Synthesis and characterization of tetraphenylporphyrin manganese(III) complexes of phenylcyanamide ligands

Several complexes of TPPMn-L, where TPP is the dianion of tetraphenylporphyrin and L is monoanion of 4-methylphenylcyanamide (4-Mepcyd) (1), 2,4-dimethylphenylcyanamide (2,4-Me₂pcyd) (2), 3,5-dimethylphenylcyanamide (3,5-Me₂pcyd) (3), 4-methoxyphenylcyanamide (4-MeOpcyd) (4), phenylcyanamide (pcyd) (5), 2-chlorophenylcyanamide (2-Clpcyd) (6), 2,5-dichlorophenylcyanamide (2,5-Cl₂pcyd) (7), 2,6-dichlorophenylcyanamide (2,6-Cl₂pcyd) (8), 4-bromophenylcyanamide (4-Brpcyd) (9), and 2,3,4,5-tetrachlorophenylcyanamide (2,3,4,5-Cl₄pcyd) (10), have been prepared from the reaction of TPPMnCl and thallium salt of related phenylcyanamide. Each of the complexes has been characterized by IR, UV-Vis and ¹H NMR spectroscopies.4-Methylphenylcyanamidotetraphenylporphyrin manganese(III) crystallized with one molecule of solvent CHCl₃ in the triclinic crystal system and space group with the following unit cell parameters of: a = 11.596(6) Å; b = 11.768(9) Å; c = 17.81(2) Å; and α, β, γ are 88.91(9)°, 88.16(7)°, 67.90(5)°, respectively; V = 2251(3) Å³; Z = 2. A total of 4234 reflections with I > 2σ(I) were used to refine the structure to R = 0.0680 and R_w = 0.2297. The Mn(III) shows slightly distorted square pyramidal coordination with the 4-methylphenylcyanamide in the axial position, coordinated from nitrile nitrogen. The reduction of each of the TPPMn-L complexes was also examined in dichloromethane and spectroelectrochemical behavior of (1) was investigated and compared to TPPMnCl.     

Synthesis and characterization of tetraphenylporphyrin iron(III) complexes with substituted phenylcyanamide ligands

Several five coordinate complexes of [(TPP)Fe^III(L)] in which TPP is the dianion of tetraphenylporphyrin and L is the monoanion of phenylcyanamide (pcyd) (1), 2,5-dichlorophenylcyanamide (2,5-Cl₂pcyd) (2), 2,6-dichlorophenylcyanamide (2,6-Cl₂pcyd) (3), and 2,3,4,6-tetrachlorophenylcyanamide (2,3,4,6-Cl₄pcyd) (4) have been prepared by the reaction of [(TPP)Fe^IIICl] with appropriate thallium salt of phenylcyanamide. Each of the complexes has been characterized by IR, UV-Vis and ¹H NMR spectroscopic data. Dark red-brown needles of [(TPP)Fe^III(2,6-Cl₂pcyd)] (C₅₁H₃₁Cl₂FeN₆ · CHCl₃) crystallize in the triclinic system. The crystal structure of Fe(III) compound shows a slight distortion from square pyramidal coordination with the 2,6-dichlorophenylcyanamide anion in the axial position through nitrile nitrogen atom. Iron atom is 0.47(1) Å out of plane of the porphyrin toward phenylcyanamide ligand. In non-coordinating solvents, such as benzene or chloroform, these complexes exhibit ¹H NMR spectra that are characteristic of high-spin (S = 5/2) species. The X-ray crystal structure parameters are also consistent with high-spin iron(III) complexes. The iron(III) phenylcyanamide complexes are not reactive toward molecular oxygen; however, these complexes react with HCl and produce TPPFe^IIICl.     

Synthesis and structural determination of new octaethylporphyrin iron(III) complexes containing cyanamide derivatives as axial ligand

The reactions of heme, [OEPFeCl] where OEP is the dianion of octaethylporphyrin, with phenylcyanamide (pcyd) ligands have been studied. Four new porphyrin complexes, [OEPFe(L)] (L = pcyd (2), 2-Clpcyd (3), 2-Mepcyd (4), 2,4-Me₂pcyd (5)), have been isolated and characterized by spectroscopic methods. ¹H NMR spectroscopy reveals that the species [OEPFe(L)] are paramagnetic and iron is five-coordinate. The structure of [OEPFe(pcyd)] (2) has been determined by X-ray diffraction analysis. The four Fe-N, bond distances have average values of 2.062 Å. The average displacement of the iron(III) atom from the mean porphinato core is 0.45 Å. Electrochemical of [OEPFe(L)] (L = pcyd (2), 2-Clpcyd (3), 2-Mepcyd (4), 2,4-Me₂pcyd (5)) have been studied by cyclic voltammetry.     

Structural change of supramolecular coordination polymers of itaconic acid and 1,10-phenanthroline along lanthanide series

Five new supramolecular lanthanide coordination polymers with three different structures, {[La₂(IA)₃(phen)₂] · 2H₂O}_n (1), {[Ln(IA)_1.5(phen)] · xH₂O}_n [x = 1, Ln = Eu (2); x = 0.25, Ln = Dy (3)], and [Ln(IA)_1.5(phen)]_n [Ln = Er (4); Yb (5)], were prepared by hydro- and solvothermal reactions of lanthanide chlorides with itaconic acid (H₂IA) and 1,10-phenanthroline (phen), and structurally characterized by single crystal X-ray diffraction. 1 Comprises 1-D double-chains that are further assembled to a 3-D supramolecular structure via hydrogen bonds and π-π stacks between phen molecules. 2 and 3 have 2-D infinite networks which are further constructed to form 3-D supramolecular architectures with 1-D channels by π-π aromatic interactions. 4 and 5 have 2-D layer structures consisting of three types of rings which are further architectured to form 3-D supramolecular structures by C-H?O hydrogen bonds. The H₂IA ligands are all completely deprotonated and exhibit tetra-, penta-, and hexadentate coordination modes in the titled complexes. The high-resolution emission spectrum of 2 shows only one Eu³⁺ ion site in 2, which is in agreement with the result of X-ray diffraction. And the magnetic property and the thermal stability of 2 were also investigated.     

Hybrid scorpionate/cyclopentadienyl titanium and zirconium complexes with alkoxide and imido ligands

The reactivity of hybrid scorpionate/cyclopentadienyl ligand-containing trichloride zirconium complexes [ZrCl₃(bpzcp)] (1) [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] and [ZrCl₃(bpztcp)] (2) [bpztcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethylcyclopentadienyl] toward several lithium alkoxides has been carried out. Thus, alkoxide-containing complexes [ZrCl₂(OR)(bpzcp)] (R = Me, 3; Et, 4; ⁱPr, 5; (R)-2-Bu, 6), [ZrCl₂(OR)(bpztcp)] (R = Me, 7; Et, 8; ⁱPr, 9; (R)-2-Bu, 10) and [Zr(OR)₃(bpztcp)] (R = Et, 11; ⁱPr, 12) were prepared by deprotonation of the appropriate alcohol group with BuⁿLi followed by reaction with 1 or 2. In addition, the imido-complex [Ti(N^tBu)Cl(bpztcp)(py)] (13) were also prepared. The structures of these complexes have been proposed on basis of spectroscopic and DFT methods.     

Studies on Zn(II) and Cd(II) heteroligand complexes with RC(S)NHP(O)(OiPr)2 (R = Ph, NH2, PhNH) and α-diimine (bpy and phen) ligands. C-Cl bond cleavage of CH2Cl2 by [Zn(phen){PhC(S)NP(O)(OiPr)2}2]

The reaction of [ZnL^I,II₂] (L^I = [NH₂C(S)NP(O)(OiPr)₂]⁻; L^II = [PhNHC(S)NP(O)(OiPr)₂]⁻) or [Cd₂L^IV₄] (L^IV = [PhC(S)NP(O)(OiPr)₂]⁻) with 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) leads to the heteroligand complexes [Zn(bpy)L^I,II₂], [Zn(phen)L^I,II₂], [Cd(bpy)L^IV₂] or [Cd(phen)L^IV₂], respectively. The introduction of the diimine ligands into the coordination sphere of the metal cation provokes a change from 1,5-O,S- to 1,3-N,S-coordination of the anionic ligands for Zn but not for the Cd species. The reaction of [Zn(phen)L^IV₂] (L^IV = PhC(S)NP(O)(OiPr)₂⁻) with CH₂Cl₂ cleaves the chlorine atoms from CH₂Cl₂ and leads to the formation of [Zn(phen)L^IVCl] and S,S′-bis(benzimidothio-N-diisopropoxyphosphoryl)methane (L^IV-CH₂-L^IV) in high yields. Using CHCl₃ or CCl₄ instead of CH₂Cl₂ does not lead to the formation of chlorine substituted products even under reflux conditions. The new compounds were investigated by ¹H and ³¹P{¹H} NMR, IR spectroscopy and microanalysis. Crystal structures of [ZnL^II₂], [Cd(phen)L^IV₂]·CH₂Cl₂, [Zn(bpy)L^I₂] and [Zn(phen)L^IVCl] were elucidated by X-ray diffraction.     

Hydrogen-halide versus alkyl-halide oxidative addition in dimethyl platinum(II) complexes: Crystal structure of [PtBr2(bpy)]

Dimethyl platinum(II) complexes [PtMe₂(NN)] {NN = bu₂bpy (4,4′-di-tert-butyl-2,2′-bipyridine) (1a), bpy (2,2′-bipyridine) (1b), phen (1,10-phenanthroline) (1c)} reacted with commercial 3-bromo-1-propanol in the presence of 1,3-propylene oxide to afford cis, trans- [PtBrMe₂{(CH₂)₃OH}(NN)] (NN = bu₂bpy (2a), bpy (2b), phen (2c)). On the other hand, [PtMe₂(NN)] (1a)-(1b) reacted with the trace of HBr in commercial 3-bromo-1-propanol to give [PtBr₂(NN)] (NN = bu₂bpy (3a), bpy (3b)). The reaction pathways were monitored by ¹H NMR at various temperatures. Treatment of 1a-1b with a large excess of 3-bromo-1-propanol at −80 °C gave the corresponding methyl(hydrido)platinum(IV) complexes [PtBr(H)Me₂(NN)] (NN = bu₂bpy (4a), bpy (4b)) via the oxidative addition of dimethyl platinum(II) complexes with HBr. The complexes [PtBr(H)Me₂(NN)] decomposed by reductive elimination of methane above −20 °C for bu₂bpy and from −20 to 0 °C for bpy analogue to give methane and platinum(II) complexes [PtBrMe(NN)] (5a)-(5b) and then decomposed at about 0 °C to yield [PtBr₂(NN)] and methane. When the reactions were performed at a molar ratio of Pt:RX/1:10, the corresponding complexes [PtBrMe(NN)] (5a)-(5b) were also obtained. The crystal structure of the complex 3b shows that platinum adopts square planar geometry with a twofold axis through the platinum atom. The Pt…Pt distance (5.164 Å) is considerably larger than the interplanar spacing (3.400 Å) and there is no platinum-platinum interaction.     

Temperature effect on the conversions of phthalato and maleato manganese(II) complexes with diamine ligands

1,10-Phenanthroline hydrogen phthalato manganese(II) dimer [Mn₂(Hphth)₂(phen)₄] · 2Hphth · 6H₂O (1), monomeric phenanthroline phthalato manganese(II) monomer [Mn(phth)(phen)₂(H₂O)] · 2.5H₂O (2), 2,2′-bipyridine phthalato manganese(II) polymer [Mn(phth)(bpy)(H₂O)₂]_n (3) and 1,10-phenanthroline maleato polymer [Mn(male)(phen)(H₂O)₂]_n · 2nH₂O (4) (H₂phth = o-phthalic acid, male = maleic acid, phen = 1,10-phenanthroline and bpy = 2,2′-bipyridine) have been synthesized and characterized spectroscopically and structurally. Each Mn(II) atom in dimeric 1 is octahedrally coordinated by two oxygen atoms of phthalate anions and by two cis-phenanthroline ligands. The hydrogen phthalato anion bridges the Mn(II) ions through the deprotonated carboxyl groups, while the carboxylic acid group remains free. In the monomeric 2, the Mn(II) ion is octahedrally surrounded by four nitrogen atoms from two cis-phen ligands, one carboxyl oxygen from a monodentate phth ion, and one coordinated water molecule. The dimeric phthalato complex 1 can be cleaved into monomer 2 under heating with deprotonation, and the course of the reaction can be qualitatively traced by IR spectra. The phthalate group in the complex 3 binds to two manganese atoms through the vicinal carboxyl-oxygen atoms in syn-syn bridging mode. The Mn(II) atoms are linked by the phthalate group to yield a one-dimensional chain running along the a-axis. The coordination polymer 3 can be obtained from the reaction of dichloro dibipyridine manganese with phthalate under heating. In polymer 4, the manganese atom is six-coordinated by two nitrogen atoms from phen, two oxygen atoms from the coordinated water molecules and two oxygen atoms from two different maleate dianions. Each maleato unit links two neighboring manganese atoms to yield one-dimensional chain along b-axis in bis-monodentate mode. The single-chain polymer 4 prepared at low temperature can be converted to double-chain coordination polymer [Mn(male)(phen)]_n · nH₂O (5) with dehydration in warm solution.     

Palladium(II), platinum(II), ruthenium(II) and mercury(II) complexes of potentially tridentate Schiff base ligands of (E, N, O) type (E = S, Se, Te): Synthesis, crystal structures and applications in Heck and Suzuki coupling reactions

Schiff bases of 2-hydroxybenzophenone (HBP) (C₆H₅)(2-HOC₆H₄)CN(CH₂)_nEAr (L1/L2: E = S, Ar = Ph, n = 2/3; L3/L4: E = Se, Ar = Ph, n = 2/3; L5/L6: E = Te, Ar = 4-MeOC₆H₄, n = 2/3) and their complexes [PdCl(L-H)] (L = L1−L6; 1, 2, 3, 5, 7, 11), [PtCl(L3-H/L5-H)] (4/8), [PtCl₂(L4/L6)₂] (6/12), [(p-cymene)RuCl(L5/L6)]Cl (9/13) and [HgBr₂(L5/L6)₂] (10/14) have been synthesized and characterized by proton, carbon-13, selenium-77 and tellurium-125 NMR, IR and mass spectra. Single crystal structures of L1, 1, 3, 4, 5 and 7 were solved. The Pd-E bond distances (Å): 2.2563(6) (E = S), 2.3575(6)−2.392(2) (E = Se); 2.5117(5)−2.5198(5) (E = Te) are near the lower end of the bond length range known for them. The Pt-Se bond length, 2.3470(8) Å, is also closer to the short values reported so far. The Heck and Suzuki reaction were carried out using complexes 1, 3, 5 and 7 as catalysts under aerobic condition. The percentage yields for trans product in Heck reaction were found upto 85%.     

Dicopper(II) complexes showing DNA hydrolase activity and monomeric adduct formation with bis(4-nitrophenyl)phosphate

Ferromagnetic dicopper(II) complexes [Cu₂(μ-O₂CCH₃)(μ-OH)(L)₂(μ-L¹)](PF₆)₂, where L = 1,10-phenanthroline (phen), L¹ = H₂O in 1 and L = dipyrido[3,2-d:2′,3′-f]quinoxaline (dpq), L¹ = CH₃CN in 2, are prepared and structurally characterized. Crystals of 1 and 2 belong to the monoclinic space group of P2₁/n and P2₁/m, respectively. The copper(II) centers display distorted square-pyramidal geometry having a phenanthroline base and two oxygen atoms of the bridging hydroxo and acetate group in the basal plane. The fifth coordination site has weak axially bound bridging solvent molecule H₂O in 1 and CH₃CN in 2. The Cu···Cu distances are 3.034 and 3.046 Å in 1 and 2, respectively. The complexes show efficient hydrolytic cleavage of supercoiled pUC19 DNA as evidenced from the mechanistic studies that include T4 DNA ligase experiments. The binuclear complexes form monomeric copper(II) adducts [Cu(L)₂(BNPP)](PF₆) (L = phen, 3; dpq, 4) with bis(4-nitrophenyl)phosphate (BNPP) as a model phosphodiester. The crystal structures of 3 and 4 reveal distorted trigonal bipyramidal geometry in which BNPP binds through the oxygen atom of the phosphate. The kinetic data of the DNA cleavage reactions of the binuclear complexes under pseudo- and true-Michaelis-Menten conditions indicate remarkable enhancement in the DNA hydrolysis rate in comparison to the control data.     

Synthesis and cellular impact of diene-ruthenium(II) complexes: a new class of organoruthenium anticancer agents

The cytostatic properties and cellular effects of novel diene-ruthenium(II) complexes of the types OC-6-13-[RuCl₂(pp)(cod)] 1-5 (pp = 2,2′-bipyridyl (bpy), phen = 1,10-phenanthroline (phen), 5,6-dimethylphenanthroline (5,6-Me2phen), dipyrido[3,2-d:2′,3′-f]quinoxaline (dpq), ethylenediamine (en)) and OC-6-24-[RuCl{(Me₂N)₂CS}(pp)(cod)](CF₃SO₃) 6-8 (pp = phen, 5,6-Me₂phen, dpq) have been studied for the human cancer cell lines MCF-7 and HT-29 and for Jurkat leukemia cells. CD spectra indicate that 7 causes a massive distortion of the CT DNA B double helix toward the A form. Whereas the neutral complexes 1, 2 and 5 exhibit only modest antiproliferative activity toward MCF-7 and HT-29 cells, the monocationic complexes are significantly more active, in particular the DNA-distorting complex 7 with its IC₅₀ values of 0.73 and 0.42 μM, respectively. As established by online monitoring with a cell-based sensor chip, this potent 5,6-Me₂phen complex invokes dose-dependent decreases in MCF-7 cellular respiration and extracellular acidification rates and causes a time-delayed decrease in the impedance of the cell layers, that can be ascribed to cell death. Treatment of Jurkat cells with 7 leads to high concentrations of reactive oxygen species and the induction of apoptosis. The pronounced dose-dependent inhibition of oxygen consumption by isolated mice mitochondria indicates the involvement of an intrinsic mitochondrial pathway in the programmed cell death process.     

Synthesis, structure and electronic spectra of new three-coordinated copper(I) complexes with tricyclohexylphosphine and diimine ligands

Three new copper(I) complexes with tricyclohexylphosphine (PCy₃) and different diimine ligands, [Cu(phen)(PCy₃)]BF₄ (1) (phen = 1,10′-phennanthroline), [Cu(bpy)(PCy₃)₂]BF₄ (2) (bpy = 2,2′-bipyridine) and [Cu(MeO-CNN)(PCy₃)]BF₄ (3) (MeO-CNN = 6-(4-methoxyl)phenyl-2,2′-bipyridine), have been synthesized and characterized. X-ray structure reveals that complexes 1 and 3 are three-coordinated with trigonal geometry, while complex 2 adopts distorted tetrahedron geometry. Complexes 1 and 3 exhibit ligand redistribution reactions in chloromethane solution by addition of excess amount of PCy₃, in which three-coordinated 1 changes into four-coordinated [Cu(phen)(PCy₃)₂]⁺, and 3 leads to form [Cu(PCy₃)₂]BF₄ and CNN-OMe. All the three complexes display yellow ³MLCT emissions in solid state at room temperature with λ_max at 558, 564 and 582 nm for 1, 2 and 3, respectively, and red-shift to 605, 628 and 643 nm at 77 K in dichloromethane solution.     

Chemistry at the apical position of square-pyramidal copper(II) complexes: Synthesis, crystal structures, and magnetic properties of homopolynuclear complexes with azido bridges containing [Cu(AA)(BB)] moieties (AA = acetylacetonate; BB = 1,10-phenanthroline, bipy = 2,2′-bipyridine)

Three new homopolynuclear complexes with azido bridges have been obtained by using [Cu(AA)(BB)]⁺ building-blocks (AA = acetylacetonate; BB = 1,10-phenanthroline or 2,2′-bipyridine). The reaction between [Cu(acac)(phen)(H₂O)](ClO₄) and NaN₃ leads to a mixture of two compounds: a binuclear complex, [{Cu(acac)(phen)}₂(μ_1,3-N₃)](ClO₄) · 2H₂O (1), and a linear tetranuclear one, [{Cu(acac)(phen)(ClO₄)}₂{Cu(phen)(μ_1,1-N₃)₂}₂] (2). The reaction between [Cu(acac)(bipy)(H₂O)](ClO₄) and NaN₃ affords also a mixture of two compounds: [{Cu(acac)(bipy)}₂(μ_1,3-N₃)]₃(ClO₄)₃ · 3.75H₂O (3) and [Cu(acac)(bipy)(N₃)][Cu(acac)(bipy)(H₂O)](ClO₄) (4). The X-ray crystal structures of compounds 1-4 have been solved (for compound 4 the crystal structure was previously reported). In compounds 1 and 3, two {Cu(AA)(BB)} fragments are bridged by the azido anion in an end-to-end fashion. Two isomers, cis and trans with respect to azido bridge, were found in crystal 3. The structure of compound 2 consists of two Cu(II) central cations bridged by two μ_1,1-azido ligands, each of them being also connected to a {Cu(acac)(phen)} fragment through another μ_1,1-azido ligand. The cryomagnetic properties of the compounds 1 and 2 have been investigated and discussed. The magnetic behaviour of compound 1 shows the absence of any interactions between the metallic ions. In the tetranuclear complex 2, the magnetic interactions between the external and central copper(II) ions(J₁), and between the central metallic ions (J₂) were found ferromagnetic (J₁ = 0.36 cm⁻¹, J₂ = 7.20 cm⁻¹).     

Synthesis and electrochemical studies of octahedral nickel β-diketonate complexes

The reaction of [Ni(tmhd)₂] and [Ni(dbm)₂] with N-donor chelating ligands in dichloromethane and acetone, respectively, yields the complexes [Ni(tmhd)₂(L-L)] (L-L = 2,2′-bpy 1, phen 2 and dmae 3) and [Ni(dbm)₂(L-L)] (L-L = 2,2′-bpy 4, phen 5, dmae 6). UV-Vis spectroscopy shows very strong bands in the UV region consistent with ligand centred π → π^∗ transitions. The electrochemical studies of 1-6 reveal oxidation to Ni(III). The [Ni(tmhd)₂(L-L)] 1-3 are more easily oxidized by ca. 300 mV and are quasi-reversible whereas for the [Ni(dbm)₂(L-L)] series only complex 6 shows significant reversibility. X-ray crystallographic studies have been conducted in the case of [Ni(dbm)₂(phen)] 5 and [Ni(dbm)₂(dmae)] 6. The structures both show that the nickel metal centre is octahedral with an O₄N₂ coordination environment. In the structures the β-diketonate ligands exhibit a cis-arrangement, with the metal displaced out of the planar chelate ring.     

First examples of ternary lanthanide 2,2′-bipyridine-3,3′-dicarboxylate coordination polymers with zigzag chains structures assembled from lanthanide ions, 2,2′-bipyridine-3,3′-dicarboxylate and 1,10-phenanthroline

Four lanthanide coordination polymers, [{Ln₂(bpdc)₃(phen)₂(H₂O)₂} · (H₂O)₆]_n (Ln = Sm (1); Eu (2); Gd (3), Tb (4)), were self-assembled from 2,2′-bipyridine-3,3′-dicarboxylic acid (H₂bpdc),1,10-phenanthroline(phen) and corresponding lanthanide oxides by hydrothermal synthesis. Compounds 1-4 are found to be isomorphous and isostructural. Single-crystal X-ray diffraction studies show that compounds 1-4 are all of one-dimensional zigzag chain structures and extend to two-dimensional networks through π-π interactions and hydrogen bonds. The pyridyl nitrogen atoms of the 2,2′-bipyridyl unit in the bpdc ligand are uncoordinated in an anti-conformation along the central C-C bond of the ligand. Thermogravimetric analysis of 1-4 showed an obvious thermal stability indicating that the coordination habit of the metal ions with bpdc and phen has an effect on the overall framework. Photoluminescence measurement indicates that compound 2 and compound 4 are strong red and green emitters, respectively.     

Bis(O2S2 macrocycle) complexes of palladium(II)

Two isomeric dibenzo-O₂S₂ macrocycles L¹ and L² have been synthesised and their coordination chemistry towards palladium(II) has been investigated. Two-step approaches via reactions of 1:1-type complexes, [cis-Cl₂LPd] (1a: L = L¹, 1b: L = L²), with different O₂S₂ macrocycle systems (L¹ and L²) have led to the isolation of the following bis(O₂S₂ macrocycle) palladium(II) complexes in the solid state: [Pd(L¹)₂](ClO₄)₂ (2a) and a mixture of [Pd(L¹)₂](ClO₄)₂ (2a) + [Pd(L²)₂](ClO₄)₂ (2b).     

Synthesis, crystal structure and photo-induced DNA cleavage activity of ternary copper(II) complexes of NSO-donor Schiff bases and NN-donor heterocyclic ligands

New ternary copper(II) complexes [CuLⁿB](ClO₄) (1-3), where HLⁿ is the NSO donor Schiff base derived from the condensation of 2-mercaptoethylamine hydrochloride with salicylaldehyde (HL¹) or 2-hydroxy-3-methoxybenzaldehyde (HL²) and B is NN-donor heterocyclic base like 2,2′-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2) or 2,9-dimethyl-1,10-phenanthroline (dmp, 3), are prepared, structurally characterized by X-ray crystallography and their DNA cleavage activity studied. The complexes show distorted square-pyramidal (4 + 1) CuN₃OS coordination geometry in which the NSO-donor Schiff base is bonded at the basal plane and the NN-donor heterocyclic base displays axial-equatorial mode of bonding [Cu-S distance: ∼2.4 Å]. The one-electron paramagnetic (μ_eff = ∼1.9 μ_B) complexes display axial EPR spectra in DMF glass at 77 K giving g_∥ = ∼2.2 (A_∥ = 162 G) and g_⊥ = ∼2.0, indicating {d_x²-y²}¹ ground state. The complexes exhibit visible spectral d-d band in MeCN near 650 nm and two charge transfer bands near 400 nm. Complexes 1 and 2 display quasireversible cyclic voltammetric response in DMF-Tris buffer (1:4 v/v, pH 7.2) for the Cu(II)/Cu(I) couple at ca. −0.1 V vs. SCE. Complex 3 exhibits an irreversible reduction process forming [Cu^I(dmp)₂]⁺. Binding of 1-3 to calf thymus DNA shows the relative order: 2 (phen) ? 3 (dmp) > 1 (bpy). Complex 2 efficiently cleaves supercoiled pUC19 DNA in the presence of mercaptopropionic acid (MPA) forming hydroxyl radical or on irradiation with light of 312, 532 and 632.8 nm wavelength in a type-II process. Complexes 1 and 3 are cleavage inactive.     

Synthesis, crystal structure and photoelectric property of Mn(II/IV) coordination complexes

Three novel coordination complexes [Mn(tpha)(phen)]_n (1); [Mn(na)₂(H₂O)₂]_n (2); {[Mn(phen)₂(OH)Cl] · Cl · (OH) · (C₉H₁₁NO₂) · 2H₂O} (3) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction (H₂tpha = terephthalic acid, Hna = nicotinic acid, phen = 1,10-phenanthroline). The tpha groups in complex 1 bridge the Mn(II) ions to an infinite 3D framework. Complex 2 exhibits a 2D network structure in which the Mn(II) ions are linked by nicotinic groups. Complex 3 is connected to a 2D coordination supramolecule by hydrogen bonds. The results of surface photovoltage spectra (SPS) of complexes 1-3 indicate that they all exhibit positive surface photovoltage (SPV) responses in the range of 300-800 nm. However, the intensity, position and numbers of SPV responses are obviously different. The distinctions can be mainly attributed to their structures, valences and coordination environments of the manganese ions in the three complexes. Moreover the external field induced surface photovoltage spectra (FISPS) of the three complexes have been measured.     

Synthesis and structures of three d metal coordination polymers constructed from flexible polycarboxylate and 1,10-phenanthroline ligands

Three novel d¹⁰ metal coordination polymers, {[Cd(H₂odpa)(phen)₂]·H₂O}_n (1), [Cd₂(odpa)(phen)(H₂O)₂]_n (2), {[Zn₄(odpa)₂(phen)₂(H₂O)₂]·H₂O}_n (3), (H₄odpa = 4,4′-oxydiphthalic acid, phen = 1,10-phenanthroline) were obtained with different metal/ligand ratios through hydrothermal method and characterized. Compound 1 forms a one dimensional zigzag chain, in which two phen ligands chelate to one cadmium atom. Compound 2 shows a three dimensional network structure comprised of new tetranuclear cadmium clusters as the nodes and (odpa)⁴⁻ anions as the linkers, exhibits an unusual topological structure. Compound 3 is an unprecedented three dimensional polymer based on octanuclear zinc clusters cross-linked by (odpa)⁴⁻ anions. In 1-3, central Cd^II/Zn^II ions and (odpa)⁴⁻ ligand display completely different coordination modes and conformations. In addition, the thermal stabilities and photoluminescence properties of 1-3 were also studied.     

A series of d transition metal coordination complexes: Structures and comparative study of surface electron behaviors (n = 9, 8, 7, 6, 5)

Ten transition metal coordination complexes [Cu₂(phen)(p-tpha)(μ-O)]_n1, [Cu(m-tpha)(imH)₂]_n2, [Ni(5-Haipa)₂(H₂O)₂]_n3, [Ni(phen)₂(H₂O)₂]·btc·[Ni(H₂O)₆]_0.5·9H₂O 4, [Co(2,5-pdc)(H₂O)₂]_n·nH₂O 5, [Co₂(2,5-pdc)₂(H₂O)₆]_n·2nH₂O 6, [Fe(2,5-Hpdc)₂(H₂O)₂]·H₂O 7, [Co(C₆H₄NO₂)₃]·H₂O 8, [Fe₂(μ₂-btec)(μ₂-H₂btec)(bipy)₂(H₂O)₂]_n9, [Mn(phen)(2,5-pdc)(H₂O)₂]·H₂O 10 (H₄btec = 1,2,4,5-benzenetetracarboxylic acid, phen = 1,10-phenanthroline, 2,5-H₂pdc = 2,5-pyridine-dicarboxylic acid, p-tpha = p-phthalic acid, m-tpha = m-phthalic acid, bipy = 2,2′-bipyridine, 5-H₂aipa = 5-aminoisophthalic acid, imH = imidazole, H₃btc = 1,3,5-benzenetricarboxylic acid) were synthesized through hydrothermal method. They were characterized by UV-Vis absorption spectra, single-crystal X-ray diffraction and surface photovoltage spectra (SPS). Structural analysis indicated that the complexes 1, 2, 3, 5, 6 and 9 were linked into infinite structures bridged by organic acid ligands. The other four complexes were molecular complexes and further connected to 2D or 3D structures by the hydrogen bonds. The SPS of complexes 1-10 indicate that there are positive response bands in the range of 300-800 nm showing different levels of photo-electric conversion properties. The intensity, position, shape and the number of the response bands in SPS are obviously different since the structure, species, valence, dⁿ electrons configuration and coordinated environment of the center metals are different. There are good relationships between SPS and UV-Vis spectra.