Dipyridyl Sulfide Research Articles

Mechanosynthesis of cyanuric and 5-aminoisophthalic acid cocrystals with Sulfur containing pyridine ligand as molecular spacer

Four binary cocrystals of cyanuric acid (CUA) and 5-aminoisophthalic acid (5AIPA) in combination with spacer aldrithiol-4 (ALDTHL) and 4,4′-dipyridyl sulfide (DPS) were prepared via Liquid Assisted grinding (LAG) method. Single crystal X-ray diffraction and powder X-ray diffraction techniques were used to elucidate their structures, which are further characterized using thermogravimetric analysis. While CUA produces 0.5:0.5 and 2:2 cocrystals with ALDTHL and DPS respectively; 5AIPA acid forms 1:1 cocrystals with both ALDTHL and DPS. Again, all the cocrystals adopt a sheet-like structure, with the exception of the (DPS)2•(CUA)2 cocrystal, which displays an interpenetrated polycatenane type of molecular packing. In order to analyze the intermolecular interactions in the four cocrystals, Hirshfeld surface analysis was performed.

Synthesis and Crystal Structure of 2D Coordination Polymer {[Cu(dps)2(DMSO)2](ClO4)2}n Based on 4,4′-Dipyridyl Sulfide

A new coordination polymer {[Cu(dps)2(DMSO)2](ClO4)2}n has been synthesized basing on 4,4′- dipyridyl sulfide. The structure of the obtained complex has been studied by single-crystal X-ray diffraction analysis.

Crystal Structure of Two-Dimensional Coordination Polymer {[Cu(dps)2(DMSO)2](ClO4)2}n Derived from 4,4'-Dipyridyl Sulfide

A new complex of general formula {[Cu(dps)2(DMSO)2](ClO4)2}n has been obtained with the aim to study the effect of perchlorate anion on the structure of coordination polymer based on 4,4'-dipyridyl sulfide. It has been established by X-ray diffraction that the compound has a layered 2D polymer structure. Each copper(II) ion is in a pseudo-octahedral donor environment. Perchlorate anions are disposed in the network voids of the polymer complex.

Platforms Formed from a Three-Dimensional Cu-Based Zwitterionic Metal-Organic Framework and Probe ss-DNA: Selective Fluorescent Biosensors for Human Immunodeficiency Virus 1 ds-DNA and Sudan Virus RNA Sequences.

We herein report a water-stable three-dimensional Cu-based metal-organic framework (MOF) 1 supported by a tritopic quaternized carboxylate and 4,4'-dipyridyl sulfide as an ancillary ligand. This MOF exhibits unique pore shapes with aromatic rings, positively charged pyridinium and unsaturated Cu(II) cation centers, free carboxylates, tessellating H2O, and coordinating SO4(2-) on the pore surface. Compound 1 can interact with two carboxyfluorescein (FAM)-labeled single-stranded DNA sequences (probe ss-DNA, delineated as P-DNA) through electrostatic, π-stacking, and/or hydrogen-bonding interactions to form two P-DNA@1 systems, and thus quench the fluorescence of FAM via a photoinduced electron-transfer process. These P-DNA@1 systems can be used as effective fluorescent sensors for human immunodeficiency virus 1 double-stranded DNA and Sudan virus RNA sequences, respectively, with detection limits of 196 and 73 pM, respectively.

Three new Co(II)/Ni(II) cordination polymers based on 3,3-biphenyl dicarboxylic acid and N-donor Co-ligands: Synthesis, crystal structures and magnetic properties

Three new Co(II)/Ni(II) cordination polymers [Co(Bpdc)(Bipy)]n (I) and [Co2(Bpdc)2(Dps)2]n (II) and [Ni(Bpdc](Dps)]n (III) (H2Bpdc = 3,3'-biphenyl dicarboxylic acid, Bipy = 2,2'-bipyridine, and Dps = 4,4'-dipyridyl sulfide) have been synthesized via hydrothermal method and characterized by elemental analysis, FT-IR, PXRD and single-crystal X-ray diffraction (CIF files CCDC nos. 994521 (I), 994522 (II), 1027995 (III)). Compound I is a 3D supremolecular structures extending through 1D double chain by the π···π stack interactions. However, compound II and III are topological isomorphic, which features a 3D four-fold interpenetrated neworks with 4-connected dia topology. Moreover, thermogravimetric analysis and magnetic properties of I and II were also discussed.

Two 1D Coordination Polymers Constructed from Copper(II) Carboxylates and 4,4′‐Dipyridyl Sulfide/4,4′‐Dipyridyl Disulfide

AbstractBy using pyridyl sulfide ligands, two CuII complexes, [{Cu2[CH3(CH)2COO]4(4‐dps)}2·1.5H2O] (1) and [Cu2[CH3(CH)2COO]4(4‐dpds)] (2) (4‐dps = 4,4′‐dipyridyl sulfide, 4‐dpds = 4,4′‐dipyridyl disulfide), were synthesized and structurally characterized. Complex 1 shows a 1D zigzag chain, further, the adjacent chains are interconnected through O–H···O hydrogen bonds to form 1D nanotubes. Complex 2 consists of alternate linking of a Cu2[CH3(CH)2COO]4 unit and a 4‐dpds ligand to construct same zigzag chains. According to the crystal structures, the full geometry optimizations of complexes 1 and 2 were carried out by using hybrid DFT methods at B3LYP/6‐31G(d) level. Meantime, the DFT‐BS approach was applied to study the magnetic coupling behavior for the two complexes, and the result reveals that the calculated exchange coupling constants J were in good agreement with the experimental θ data. Both 1 and 2 showed antiferromagnetic behavior.

Sandwich-like octacyanometalate-based cadmium assemblies with the 4,4′-dipyridyl sulfide ligand

The self-assembly of octacyanotungstate, cadmium ions, and 4,4′-dipyridyl sulfide ligands has isolated the first octacyanometalate-based cadmium compounds, which exhibit novel sandwich-like coordination networks. The effect of solvent and temperature on the formation of products was discussed.

10-(3′-Nitro-4′-pyridyl)-1,8-diazaphenothiazine as the double Smiles rearrangement product

Abstract The modification of the phenothiazine structure via the substitution of the benzene ring with the pyridine ring may proceed through the Ullmann cyclization or the Smiles rearrangement of the appropriate sulfide followed by cyclization. Reaction of dipyridyl sulfide (4) with 4-chloro-3-nitropyridine (5) in DMF can lead to one of the isomeric nitropyridyldiazaphenothiazines (7, 9 or 10). Two-dimensional 1H NMR experiments (COSY and ROESY) and a single crystal X-ray diffraction study were used to reveal the right product structure 10, being the result of an uncommon reaction mechanism involving the double Smiles rearrangement of the S–N type. The tricyclic diazaphenothiazine system is not planar, folded along the S–N axis with the butterfly angle of 149.38(7)° between two pyridine rings. The central thiazine ring is in boat conformation with the nitropyridyl substituent located in equatorial position with the S5⋯N10–C11 angle of 162.3(2)°. The pyridyl substituent plane bisects the tricyclic ring system showing the dihedral angle between this plane and the C4a/C5a/C9a/C10a plane of 70.7(7)°. The nitro group is located intra the dipyridothiazine system and is tilted from the pyridine ring by 30.4(2)°.

Syntheses, crystal structures and properties of six coordination compounds with flexible dps ligand

Six new compounds: [M(dps)(dca) 2] ∞ ( 1, M = Cd; 2, M = Fe), [Cu(dps)(dca) 2(CH 3OH) 2] ∞ ( 3), [M(dps) 2(SCN) 2(H 2O) 2] ∞ ( 4, M = Cd; 5, M = Fe), [Cu(dps) 4(SCN) 2] ∞ ( 6), (dps = 4,4′-dipyridyl sulfide, dca = dicyanamide) were synthesized, characterized by FT-IR, element analysis and TG. Their structures were determined by single crystal X-ray diffraction. According to the structure analysis, compounds 1 and 2 are three-dimensional microporous frameworks constructed by Cu–dps–Cu and Cu–dca–Cu bridges; compound 3 shows a zigzag chain constructed by a Cu–dps–Cu bridge; compounds 4 and 5 show double-stranded chains constructed by a Cu–(dps) 2–Cu bridge while thiocyanate anions act as terminal groups; compound 6 is a mononuclear compound. Moreover, compound 1 shows visible yellow luminescence under UV light irradiation and such phenomenon is mainly attributed to inter-ligand transitions.

Dicarboxylate anion-dependent assembly of Ni(II) coordination polymers with 4,4′-dipyridyl sulfide

Four new coordination polymers, [Ni(isop)(bps)(H2O)]2n·5H2O (1), [Ni(O2N–BDC)(bps)(H2O)]2n (2), [Ni(OH–BDC)(bps)2(H2O)]n (3) and {[Ni2(H2O)(tbip)2(bps)2]}n (4) (bps = 4,4′-dipyridyl sulfide, H2isop= isophthalic acid, O2N–BDC = 5-nitroisophthalic acid, OH–BDC = 5-hydroxyisophthalic acid, H2tbip = 5-tert-butyl isophthalic acid), have been isolated from parallel hydrothermal reactions of Ni(OAc)2·4H2O and bps with isop, O2N–BDC, OH–BDC and H2tbip, respectively. Compound 1 is an unusual 2D double layered supramolecular motif generated by hydrogen bonding interactions of two single 2D (4,4) networks. Compound 2 has a highly puckered 2D (4,4) sheet and further stack viaO⋯O intermolecular contacts to form a 3D supramolecular structure. Compound 3 features a 2D rectangular grid layer with terminal bps ligands projecting into the interlayer space, leading to a highly interdigitated packing motif and further expansion to generate a 3-D network through interlayer C–H⋯π stacking interactions. Compound 4 contains [Ni2(H2O)]4+ dimers bridged by pairs of ligands into a single 3D diamond network with alternately left-handed and right-handed helical channels. As compared to isop, the coexistence of electron-donating (–OH, –C(CH3)3) or electron-withdrawing (–NO2) groups in the dicarboxylate derivatives has a significant effect on the molecular self-assembly. Variable-temperature magnetic susceptibility measurements reveals the existence of weak ferromagnetic interactions between the nickel centers in 4.

Influence of coanions on construction of copper(II)/4,4′-dipyridyl sulfide(dps) coordination polymers

The influence of coanion on self-assembly of CuSO 4 and 4,4′-dipyridyl sulfide (dps) was studied in this paper. During the formation of Cu(II)/dps coordination polymers, coanions Cl −, SCN − and PF 6 - were added in the solution respectively. Three novel coordination polymers were obtained, {[Cu(dps) 2 · (SO 4) 2][Cu(dps) · Cl · (H 2O) 2] 2 · 12H 2O} n ( 1 · 12H 2O, a 3D network), {[Cu(SCN) 2(dps)(CH 3OH) 2][Cu(dps) 2 · SO 4][Cu(dps)(CH 3CH 2OH) 2 · SO 4] · 5H 2O} n ( 2 · 5H 2O, a 3D network), and {[Cu(dps) 2(H 2O) 2] · (PF 6) 2 · 3H 2O} n ( 3 · 3H 2O, a 2D lattice network). Different coanion shows different influence on framework construction. In 1 and 2, Cl − and SCN − act as terminal ligands and similar 3D frameworks were composed of [Cu(dps)] layer with larger cavity (ca. 400 Å) and sulfate bridge; in 3, PF 6 - replaces SO 4 2 - entirely and the 3D framework was broken due to the removal of bridging SO 4 2 - anions. However, a 2D [Cu(dps)] 4 undulating grid was preserved in 3.

Synthesis, structures and NLO properties of five non-centrosymmetric coordination compounds from the copper(II)/dps system (dps = 4,4′-dipyridyl sulfide)

The formation, crystal structure and properties of five copper(II) coordination compounds with the angular ligand, 4,4′-dipyridyl sulfide (dps) are described, {[Cu 3(μ-dps) 4(μ-SO 4) 2(SO 4)(H 2O) 5] · 10H 2O} ∞ ( 1 · 10H 2O), [Cu(dps) 4(H 2O) 2] · (ClO 4) 2 · H 2O ( 2 · H 2O), {[Cu(μ-dps) 2(DMF) 2](ClO 4) 2} ∞ ( 3), {[Cu(μ-dps) 2(H 2O) 2] · (NO 3) 2 · 2H 2O} ∞ ( 4 · 2H 2O) and {[Cu 3(μ-dps) 6(DMF) 2(H 2O) 4] · (NO 3) 6 · (DMF) · 6H 2O} ∞ ( 5 · DMF · 6H 2O). The topological architectures of all these coordination compounds are strongly dependent on the counteranions, with the aid of guest solvents, and include a chiral 3D non-interpenetrated structure for 1, an acentric mononuclear structure for 2, acentric 2D undulating networks for 3 and 5, and a chiral 1D double-stranded chain for 4. In particular, all these acentric or chiral coordination architectures are generated from an achiral ligand as a building unit, and their second-order non-linear optical (NLO) properties are also studied in this paper.

Ligand Concentration Controlled Supramolecular Isomerism in Two CuSCN Based Coordination Polymers with in Situ Synthesized 4,4‘-Dipyridylsulfide as a Co-Ligand

Reactions of CuCl2, 4-pyridylthiol, and NH4SCN in mixed acetonitrile and water solutions at 140 °C and 96 h led to two polymorphs of CuSCN coordination polymers with stoichiometry [Cu2(SCN)2(dps)]∞ (dps = 4,4‘-dipyridyl sulfide). The dps ligand is generated in situ via desulfation coupling of 4-pyridinethiol during the hydrothermal treatment. Polymorph 1 is a two-dimensional (2D) tubular sheet constructed by an unprecedented [CuSCN]∞ column and dps ligand. The [CuSCN]∞ column can be described as two zigzag chains arranged with approximate C2v symmetry, one chain being connected to the other by Cu−S contacts. An alternative description of the [CuSCN]∞ column is the stacking of [CuSCN]2 dimers, alternately rotated by 90° and linked by Cu−N contacts. Polymorph 2 is a 2D planar sheet constructed by [Cu(SCN)]∞ staircase chains and dps ligands. The [CuSCN]∞ staircase can be viewed as an alternating fusion of four-membered Cu−S−Cu−S rings and eight-membered Cu−S−C−N−Cu−S−C−N rings. The two polymorphs are very rare examples of coordination polymers that exhibit a similar local coordination geometry of metal and the same topology but different CuSCN structural motifs. Interestingly, 1 and 2 show quite different photoluminescent properties: the former has emission maxima at 538 nm assigned to a ligand-centered excited state, while the latter shows emission maxima at 636 nm tentatively attributed to both ligand-to-metal and metal-centered transitions.

Three-dimensional molecular network, [{Cu(dps) 2(SO 4)}·3H 2O·DMF] n, and its different third-order NLO performance (dps=4,4′-dipyridyl sulfide)

A new three-dimensional non-interpenetrating coordination polymer, [{Cu(dps) 2(SO 4)}·3H 2O·DMF] n ( 1) (dps=4,4′-dipyridyl sulfide) was synthesized and structurally characterized. 1 crystallizes in triclinic system, space group P−1 with cell parameters of a=10.9412(1) Å, b=11.8999(1) Å, c=12.5057(1) Å, V=1400.7(3) Å 3, Z=2, D c=1.573 g cm −3, F(0 0 0)=686, μ=1.059 mm −1. R 1=0.0436, w R 2=0.1148. In the polymeric architecture, SO 4 2 - serve as bridging coligands to connect highly puckered [Cu 2(dps) 2] n frameworks resulting in a 3D motif containing channels for guest molecule inclusion. Quantum chemistry calculation shows that the third-order NLO properties of polymer 1 are controlled by SO 4 2 - groups and dps ligands, and metal ions have less influence on the third-order NLO properties.

New discrete and polymeric supramolecular architectures derived from dinuclear (bis-β-diketonato)copper(ii) metallocycles

New examples of adducts between di- (and, in one instance, tetra-) functional nitrogen ligands and planar 'platform-like' dinuclear copper(II) complexes, [Cu2L2], incorporating the 1,3-aryl linked bis-beta-diketonato bridging ligand 1,1'-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione) (H2L) have been synthesised. The X-ray structures of six adduct species are reported. The interaction of [Cu2(L)2] with the ditopic ligand aminopyrazine (apyz) yielded the sandwich-like tetranuclear species [(Cu2L2(apyz))2]. A variable-temperature magnetochemical investigation of this product indicated weak antiferromagnetic coupling between the (five-coordinate) copper centres, mediated by the 2-aminopyrazine linkers. An analogous structure, [(Cu2L2(dabco))2] (dabco=1,4-diazabicyclo[2.2.2]octane), was generated when dabco was substituted for aminopyrazine while use of 4,4'-dipyridyl sulfide (dps) and 4,4'-(1,3-xylylene)-bis(3,5-dimethylpyrazole) (xbp) as the ditopic 'spacer' ligands resulted in polymeric species of type [Cu2L2(dps)]n and [Cu2L2(xbp)]n, respectively. These latter species exist as one-dimensional chain structures in which copper(II) centres on different dinuclear platforms are linked in a 'zigzag' fashion. In contrast, with 2,2'-dipyridylamine (dpa) a discrete complex of type [Cu2L2(dpa)2] formed in which one potential pyridyl donor from each 2,2'-dipyridylamine ligand remains uncoordinated. The use of the potentially quadruply-bridging hexamethylenetetramine (hmt) ligand as the linker unit was found to give rise to an unusual two-dimensional polymeric motif of type [(Cu2(L2)2)3(hmt)2]n. The product takes the form of a (6,3) network, incorporating triply bridging hexamethylenetetramine units.

Polymeric hydrogen-bonded supramolecules by self-assembling of adamantane derivatives with bipyridines

Eight new supramolecular structures have been prepared by 4,4′-(1,3-adamantanediyl)diphenol (ADP), 1,3-adamantanedicarboxylic acid (ADC) and/or 1,3-adamantanediacetic acid (ADA) with bipyridine bases 1,2-di(4-pyridyl)ethylene (dipy-ete), 1,2-bis(4-pyridyl)ethane (bipy-eta), 4,4′-dipyridyl sulfide (dipy-sul), 4,4′-dipyridyl disulfide (dipy-dis) and 4,4′-dipyridyl N,N′-dioxide (dipy-dox). These molecular complexes are (ADP)·(dipy-ete) 1, (ADP)·(dipy-sul) 2, (ADP)·(dipy-dox) 3, (ADC)·(dipy-ete) 4, (ADC)2·(bipy-eta) 5, (ADC)·(dipy-dis) 6, (ADA)·(dipy-ete) 7, (ADA)·(bipy-eta) 8, respectively. Their crystal structures have been determined by single-crystal X-ray diffraction. All these molecular complexes exhibit supramolecular structures via O–H⋯N or O–H⋯O hydrogen bondings. 1, 2, 3, 4 and 6 generate zigzag chain structures. 5, 7 and 8 form 1-D linear chain structures.

Synthesis and DNA-binding properties of binuclear platinum complexes with two trans-[Pt(NH3)2Cl]+ units bridged by 4,4?-dipyridyl sulfide or selenide

Two novel dinuclear platinum complexes, {trans-[Pt(NH3)2Cl]2(dpsu)}(NO3)2(1) and {trans-[Pt(NH3)2Cl]2 (dpse)}(NO3)2(2) (dpsu = 4,4′-dipyridyl sulfide and dpsu = 4,4′-dipyridyl selenide) have been prepared for use as potential antitumor drugs. Compared to the known monofunctional complex, [cis-Pt(NH3)2Cl(4-methylpyridine)]NO3, (1) exhibits an almost two-fold stronger DNA-binding ability, a result suggesting that (1) may bind bifunctionally to DNA. Kinetic studies show that (1) significantly impedes intercalation of ethidium bromide (EtdBr) into DNA in 0.3 mol dm−3 KNO3 but not in 0.3 mol dm−3 KCl, indicating that the hydrolysis is the first step upon addition of the complex to DNA. Also, the complex may interact with DNA by non-intercalation. Unlike its dinuclear analogs linked by aliphatic diamines, complex (1) does not induce a transition of poly(dG–dC) · poly(dG–dC) from the B form to the Z form. Moreover, complex (1) significantly inhibits the cleavage activity of BamHI endonuclease, but has no effect on that of EcoRI endonuclease. In contrast, its cis analog containing two [cis-Pt(NH3)2Cl]+ units greatly inhibits those of both BamHI and EcoRI, a result suggesting that the two isomers with the same aromatic ligand probably have different properties of DNA binding, and that (1) possibly shows higher DNA-binding selectivity than its cisanalog.

Crystal structures and physico-chemical properties of two new one-dimensional zinc(II) complexes with sulfide bridging bispyridines

4,4′-Dipyridyl sulfide ( L 1 ) and 4,4′-di(3-methyl)pyridyl ( L 2 ) sulfide coordination compounds of the general formula Zn( L)(X) 2 ( L 1 =4,4′-dipyridyl sulfide; L 2 =4,4′-di(3-methyl)pyridyl sulfide; X=CH 3COO −, Cl −), have been obtained. The compounds were characterized by single crystal X-ray diffraction, elemental analysis, IR and 1H NMR. Both compounds are of one-dimensional coordination polymers and crystallize in the orthorhombic systems, while in different space groups with Pnc2 for [Zn L 1 (CH 3COO) 2] 1 and Pna2(1) for [Zn L 2 Cl 2] 2, respectively. X-ray analysis and 1H NMR experiments indicate that variation of ligands rather than counter anions, CH 3COO − and Cl −, leads to the change in the modes of the dimensionality array, that is, complexes 1 prefers a linear coordination fashion while complexes 2 exhibits a zigzag conformation.

Molecular Networks Consisting of Dumbbell-cage Motif: Structure and Anion Exchangeability of [Ag(Py2S)2·BF4]n (Py2S = 4,4′-Dipyridyl Sulfide)

Abstract The silver(I) network with Py2S has the face-to-face (π–π) interactions to generate unusual dumbbell-cage motif. The BF4− counteranion within each cage has been reversibly exchanged with the similar anions in size.

(2,2'-dipyridyl sulfide-N,N')hydroxy-bis(nitrito-Q)(nitrogen monoxide-N)ruthenium(III)

The title compound, [Ru(NO2)2(OH)(C10H8N2S)(NO)], is the main product of the reaction between RuCl3 and dps (dps is 2,2′-dipyridyl sulfide, C10H8N2S) in ethanol–water at room temperature followed by reaction with NaNO2 at a higher temperature. The Ru atom has a distorted octahedral coordination geometry with the dps mol­ecule behaving as an N,N′-bidentate ligand. The six-membered chelate ring adopts a boat conformation.