Zhi-Biao Zhu

New family of silver(I) complexes based on hydroxyl and carboxyl groups decorated arenesulfonic acid: syntheses, structures, and luminescent properties.

Self-assembly of silver(I) salts and three ortho-hydroxyl and carboxyl groups decorated arenesulfonic acids affords the formation of nine silver(I)-sulfonates, (NH(4))·[Ag(HL1)(NH(3))(H(2)O)] (1), {(NH(4))·[Ag(3)(HL1)(2)(NH(3))(H(2)O)]}(n) (2), [Ag(2)(HL1)(H(2)O)(2)](n) (3), [Ag(2)(HL2)(NH(3))(2)]·H(2)O (4), [Ag(H(2)L2)(H(2)O)](n) (5), [Ag(2)(HL2)](n) (6), [Ag(3)(L3)(NH(3))(3)](n) (7), [Ag(2)(HL3)](n) (8), and [Ag(6)(L3)(2)(H(2)O)(3)](n) (9) (H(3)L1 = 2-hydroxyl-3-carboxyl-5-bromobenzenesulfonic acid, H(3)L2 = 2-hydroxyl-4-carboxylbenzenesulfonic acid, H(3)L3 = 2-hydroxyl-5-carboxylbenzenesulfonic acid), which are characterized by elemental analysis, IR, TGA, PL, and single-crystal X-ray diffraction. Complex 1 is 3-D supramolecular network extended by [Ag(HL1)(NH(3))(H(2)O)](-) anions and NH(4)(+) cations. Complex 2 exhibits 3-D host-guest framework which encapsulates ammonium cations as guests. Complex 3 presents 2-D layer structure constructed from 1-D tape of sulfonate-bridged Ag1 dimers linked by [(Ag2)(2)(COO)(2)] binuclear units. Complex 4 exhibits 3-D hydrogen-bonding host-guest network which encapsulates water molecules as guests. Complex 5 shows 3-D hybrid framework constructed from organic linker bridged 1-D Ag-O-S chains while complex 6 is 3-D pillared layered framework with the inorganic substructure constructing from the Ag2 polyhedral chains interlinked by Ag1 dimers and sulfonate tetrahedra. The hybrid 3-D framework of complex 7 is formed by L3(-) trianions bridging short trisilver(I) sticks and silver(I) chains. Complex 8 also presents 3-D pillared layered framework, and the inorganic layer substructure is formed by the sulfonate tetrahedrons bridging [(Ag1O(4))(2)(Ag2O(5))(2)](∞) motifs. Complex 9 represents the first silver-based metal-polyhedral framework containing four kinds of coordination spheres with low coordination numbers. The structural diversities and evolutions can be attributed to the synthetic methods, different ligands and coordination modes of the three functional groups, that is, sulfonate, hydroxyl and carboxyl groups. The luminescent properties of the nine complexes have also been investigated at room temperature, especially, complex 1 presents excellent blue luminescence and can sensitize Tb(III) ion to exhibit characteristic green emission.

Structure modulations in luminescent alkaline earth metal-sulfonate complexes constructed from dihydroxyl-1,5-benzenedisulfonic acid: Influences of metal cations, coordination modes and pH value

Seven novel alkaline earth (AE) metal-sulfonate complexes constructed from ortho-hydroxyl arenedisulfonic acids, [Mg2(H2L)2(H2O)4]·8H2O (1), {[Ca(H2L)(H2O)]n·3nH2O} (2), {[Ca4L2(H2O)12]n·7nH2O} (3), {[Sr(H2L)(H2O)]n·3nH2O} (4), {[Sr2L(H2O)4]n·nH2O} (5), {[Ba(H2L)(H2O)2]n·2nH2O} (6), and [Ba2L(H2O)4]n (7) (H4L = 2,4-dihydroxyl-1,5-benzenedisulfonic acid), have been synthesized and characterized by elemental analysis, IR, TG, PL, powder and single-crystal X-ray diffraction. Complex 1 is a dinuclear unit which is extended by intermolecular hydrogen-bonding interactions into a 3-D supramolecular network. Complexes 2, 4 and 6 exhibit 2-D hybrid layer motifs formed by phenyl rings bridged by infinite 1-D M–O chains, in which the H2L2− dianions act in different μ4:η6 (complex 2), μ4:η7 (complex 4) and μ4:η8 (complex 6) coordination modes. In comparison, complexes 3, 5 and 7 exhibit 3-D pillared layered networks formed by phenyl rings bridged by infinite 2-D M–O layers, in which the L4− tetraanions act in different μ6:η9 (complex 3), μ6:η9 (complex 5) and μ8:η14 (complex 7) coordination modes. The interspaces of the layer motifs in complexes 2, 4 and 6 are filled by lattice water molecules, and the channels in complexes 3 and 5 are also filled by lattice water molecules. It should be noted that the coordination modes of the sulfonate group in complexes 3 (μ3:η3), 4 (μ2:η3), 5 (μ4:η5), 6 (η2 and μ3:η4) and 7 (μ4:η5) are reported for the first time in the corresponding AE-arenesulfonates. The structural diversities and evolution of these complexes can be attributed to the nature of the metal cations, coordination modes of the sulfonate groups and the hydroxyl groups induced by the pH value. The solid-state luminescent properties demonstrate that complexes 2–7 exhibit violet emission at room temperature and the luminescent emission intensities of the H2L2− containing complexes are evidently stronger than those of the L4− containing complexes. Moreover, the complexes can sensitize Tb(III) ion to exhibit its characteristic green emission.

The first in situ organosulfonate-templated 3-fold interpenetrating framework built from rare tetrahedral [Cu4(μ4-SO4)] SBUs

An interpenetrating framework, [Cu4(SO4)(4,4-bipy)4]n·2n(C6H5SO4) [4,4′-bipyridine = 4,4′-bipy], has been successfully synthesized viahydrothermal reaction, in which the in situ generated p-hydroxybenzenesulfonate as guests are encapsulated within the channels. The tetrahedral [Cu4(μ4-SO4)] SBUs, reported for the first time in 3D architectures, are linked by parallel double 4,4′-bipys to generate a diamondoid network formed of large adamantanoid cages which causes the 3-fold interpenetration of the networks by self-clathration. Furthermore, the existence of strong π⋯π interactions between adjacent 4,4′-bipys stabilizes the interpenetrating framework. The binding energies of the Cu 2p3/2 level in the XPS spectrum are typical for a Cu(I) oxidation state. For the O1s, the XPS spectrum could be deconvoluted into three peaks corresponding to the three kinds of O atoms with different chemical environments. This work provides a method for constructing in situ organosulfonate-templated interpenetrating metal–organic frameworks.

Influence of solvents and assembly methods on the supramolecular patterns and luminescent properties of organic salts comprising 4,4′-dihydroxybiphenyl-3,3′-disulfonate and triphenylmethanaminium

Twelve organic salts, namely 2(HTPMA)+·(H2M)2−·4(H2O) (1), 2(HTPMA)+·(H2M)2−·2(H2O) (2), 2(HTPMA)+·(H2M)2−·2(MeOH)·(H2O) (3), 2(HTPMA)+·(H2M)2−·4(MeOH) (4), 2(HTPMA)+·(H2M)2−·(MeOH) (5), 2(HTPMA)+·(H2M)2−·2(EtOH)·2(H2O) (6), 2(HTPMA)+·(H2M)2−·2(n-PrOH) (7), 2(HTPMA)+·(H2M)2−·2(n-BuOH) (8), 2(HTPMA)+·(H2M)2−·2(n-PeOH) (9), 2(HTPMA)+·(H2M)2−·2(DO) (10), 2(HTPMA)+·(H2M)2−·2(DMF) (11), and 2(HTPMA)+·(H2M)2−·2(DMSO) (12) (H4M = 4,4′-dihydroxybiphenyl-3,3′-disulfonic acid, TPMA = triphenylmethylamine, DO = 1,4-dioxane) have been obtained from the reaction of H4M and TPMA in different solvents by two assembly methods and characterized by elemental analysis, IR, TG, PL, powder and single-crystal X-ray diffraction. Structural analyses indicate that the nature of the solvent molecules can effectively influence the ⋯(–SO3)⋯(–NH3)⋯(solvent)⋯ patterns, which then result in diverse packing diagrams. In salts 1 and 3, pairs of HTPMA+ cations arrange in a tail-to-tail mode to form column motifs which extend the layers of H2M2− dianions into a pillared layered network. On the contrary, pairs of HTPMA+ cations in salt 2 arrange in head-to-head mode and form layer structures together with pairs of H2M2− dianions. The HTPMA+ cations and H2M2− dianions in salts 4 and 6 are alternately arranged to form a column motif, which then pack with each other to form a supramolecular network. Pairs of head-to-head HTPMA+ cations in salts 7–9 are sandwiched between the –SO3 groups through hydrogen bonding interactions, generating a graphite-like structure. The HTPMA+ cations in salts 5 and 10–12 arrange in tail-to-tail mode to form column motifs which are then sandwiched between biphenyl rings instead of the –SO3 groups. Moreover, different assembly processes are also responsible for the diverse structures. Small solvent molecules, such as H2O and MeOH, tend to form different structures (1 and 2, 3 and 4), while large molecules usually present the same structures (6–12). It is interesting to note that salt 4 can transform into salt 5 after being exposed to the air for several hours. Luminescence investigation reveals that the emission maximum of salts 1–12 varies from 365 to 371 nm.

Effect of ligand configurations, secondary Pb–O interactions and auxiliary ligands on Pb(II)–mono/disulfonate complexes: syntheses, structures, and luminescence properties

Eight new Pb(II)–mono/disulfonate complexes, [Pb2(L1)2(H2O)]n (1), [Pb(L1)(2,2′-bipy)] (2), [Pb(L1)(phen)]·H2O (3), [Pb(L1)(H2O)]·0.5(4,4′-bipy) (4), [Pb(HL2)(H2O)3]n (5), [Pb4(L2)2(AcO)2(2,2′-bipy)(H2O)]n (6), [Pb3(L2)2(phen)(H2O)5]·2H2O (7) and [Pb(HL2)(4,4′-bipy)(H2O)]·H2O (8) (H2L1 = 2-hydroxy-5-chlorobenzenesulfonic acid, H3L2 = 2-hydroxy-5-chloro-1,3-benzenedisulfonic acid, phen = 1,10-phenanthroline, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine, AcO− = acetate), have been synthesized by the reaction of a Pb(II) salt, mono- or disulfonate, with three N-heterocyclic auxiliary ligands and characterized by elemental analysis, IR, TG, PL, powder and single-crystal X-ray diffraction. With the primary Pb–O bonds, these eight complexes exhibit diverse dinuclear (2, 3, 4 and 8), hexanuclear (7), linear chain (1) and layer structures (5 and 6). The Pb(II) cations in these complexes present a hemidirected geometry, except for complex 6, in which the Pb(II) cations present rarely hemidirected and holodirected geometries in one system. Taking the secondary Pb–O bonds into account, chain structures for complexes 2 and 8 and layer motifs for complexes 1 and 4–7 are observed with the Pb(II) cations showing more intricate hemi- and holodirected geometries. Meanwhile, the disulfonate anions present more coordination sites to Pb(II) cations, thus leading to high-dimensional structures in comparison with the monosulfonate anions. Moreover, ligand configurations and the introduction of the N-heterocyclic auxiliary ligands also play important roles in modulating the structures of the Pb(II)–sulfonate complexes. Luminescence analyses indicate that complexes 6–8 present purple emission at 400, 397 and 399 nm at room temperature.

Poly[bis[aqua­mercury(I)]-di-μ-aqua-μ-1,5-naphthalene­disulfonato]

In the crystal structure of the title polymeric complex, [Hg2(C10H6O6S2)(H2O)4]n, the metal atom of an H2O→Hg⋯Hg←H2O unit [Hg←Owater = 2.124 (7) A] is linked to the metal atom of an adjacent unit by two water molecules [Hg←Owater = 2.619 (7) and 2.872 (7) A], giving rise to a polycationic chain. Adjacent chains are linked through the dianion via a weaker interaction [Hg⋯Osulfonate = 3.062 (7) A] to form layers. The H2O→Hg⋯Hg←H2O unit, the (H2O→Hg)2 parallelogram and the dianion all lie on centres of inversion. Hydrogen bonding consolidates the layers of the structure into a three-dimensional network architecture.

Nature of reactant and influence of water on the supramolecular patterns and luminescent properties of organic salts comprising (1,1′-biphenyl)-4,4′-disulfonate and triphenylmethanaminium

The solvent reaction of 1,1′-biphenyl-4,4′-disulfonic acid (H2BPDSA) and triphenylmethylamine (TPMA) gives rise to fourteen supramolecular compounds, namely, 2(HTPMA)+·(BPDSA)2−·(H2O) (1), 2(HTPMA)+·(BPDSA)2−·(MeOH) (2), 2(HTPMA)+·(BPDSA)2−·(EtOH) (3), 2(HTPMA)+·(BPDSA)2−·3(n-PrOH) (4), 2(HTPMA)+·(BPDSA)2−·2(n-BuOH) (5), 2(HTPMA)+·(BPDSA)2−·2(n-PeOH) (6), 2(HTPMA)+·(BPDSA)2−·4(DMF) (7), 2(HTPMA)+·(BPDSA)2−·4(DMSO) (8), 2(HTPMA)+·(BPDSA)2−·(DO) (9), 2(HTPMA)+·(BPDSA)2−·2(H2O)·2(MeOH) (10), 2(HTPMA)+·(BPDSA)2−·(H2O)·2(n-PrOH) (11), 2(HTPMA)+·(BPDSA)2−·(H2O)·2(n-BuOH) (12), 2(HTPMA)+·(BPDSA)2−·(H2O)·2(n-PeOH) (13) and 2(HTPMA)+·(BPDSA)2−·4(H2O)·2(DMF) (14) (DO = 1,4-dioxane), which have been characterized by elemental analysis, IR, TG, PL, and powder and single-crystal X-ray diffraction. Structural analyses indicate that salts 1–14 show seven types of packing diagram. Moreover, salts 1–9 present regular supramolecular structural variations with the change of the nature of the solvent molecules. Salts 1–3 exhibit double chain motifs with small molecules of H2O, MeOH and EtOH. Salts 4–7 present single chain structures with larger n-PrOH, n-BuOH, n-PeOH and DMF molecules. Salt 8 only exhibits a simple discrete motif owing to the triangular pyramid configuration of the DMSO molecule. In contrast, the DO molecules in salt 9 have two opposite acceptor O atoms, which extend adjacent HTPMA+ cations and BPDSA2− dianions into a (4,4) layer motif. Furthermore, the involvement of water molecules could modulate the dimension level of supramolecular patterns according to the different hydrogen bonding modes of H2O molecules. Salts 10 and 14 present different double and single chain structures from the single chains in salts 2 and 7 owing to the HB′3 and HB′2 modes of H2O molecules. Similarly, salts 11–13 show different (4,4) layer motifs from the chain structures in salts 4–6 with the assistance of the H2O molecules in HB4 mode. Luminescence investigations reveal that the emission maximum of salts 1–9 varies from 343 to 358 nm. In comparison, salts 10 and 14 show stronger emission intensity, whereas salts 12 and 13 show weaker emission intensity than their corresponding anhydrous salts owing to the structure transformations induced by the involvements of water molecules.

4-Hy-droxy-pyridinium-3-sulfonate.

The reaction of 4-hydroxypyridine and oleum produces 4-hydroxypyridinium-3-sulfonate, C5H5NO4S, which shows delocalized bonds in the six-membered ring. In the crystal, adjacent zwitterions are linked by N—H⋯O and O—H⋯O hydrogen bonds into a layer motif. The crystal studied was a racemic twin.

4-Amino­pyridinium-3-sulfonate monohydrate

The reaction of 4-aminopyridine and oleum yielded the title hydrated zwitterion, C5H6N2O3S·H2O. There are two formula units in the asymmetric unit. The H and non-H atoms of both zwitterions lie on a mirror plane except for one sulfonate O atom. The water molecules are also situated on a mirror plane. In the crystal, the zwitterions and water molecules are linked by O—H⋯O and N—H⋯O hydrogen bonds, generating a three-dimensional network.

The first continuous silver polyhedra framework containing four kinds of coordination spheres

The first continuous silver polyhedra framework containing four kinds of coordination spheres has been successfully prepared by the reaction of silver(I) nitrate and 4(1H)-pyridone-3-sulfonic acid. This polyhedra framework is constructed from four kinds of silver(I) polyhedra by sharing corners, edges and faces.