were also investigated.

High proton mobility, solvent induced single crystal to single crystal structural transformation, and related studies on a family of compounds formed from Mn3 oxo-clusters.

The reaction between 4,4'-sulfonyldibenzoic acid (H2SDBA) and manganese under mild conditions resulted in the isolation of two new three-dimensional compounds, [Mn4(C14H8O6S)4(DMA)2]·3DMA, I, and [Mn3(C14H8O6S)3(DMA)2(MeOH)]·DMA, IIa. Both structures have Mn3 trimer oxo cluster units. While the Mn3 oxoclusters are connected through octahedral manganese forming one-dimensional Mn-O-Mn chains in I, the Mn3 units are isolated in IIa. The SDBA units connect the Mn-O-Mn chains and the Mn3 clusters giving rise to the three-dimensional structure. Both compounds have coordinated and free solvent molecules. In IIa, two different solvent molecules are coordinated, of which one solvent can be reversibly exchanged by a variety of other similar solvents via a solvent-mediated single crystal to single crystal (SCSC) transformation. The free lattice DMA solvent molecules in I can be exchanged by water molecules resulting in hydrophilic channels. Proton conductivity studies on I reveals a high proton mobility with conductivity values of ∼0.87 × 10(-3) Ω(-1) cm(-1) at 34 °C and 98% RH, which is comparable to some of the good proton conductivity values observed in inorganic coordination polymers. We have also shown structural transformation of I to IIa through a possible dissolution and recrystallization pathway. In addition, both I and IIa appear to transform to two other manganese compounds [H3O][Mn3(μ3-OH)(C14H8O6S)3(H2O)](DMF)5 and [H3O]2[Mn7(μ3-OH)4(C14H8O6S)6(H2O)4](H2O)2(DMF)8 under suitable reaction conditions. We have partially substituted Co in place of Mn in the Mn3 trimer clusters forming [CoMn2(C14H8O6S)3(DMA)2(EtOH)]·DMA, III, a structure that is closely related to IIa. All the compounds reveal antiferromagnetic behavior. On heating, the cobalt substituted phase (compound III) forms a CoMn2O4 spinel phase with particle sizes in the nanometer range.

The effect of cluster size on the optical band gap energy of Zn-based metal–organic frameworks

We have synthesized three Metal-Organic Frameworks (MOFs) in which Zn metal ions form the secondary building unit, and 4,4'-sulfonyldibenzoic acid (SDB) serves as the ligand: [[Zn(DMF)(SDB)](DMF), 1, [Zn(3)(DMF)(3)(SDB)(3)](DMF), 2 and [Zn(3)(OH)(2)(SDB)(2)] (DMF)(2), 3, where DMF = dimethyl formamide]. Compound contains a paddle-wheel type Zn dimer, compound contains a Zn trimer motif, and contains a one-dimensional Zn-OH-Zn chain. These building units may be considered to be Zn clusters. We have measured and theoretically calculated the band gap energy and by theoretical investigations we found that the cluster size plays an important role in the band gap energy, however additional effects are observed. The larger cluster size corresponds to a larger band gap energy, however the cavity of the trimer based compound (2) traps a solvent molecule that decreases the band gap energy.

New Al-MOFs based on sulfonyldibenzoate ions: a rare example of intralayer porosity.

A new sulfone-functionalized metal-organic framework [Al(OH)(SDBA)]·0.25DMF, denoted CAU-11, was synthesized using a V-shaped linker molecule 4,4'-sulfonyldibenzoic acid (H2SDBA). The crystal structure was solved from synchrotron X-ray powder diffraction data. Chains of trans corner-sharing AlO6 octahedra are interconnected by the carboxylate groups to form layers (ABAB stacking). Within the layers, hydrophobic lozenge-shaped pores with a diameter of 6.4 × 7.1 Å(2) are present inducing permanent porosity (aBET = 350 m(2) g(-1) and Vmicro = 0.17 cm(3) g(-1)). With the application of HT-methods (HT = high throughput), the isoreticular carboxylate functionalized compound [Al(OH)(H2DPSTC)]·0.5H2O (CAU-11-COOH) was synthesized using the linker molecule 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DPSDA), which hydrolyzes under the reaction conditions. Due to the additional noncoordinating carboxylic acid groups the pores are hydrophilic. Changing the molar ratio of Al(3+) to linker lead to the discovery of a second new compound [Al2(OH)2(DPSTC)(H2O)2]·0.5H2O (CAU-12). In CAU-12 the linker molecule is fully deprotonated which leads to different connectivity compared to the structure of CAU-11-COOH. Thermal activation of CAU-12 leads to dehydration and transformation of the structure to [Al2(OH)2(DPSTC)]·nH2O (CAU-12-dehy). Coordinated water molecules were removed, and the coordination site is replaced by the previously noncoordinating O atom of the adjacent carboxylate group. The SO2-groups point into the pores resulting in a highly hydrophobic three-dimensional framework. The compounds exhibit high thermal stability in air at least up to 420 °C. Synthesis of CAU-11 can be easily scaled up in very high yields (98%).

Stabilization of Co3 – Oxoclusters in a pcu Net: Synthesis, Structure, Solvent Exchange (Single Crystal to Single Crystal) and Magnetic Studies

AbstractThe solvothermal reaction of CoCl2·4H2O and 4,4′‐sulfonyldibenzoic acid (H2SDBA) resulted in the formation of a three‐dimensional coordination polymer [Co3(C14H8O6S)3(DMA)2(MeOH)].DMA (Ia) consisting of trinuclear Co3 oxo‐cluster units. The Co3 trimeric units are connected by SDBA2– anions leading to a three dimensional structure with a pcu topology. The terminal methanol molecules could be exchanged in a single crystal to single crystal (SCSC) fashion by other similar solvent molecules (ethanol, acetonitrile, water, ethyleneglycol). Magnetic studies on the parent compound, Ia, indicate antiferromagnetic interactions between the central metal atoms.