Carboxylate Sulfonate Research Articles

Four new transition metal coordination polymers based on mixed 4-imidazole and carboxylate–sulfonate ligands: Syntheses, structures, and properties

Four new metal-organic coordination polymers [Zn(HL)(SIP)(H2O)]·2H2O (1), [Cd2(L)(H2L)(SIP)2] (2), [Cu2(L)2(SIP)(OH)]·2H2O (3) and [Ni3(L)4(SIP)2(H2O)4]·6.5H2O (4) were obtained by reactions of the different metal(II) salts with mixed ligands including sodium 5-sulfoisophthalate (Na3SIP) and 1,4-di(1H-imidazole-4-yl)benzene (L), respectively. All compounds were characterized by FT-IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The study indicates that different natures of metal ions play crucial roles in modulating the formation of the resulting frameworks. Compound 1 is a one-dimensional (1D) chain structure, and 2 is a (3, 8)-connected tfz-d three-dimensional (3D) net with a Point (Schlafli) symbol of (43)2(46·618·84). Complex 3 has (3, 5)-connecting node two-dimensional (2D) network with a Point (Schlafli) symbol of (42·67·8)(42·6) based on the {Cd2(OH)(SO3)}n2+ binuclear Cd(II) motif, while 4 is a rare 2D ​+ ​2D → 3D polycatenated framework resulting from two different kinds of (4, 4) 2D layers. The photoluminiscent properties as well as quantum yield (QY) and luminescence lifetime are also investigated for compounds 1 and 2 in the solid state.

A novel second-order non-linear optical coordination polymer with three-fold interpenetrated CdSO4-type network constructed by carboxylate–sulfonate ligands and strontium ions

A novel strontium carboxylate–sulfonate coordination polymer, [Sr(HSIP)(H2O)3]n·nH2O (1) (NaH2SIP=5-sulfoisophthalic monosodium salt) has been synthesized by hydrothermal reaction. It was characterized by X-ray single crystal diffraction, infrared spectroscopy, elemental and thermogravimetric analysis. Each strontium atom is eight-coordinate with a distorted bicapped trigonal prismatic arrangement. The whole HSIP2− ligand acts as a η5μ4 bridge to generate three-fold interpenetrated CdSO4-type network structure, which is constructed from the left- and right-handed helixes paralleled to each other bridged by the HSIP2− ligands. The luminescence spectrum indicates an emission maximum at 459nm. Compound 1 shows a second harmonic generation (SHG) response that is 4 times that of KH2PO4.

Structure, spectroscopic, and magnetic properties of a new cobalt(II) complex with 5-sulfoisophthalic anion

A complex of [Co(H2SIP)(Phen)(H2O)3] ⋅ H2O (H2SIP = 5-sulfoisophthalic anion, Phen = 1,10-phenanthroline) has been synthesized by hydrothermal reaction. Crystal structure determination revealed that the complex crystallizes in the monoclinic space group P2(1)/c, in which Co(II) is distorted octahedral coordinating with one carboxylate sulfonate ligand, one phen, and three coordinated waters. Molecules of [Co(H2SIP)(Phen)(H2O)3] ⋅ H2O are connected to form a 3-D structure by intermolecular hydrogen bonds and π–π stacking interactions. IR spectra, UV-Vis spectra, and magnetic susceptibilities have been analyzed to obtain values of the ligand field and magnetic parameters: Α = 1.33, λ = −102.3 cm−1, κ = 0.96, and Δ = 252.2 cm−1.

Two new lead(II) diphosphonates with second ligands as an intercalated species or a multidentate metal linker

Hydrothermal reactions of lead(II) acetate with N, N′-piperazinebis(methylenephosphonic acid) (H 2O 3PCH 2N(C 2H 4) 2NCH 2PO 3H 2, H 4L 1) and 5-sulfoisophalic acid monosodium salt (NaH 2SIP) or lead(II) acetate with isopropylimino-bis-(methylenephosphonic acid) ((CH 3) 2CHN (CH 2PO 3H 2) 2, H 4L 2) and succinic acid afforded two new lead(II) phosphonate hybrids, namely, Pb 4(H 2L 1)(SIP) 2(H 2O) 4·2H 2O 1 and Pb 4(L 2) 2·(HO 2CH 2CH 2CO 2H) 2. The structure of compound 1 features a 3D network formed by Pb(II) ions interconnected by H 2L 1 and the carboxylate–sulfonate SIP anions. The 3D network can be viewed as the neighboring layers of Pb 4(SIP) 2 being interconnected by H 2L 1 ligands to form a pillared layered architecture. The phosphonate groups of the diphosohonate ligands bridge the Pb(II) ions of the Pb 4(SIP) 2 layer to form a lead(II) phosphonate–sulfonate hybrid layer and the organic group of phosphonate ligand as pillars. In compound 2, the interconnection of the lead(II) ions via diphosphonate ligands lead to a 〈400〉 lead(II) diphosphonate layer. The succinic acid remains protonated and is located at interlayer space. The second ligand in compound 1 acts as a multidentate metal linker, whereas the succinic acid in compound 2 functions as an intercalated species in between the 2D layers.

Syntheses, characterizations and crystal structures of two lead(II) phosphonate–sulfonate hybrid materials

Hydrothermal reactions of lead(II) acetate with 5-sulfoisophthalic acid monosodium salt (NaH 2BTS) and N-(phosphonomethyl)- N-methylglycine, MeN(CH 2CO 2H)(CH 2PO 3H 2) (H 3L 1), or a new aminodiphosphonic acid, 3-Pyridyl-CH 2N(CH 2PO 3H 2) 2 (H 4L 2), afforded two novel lead(II) phosphonate–sulfonate hybrids, namely, Pb 3[L 1][BTS][H 2O]·H 2O 1 and Pb 2[HL 3][BTS]·H 2O 2 (H 2L 3=3-Pyridyl-CH 2(Me)N(CH 2PO 3H 2)). H 2L 3 was formed as a result of the decomposition of one phosphonate group in H 4L 2 during the reaction. Compound 1 crystallizes in the triclinic space group P 1 ̄ with a=9.9148(4) Å, b=10.4382(4) Å, c=10.6926(2) Å, α=96.495(2)°, β=110.599(2)°, γ=98.433(2)°, V=1008.31(6) Å 3, and Z=2. The structure of compound 1 features a 3D network built from the interconnection of hexanuclear Pb 6(L 1) 2 units and 1D double chains of lead(II) carboxylate–sulfonate. Compound 2 crystallizes in the monoclinic space group P2 1/ c with a=9.5403(7) Å, b=11.6170(8) Å, c=19.7351(15) Å, β=97.918(2)°, V=2166.4(3) Å 3, and Z=4. Compound 2 has a 3D network structure built by the cross-linkage of 1D double chains of lead(II) phosphonates and 2D layers of lead(II) carboxylate–sulfonate.

Synthesis, characterization, and crystal structures of three new divalent metal carboxylate-sulfonates with a layered and one-dimensional structure.

Hydrothermal reactions of 5-sulfoisophthalic acid (HO(3)SC(6)H(3)-1,3-(CO(2)H)(2), H(3)L) with M(II) carbonate (or oxide) and 4,4'-bipyridine (4,4'-bipy) (or 2,2'-bipyridine, 2,2'-bipy) resulted in three new metal carboxylate-sulfonate hybrids, namely, [CdL(H-4,4'-bipy)] (1) and [Cd(3)L(2)(2,2-bipy)(4)(H(2)O)(2)].2H(2)O (2) with layered structures and [ZnL(H-4,4'-bipy)(H(2)O)].2H(2)O (3), whose structure features a one-dimensional double chain. The cadmium(II) ion in complex 1 is seven-coordinated by five carboxylate oxygen atoms and one sulfonate oxygen atom from four ligands and a unidentate 4,4'-bipyridine. The interconnection of the cadmium(II) ions through bridging carboxylate-sulfonate ligands resulted in the formation of a <002> double layer with the bipyridyl rings orientated toward the interlayer space. Complex 2 has a different layered structure. Cd(1) is seven-coordinated by two bidentate chelating carboxylate groups from two ligands, a bidentate chelating 2,2'-bipy and an aqua ligand, and Cd(2) is octahedrally coordinated by two bidentate chelating 2,2'-bipy's, a sulfonate oxygen, and an aqua ligand. The coordination geometry around Cd(3) is similar to that of Cd(1) with the aqua ligand being replaced by an oxygen atom from the sulfonate group. The carboxylate-sulfonate ligand acts as pentadentate ligand, bridging with three cadmium(II) ions. The bridging of cadmium(II) ions through the carboxylate-sulfonate ligands resulted in the formation of <006> and <003> layers; the 2,2'-bipy molecules and [Cd(2)(2,2'-bipy)(2)(H(2)O)] cations are orientated to the interlayer space. Complex 3 features a 1D metal carboxylate-sulfonate double chain along the diagonal of the a- and b-axes. The zinc(II) ion is octahedrally coordinated by four carboxylate O atoms from three ligands, a unidentate 4,4'-bipy, and an aqua ligand. Each pair of zinc(II) ions is bridged by two carboxylate groups from two ligands to form a dimer, and such dimeric units are interconnected by bridging ligands to form a double chain. The sulfonate group of the carboxylate sulfonate ligand remains noncoordinated and forms a number of hydrogen bonds with aqua ligands as well as lattice water molecules.

Syntheses, characterizations and crystal structures of two new lead(II) amino and carboxylate–sulfonates with a layered and a pillared layered structure

Reactions of lead(II) acetate with m-aminobenzenesulfonic acid (H L 1) and 5-sulfoisophthalic acid (H 3 L 2) afforded two new lead(II) sulfonates, Pb( L 1) 2 1 and Pb 2( L 2)( μ 3-OH)(H 2O) 2. In compound 1, the lead(II) ion is eight-coordinated by two sulfonate groups bidentately, two sulfonate groups unidentately and two amino groups from six ligands. Each L 1 ligand is tetradentate and bridges with three Pb(II) ions. The interconnection of the Pb(II) ions via bridging sulfonate ligands resulted in 〈100〉 and 〈200〉 layers. In compound 2, one Pb(II) ion is six-coordinated by a carboxylate group bidentately, by two carboxylate groups unidentately, by a sulfonate oxygen atom and by an OH anion, whereas the other one is six-coordinated by a bidentate chelating carboxylate group, two μ 3-OH anions, a sulfonate oxygen atom and an aqua ligand. The interconnection of irregular PbO 6 polyhedra via carboxylate–sulfonate ligands resulted in the formation of a pillared layered structure with the 2D layer being formed; the lead(II) ions, hydroxyl groups, carboxylate and sulfonate groups and the benzene ring as the pillar agent.