Syntheses and crystal structures of trimethyltin(IV) coordination polymers based on mixed ligands of 5-nitroisophthalate and 2,2′(4,4′)-bipy or phen

The trimethyltin(IV) polymer [(Me₃Sn)₂(nip) · EtOH]_n (1) of 5-nitroisophthalic acid (H₂nip) and its three derivatives with mixed organic N-donor ligands 2,2′-bipy [(Me₃Sn)₂(nip) · 2H₂O] · [(Me₃Sn)₂(nip) · H₂O] · 2(2,2′-bipy) (2) 4,4′-bipy {[(Me₃Sn)₂(nip)]₂(4,4′-bipy)}_n (3) or phen [(Me₃Sn)₂(nip) · H₂O] · (phen) (4) have been synthesized by the reaction of trimethyltin(IV) chloride and H₂nip when sodium ethoxide was added in the presence of 2,2′-bipy 4,4′-bipy or phen. All complexes 1–4 were characterized by elemental, IR, ¹H, ¹³C, and ¹¹⁹Sn NMR spectroscopy and X-ray crystallography analyses. Crystal, data collection and structure refinement parameters for complexes 1, 2, 3 and 4 are shown in Table 1, Table 2, respectively. The X-ray data showed the geometries of all the tin atoms in complexes 1–4 are trigonal bipyramidal. The X-ray analysis of 1 showed that the structure was a polymeric infinite chain with neighboring triorganotin centers being linked by dicarboxylate ligands and hydrogen bonds were found between adjacent chains. For 2, two different monomers were found, in one monomer, Me₃Sn were coordinated to both carboxyl groups of the ligand and water molecules were coordinated to the two Sn(IV) centers. In the other monomer, water molecules were coordinated to only one Sn center. Co-crystallized2,2′-bipy was found in 2 and a 2D supermolecular structure was formed via O–H⋯O and O–H⋯N (N atoms derived from 2,2′-bipy) hydrogen bonds. In 3 however, a 2D polymeric block was formed due to the inversion center of the 4,4′-bipy. For 4, due to the O–H⋯O and O–H⋯N (N atoms derived from phen) hydrogen bonds and intermolecular Sn⋯O bonds, a 2D polymeric structure was formed.     

Synthesis, structure and magnetic properties of two μ-oxo and thiocyanato-bridged manganese(II)-mercury(II) coordination polymers

Mixed-metal thiocyanate complexes [MnHg(SCN)₄(NOP)] (1) and [MnHg(SCN)₄(DMSO)] (2) (NOP = 3-methyl-4-nitropyridine-N-oxide, DMSO = dimethylsulfoxide) have been synthesized and structurally characterized by single crystal X-ray analysis. Complex 1 and 2 both contain a [Mn₂(μ₂-O)₂] lozenge, which is bridged to Hg(II) ions by end-to-end thiocyanate groups to form a 2-D and 3-D polymeric network, respectively. Magnetic studies indicate that both complexes are anti-ferromagnets, with 1 showing anti-ferrimagnetic ordering below 8.0 K.     

Syntheses, structures and magnetic properties of μ1,5 dicyanamide bridged coordination polymers of copper(II) and nickel(II) containing a tetradentate N-donor Schiff base

One neutral [Cu₂(enbzpy)(dca)₄]_n (1) and one polycationic [Ni(enbzpy)(dca)]_n(ClO₄)_n (2) [enbzpy = N,N′-(bis-(pyridin-2-yl)benzylidene)ethane-1,2-diamine; dca = dicyanamide] 1D coordination polymers are synthesized and characterized. X-ray structural analyses reveal each copper(II) center in 1 to adopt a distorted square pyramidal geometry with a CuN₅ chromophore coordinated through two N atoms of the Schiff base behaving as a binucleting bis(bidentate) ligand and three nitrile N atoms of one terminal and two single μ_1,5 dca units leading to a 1D ladder structure. In 2, each nickel(II) center has a distorted octahedral coordination environment with an NiN₆ chromophore bound by four N atoms of enbzpy through tetradentate chelation and two nitrile N atoms of two different single bridged μ_1,5 dca units; the latter connects other neighboring metal centers in a non-ending fashion affording a 1D chain. Variable-temperature magnetic susceptibility measurements of 1 and 2 show weak antiferromagnetic interactions among the metal centers through μ_1,5 dca bridges.     

Synthesis,crystal structure,and DNA-binding properties of a new copper (II) complex containing mixed-ligands of 2,2′-bipyridine and p-methylbenzoate

A novel copper complex of [Cu(bpy)(pba)₂ · H₂O] · 0.5H₂O (bpy = 2,2′-bipyridine, pba = p-methylbenzoate) was synthesized. The interaction of the complex to native fish sperm DNA was investigated through electrochemistry, electronic absorption spectroscopy and viscosity experiments. In the X-ray crystallography structure, the copper (II) ion is coordinated by two oxygen atoms of two p-methylbenzoate groups, two nitrogen atoms of 2,2′-bipyridine and one water molecule. The observed changes in the physicochemical features of the copper (II) complex on binding to DNA suggested that the complex bind to DNA with intercalation mode via 2,2′-bipyridine ring into DNA base pairs. Electrochemical studies revealed that the complex prefer to bind to DNA in Cu(I) form rather than Cu(II) oxidation state form. Additionally, the nuclease activity of the title complex was assessed by gel electrophoresis assay and the results shown that the copper complex can cleave pBR322 DNA effectively in the presence of ascorbic acid.     

Syntheses, structures, and magnetic properties of two new μ-alkoxo-μ-pyrazolato bridged dicopper(II) complexes

The syntheses, structures, and magnetic properties of two new μ-alkoxo-μ-pyrazolato heterobridged compounds, [Cu ^II₂(L¹-F)(μ-prz)] (1) and [Cu ^II₂(L¹-2OMe) (μ-prz)] · 0.5 CH₃CN (2) (prz=pyrazolato; H₂L¹-F=1,3-bis(3-fluorosalicylideneamino)-2-propanol; H₂L¹-2OMe=1,3-bis(4,6-dimethoxy salicylideneamino)-2-propanol) have been reported. Compound 1 crystallizes in triclinic space group with a=8.6392(10) Å, b=10.6431(9) Å, c=11.6809(13) Å, α=85.972(8)°, β=71.492(9)°, and γ=72.221(9)°, while the unit cell parameters of 2 are as follows: space group: monoclinic C2/c, a=28.2948(5) Å, b=7.3033(2) Å, c=26.3933(5) Å, and β=96.243(1)°. The variable-temperature magnetic susceptibility measurements reveal that the metal centers in both the compounds are antiferromagnetically coupled with J=−200 cm⁻¹ for 1 and J=−175 cm⁻¹ for 2. The magnetic behaviors have been explained on the basis of two opposing factors, complementarity and countercomplementarity of magnetic orbitals.     

Synthesis, properties and crystal structures of new binuclear lead(II) complexes based on phenyl, naphthyl-containing fluorine β-diketones and substituted 2,2′-bipyridines

Four lead(II) complexes with substituted 2,2′-bipyridine adducts and β-diketonates ligands, [Pb(5,5′-dm-2,2′-bpy)(tfpb)₂]₂1, [Pb(4,4′-dmo-2,2′-bpy)(tfpb)₂]₂2, [Pb(4,4′-dm-2,2′-bpy)(tfnb)₂]₂3 and [Pb(5,5′-dm-2,2′-bpy)(tfnb)₂]₂4, (“4,4′-dm-2,2′-bpy”, “5,5′-dm-2,2′-bpy”, “4,4′-dmo-2,2′-bpy”, “Htfpb” and “Htfnb” are the abbreviations of 4,4′-dimethyl-2,2′-bipyridine, 5,5′-dimethyl-2,2′-bipyridine, 4,4′-dimethoxy-2,2′-bipyridine, 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, respectively) have been synthesized and characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy and also studied by thermal and electrochemical as well as X-ray crystallography. The supramolecular features in these complexes are guided/controlled by weak directional intramolecular interactions.     

Syntheses, structures and magnetic properties of tetranuclear and trinuclear nickel(II) complexes with β-diketone-functionalized pyridinecarboxylate ligand

The new β-diketone-functionalized pyridinecarboxylate ligand 2-(3-oxo-3-phenyl-propionyl)-6-pyridinecarboxylic acid (H₂L) has been synthesized and fully characterized. Its tetranuclear and trinuclear nickel(II) coordination compounds [Ni₄L₄(DMF)(H₂O)₃]·2.5DMF·3H₂O (1) and [Ni₃L₂(OAc)₂(DMF)₂ (H₂O)₂]·DMF·H₂O (2) have also been synthesized and characterized by single crystal X-ray diffraction. Compound 1 has a [2 × 2] molecular grid structure and 2 is a trinuclear structure. The magnetic properties study of 1 and 2 revealed the intramolecular antiferromagnetic exchange coupling between the Ni(II) ions exists.     

A systematic study on the thermal decomposition reactions of coordination polymers based on metal(II) selenocyanates and 4,4′-bipyridine: Directed synthesis of a μ-1,3 bridging selenocyanate

Reaction of manganese(II), iron(II), cobalt(II) and nickel(II) selenocyanate with 4,4′-bipyridine (bipy) in water at room temperature leads to the formation of the ligand-rich 1:2 hydrates [{M(bipy)(NCSe)₂(H₂O)₂}·bipy]_n (bipy = 4,4′-bipyridine) with M = Mn (1-Mn), Fe (1-Fe), Co (1-Co) and Ni (1-Ni). In their crystal structures, the metal cations are coordinated by two terminally N-bonded selenocyanato anions, two water molecules, and two bridging bipy ligands in an octahedral coordination mode. These building blocks are connected into linear M-bipy-M chains, which are further linked by hydrogen bonds between the water molecules and non-coordinated bipy ligands into layers. On heating these precursor compounds, they decompose into ligand-rich 1:2 anhydrates [M(NCSe)₂(bipy)₂]_n with M = Mn (2-Mn), Fe (2-Fe), Co (2-Co) and Ni (2-Ni). After water removal the coordination spheres of the metal cations are completed by N-coordination of the bipy ligand which formerly was involved in OH···N hydrogen bonding. On further heating, the manganese(II) compound loses half of its bipy ligands leading to a new ligand-deficient 1:1 intermediate [Mn(NCSe)₂(bipy)]_n (3-Mn) with μ-1,3-bridging selenocyanato anions. In contrast, all other compounds decompose without the formation of ligand-deficient intermediates. These structural changes are accompanied with a dramatic change in their magnetic properties: Whereas all ligand-rich 1:2 compounds 1-M and 2-M (M = metal) show only Curie-Weiss paramagnetism, in the ligand-deficient 1:1 intermediate 3-Mn an antiferromagnetic long-range ordering at T_N = 10.5 K is found. The thermal and magnetic properties are qualitatively compared with those of the related ligand-rich and ligand-deficient selenocyanato and thiocyanato compounds based on bipy, pyrazine and pyrimidine as ligand.     

Synthesis, crystal structures and magnetic properties of two bis(μ-phenoxido)dicopper(II) complexes derived from reduced Schiff base ligands

Two phenoxido bridged dinuclear Cu(II) complexes, [Cu₂(L¹)₂(NCNCN)₂] (1) and [Cu₂(L²)₂(NCNCN)₂]·2H₂O (2) have been synthesized using the tridentate reduced Schiff-base ligands 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol (HL¹) and 2-[1-(3-methylamino-propylamino)-ethyl]-phenol (HL²), respectively. The complexes have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Both the complexes present a diphenoxido bridging Cu₂O₂ core. The geometries around metal atoms are intermediate between trigonal bipyramid and square pyramid with the Addison parameters (τ) = 0.57 and 0.49 for 1 and 2, respectively. Within the core the Cu–O–Cu angles are 99.15° and 103.51° and average Cu–O bond distances are 2.036 and 1.978 Å for compounds 1 and 2, respectively. These differences have marked effect on the magnetic properties of two compounds. Although both are antiferromagnetically coupled, the coupling constants (J = −184.3 and −478.4 cm⁻¹ for 1 and 2, respectively) differ appreciably.     

One- and two-dimensional copper benzenedicarboxylate coordination polymers incorporating the flexible tethering diimine N,N′-bis(3-pyridylmethyl)piperazine: Synthesis,structure, and thermal properties

A family of three copper benzenedicarboxylate coordination polymers has been constructed using the conformationally flexible and hydrogen-bonding capable tethering ligand N,N′-bis(3-pyridylmethyl)piperazine (3-bpmp). These three coordination polymers have been characterized via single crystal X-ray diffraction, infrared spectroscopy and elemental and thermogravimetric analysis. {[Cu(ph)(Hph)(H3-bpmp)(H₂O)] · 3H₂O} (1, ph = phthalate) manifests a 1-D chain motif held into a pseudo 3-D supramolecular structure through hydrogen bonding. While both {[Cu(ip)(3-bpmp)(H₂O)] · 2H₂O} (2, ip = isophthalate) and [Cu(tp)(3-bpmp)] (3, tp = terephthalate) exhibit 2-D (4,4) rhomboid grid-like layers, they possess different layer stacking patterns and supramolecular interactions due to coordination geometry variances.     

Influence of 4′-6-diamidino-2-phenylindole on the secondary structure and template activities of DNA and polydeoxynucleotides

Summary The interaction between 4-6-Diamidino-2-Phenylindole-hydrochloride (DAPI) and a variety of DNAs and synthetic polydeoxynucleotides was investigated in order to delineate the nucleic acid structural features necessary for binding. The spectra of DAPI-DNA complexes, measured at various DAPI-DNA molar ratios (r), are hypochromic relative to DNA in the region of its maximum absorption. All the curves pass through an isosbestic point at 268 nm. A new maxima appears in the region of 380–392 nm for DAPI-DNA complexes. The magnitude of the peaks in the region are directly proportional to the amount of drug present in the complex.Studies with various DNA types and synthetic polydeoxynucleotides indicate that the drug preferentially binds to dAT-rich regions of DNA. This was also confirmed by enzymatic studies. The inhibition of template action by DAPI in a purified DNA-polymerase reaction was dependent on the dAT-content of the template. The implication of these data to explain a selective binding of DAPI to mitochondrial DNA have been discussed.     

Preparation,properties and crystal structures of nickel(II) complexes with acyclic schiff bases derived from 2,6-diformyl-4-chlorophenol and 1,5-diamino-3-thiapentane or 3,3′-diamino-N-methyl-dipropylamine

Nickel(II) complexes with the compartmental Schiff bases derived from 2,6-diformyl-4-chlorophenol and 1,5-diamino-3-thiapentane (H₂L¹) or 3,3′-diamino-N-methyl-dipropylamine (H₂L²) were synthesized, and the crystal structures of [Ni(L¹)- (py)₂] and [Ni(L²)(dmf)]·H₂0 were determined by X-ray crystallography.Ni(L¹)(py)₂ is monoclinic, space group C2/c, with a= 18.457(6), b = 11.116(7), c= 16.098(6) Å, and β = 115.79(5)°; D_c = 1.49 g cm⁻³ for Z = 4. The structure was refined to the final R of 6.9%. The molecule has C₂ symmetry. The nickel atom is six-coordinated octahedral. Selected bond lengths are: NiO 2.04(1) Å, NiN (L¹) 2.08(1) Å, NiN(py) 2.17(1) Å.[Ni(L²)(dmf)]·H₂O is monoclinic, space group P2₁/n, with a = 17.329(6), b = 13.322(7), c = 12.476(7) Å and β = 95.43(5)°; D_c = 1.45 g cm⁻³ for Z = 4. The structure was refined to the final R of 5.1%. The nickel atom is bonded in the octahedral geometry to the bianionic pentadentate ligand L² and to one molecule of dimethylformamide. Selected bond lengths are: NiO (charged) 2.063(3) Å (mean value), NiO (neutral) 2.120(3) Å, NiN (planar) 2.050(3) Å (mean value), NiN (tetrahedral) 2.177(3) Å.     

The effects of structural variations of thiophene-containing Ru(II) complexes on the acid–base and DNA binding properties

A phenylthiophenyl-bearing Ru(II) complex of [Ru(bpy)₂(Hbptip)](PF₆)₂ {bpy?=?2,2′-bipyridine, Hbptip?=?2-(4-phenylthiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline} was synthesized and characterized by elemental analysis, ¹H NMR spectroscopy, and electrospray ionization mass spectrometry. The ground- and excited-state acid–base properties of the complex were studied by UV–visible absorption and photoluminescence spectrophotometric pH titrations and the negative logarithm values of the ground-state acid ionization constants were derived to be pK _a1?=?1.31?±?0.09 and pK _a2?=?5.71?±?0.11 with the pK _a2 associated deprotonation/protonation process occurring over 3 pK _a units more acidic than thiophenyl-free parent complex of [Ru(bpy)₂(Hpip)]²⁺ {Hpip?=?2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline}. The calf thymus DNA-binding properties of [Ru(bpy)₂(Hbptip)]²⁺ in Tris–HCl buffer (pH 7.1 and 50?mM NaCl) were investigated by DNA viscosities and density functional theoretical calculations as well as UV–visible and emission spectroscopy techniques of UV–visible and luminescence titrations, steady-state emission quenching by [Fe(CN)₆]^4?, DNA competitive binding with ethidium bromide, DNA melting experiments, and reverse salt effects. The complex was evidenced to bind to the DNA intercalatively with binding affinity being greater than those for previously reported analogs of [Ru(bpy)₂(Hip)]²⁺, [Ru(bpy)₂(Htip)]²⁺, and [Ru(bpy)₂(Haptip)]²⁺ {Hip?=?1H-imidazo[4,5-f][1,10]phenanthroline, Htip?=?2-thiophenimidazo[4,5-f][1,10]phenanthroline, Haptip?=?2-(5-phenylthiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline}.     

Influence of counter anions on the structures and magnetic properties of trinuclear Cu(II) complexes containing a μ3-OH core and Schiff base ligands

Four trinuclear Cu(II) complexes, [(CuL¹)₃(μ₃-OH)](NO₃)₂ (1), [(CuL²)₃(μ₃-OH)](I)₂·H₂O (2), [(CuL³)₃(μ₃-OH)](I)₂ (3) and [(CuL¹)₃(μ₃-OH)][Cu^II₃] (4), where HL¹ (8-amino-4-methyl-5-azaoct-3-en-2-one), HL² [7-amino-4-methyl-5-azaoct-3-en-2-one] and HL³ [7-amino-4-methyl-5-azahept-3-en-2-one] are the three tridentate Schiff bases, have been synthesized and structurally characterized by X-ray crystallography. All four complexes contain a partial cubane core, [(CuL)₃(μ₃-OH)]²⁺ in which the three [CuL] subunits are interconnected through two types of oxygen bridges afforded by the oxygen atoms of the ligands and the central OH⁻ group. The copper(II) ions are in a distorted square-pyramidal environment. The equatorial plane consists of the bridging oxygen of the central OH⁻ group together with three atoms (N, N, O) from the Schiff base. The oxygen atom of the Schiff base also coordinates to the axial position of Cu(II) of another subunit to form the cyclic trimer. Magnetic susceptibilities have been determined for these complexes over the temperature range of 2-300 K. The isotropic Hamiltonian, H = −J₁₂S₁S₂ − J₁₃S₁S₃ − J₂₃S₂S₃ has been used to interpret the magnetic data. The best fit parameters obtained are: J = −54.98 cm⁻¹, g = 2.24 for 1; J = −56.66 cm⁻¹, g = 2.19 for 2;J = −44.39 cm⁻¹, g = 2.16 for 3; J = −89.92 cm⁻¹, g = 2.25 for 4. The EPR data at low temperature indicate that the phenomenon of spin frustration occurs for complexes 1-3.     

Syntheses, structures and magnetic properties of μ1,5-dicyanamide bridged di- and polynuclear manganese(II) complexes containing neutral N-donor Schiff bases: Control of coordination number and nuclearity by varying denticity

Two hexacoordinated dinuclear compounds [Mn(L1)(dca)]₂(ClO₄/PF₆)₂·CH₃OH (1/2) and two heptacoordinated coordination polymers [Mn(L2)(dca)]_n(ClO₄/PF₆)_n (3/4) [L1 = N,N′-(bis-(pyridin-2-yl)benzylidene)-1,3-propanediamine; L2 = N,N′-(bis-(pyridin-2-yl)benzylidene)diethylenetriamine; dca = dicyanamide] are synthesized and characterized. Structures of 1-3 have been solved by X-ray diffraction measurements. Each manganese(II) center in 1/2 is located in a distorted octahedral environment with an MnN₆ chromophore coordinated by the four N atoms of L1 and two nitrile N atoms of bibridged μ_1,5 dca. Interestingly, the coordination polymer 3 forms a 1D chain through single Mn-(NCNCN)-Mn units in which each manganese(II) center adopts a pentagonal bipyramidal geometry with an MnN₇ chromophore occupied with five N atoms of L2 and two nitrile N atoms of monobridged μ_1,5 dca. Magnetic susceptibility measurements of 1-3 in the 2-300 K temperature range reveal weak antiferromagnetic interactions.     

Influence of ambient and enhanced ultraviolet-B radiation on the plant growth and physiological properties in two contrasting populations of Hippophae rhamnoides

Two contrasting sea buckthorn (Hippophae rhamnoides L.) populations from low and high altitude regions were employed to investigate the effects of prevailing and enhanced ultraviolet-B (UV-B) radiation on plant growth and physiological properties under a UV-B-enhanced/exclusion system. The experimental design included three UV-B regimes, including excluded (-UVB), near-ambient (NA) and enhanced UV-B (+UVB) radiation. Compared with the control (-UVB), NA caused the formation of smaller but thicker plant leaves in both sea buckthorn populations, paralleled with significant increments of carotenoids and UV-absorbing compounds as well as improved water economy. NA also induced more biomass partition from shoot to root, but CO(2) assimilation rate (A), photosynthetic area and biomass accumulation were unaffected. The low-altitude population seemed sensitive to +UVB, as indicated by the decreases in total biomass, A and ascorbic acid content (Asa, an antioxidant) compared with NA. However, little +UVB effect occurred on the high-altitude population, and we suggest that the higher tolerance of this population could be associated with its specific morphological and physiological characteristics, such as small but thick leaves and high-level of Asa content, as well as its greater physiological modification in response to NA, e.g., increases in protective compounds (carotenoids and UV-absorbing compounds) and improvement in water economy, in comparison to the low-altitude population, which form an effective adaptation strategy to enhanced UV-B stress.     

Emission polarization study of the interaction of stellacyanin with tris(2, 2′-bipyridine)osmium(II)

The association of Os(bpy)₃²⁺ and stellacyanin was investigated by measuring the emission polarization of the excited state of the complex [*Os-(bpy)₃²⁺]. At high protein concentration (≥1 mM) Os(bpy)₃²⁺ appears to bind weakly to reduced stellacyanin and to oxidized stellacyanin to a lesser extent. These results are consistent with those obtained in a previous kinetic study on the redox quenching of *Ru(bpy)₃²⁺ by stellacyanin [1]. On excitation at 480 nm, the limiting polarization (P_o) of the *Os(bpy)₃²⁺ emission at 715 nm is 0.100. From P_o we concluded that (1) protein-bound Os(bpy)₃²⁺ has considerable rotational freedom independent of the protein-probe complex, and (2) the emission dipole of *Os(bpy)₃²⁺ is at ∼45° to the C₃ molecular axis.     

Inductive influence of 4′-terpyridyl substituents on redox and spin state properties of iron(II) and cobalt(II) bis-terpyridyl complexes

A series of iron and cobalt bis-terpyridine (terpy) complexes were prepared with the general formula [M(R-terpy)₂](PF₆)₂, where M represents Co(II) and Fe(II), and R is the following terpyridine substituents in order of increasing electron-withdrawing behavior [(C₄H₈)N, (C₄H₉)NH, HO, CH₃O, CH₃-phenyl, H, Cl, CH₃SO, CH₃SO₂]. The complexes were prepared to investigate the extent of redox and spin state control that is attainable by simply varying the electron donating/withdrawing influence using a single substituent site on the terpyridine ligand. Cyclic voltammetry was used to assess the substituents influence on the M(III/II) redox couple. A plot of the M(III/II) redox potential (E_1/2) versus the electron donating/withdrawing nature of the substituents (Hammett constants), shows a strong linear trend for both metals; however, the substituents were observed to have a stronger influence on the Fe(III/II) couple. Solution magnetic susceptibility measurements at room temperature were carried out using standard NMR methodology (modified Evans method) where all of the Fe(II) complexes exhibited a diamagnetic, low spin (S = 0) behavior. In the cobalt series where R = H for [Co(R-terpy)₂]²⁺, the complex is known to be near the spin cross-over where the room temperature effective magnetic moment (μ_eff) in solution is ≈3.1 Bohr magnetons; however, in this study the μ_eff is observed to vary between 2.7 and 4.1 Bohr magnetons depending on the R-substituent.     

Synthesis, crystal structures and spectroscopic properties of copper(I) complexes containing β-dialdiminato supporting ligands

Two mononuclear neutral copper(I) complexes, Cu(L¹)PPh₃ (1), Cu(L²)(PPh₃)₂ (2) ([L¹]⁻ = [{N(C₆H₃ⁱPr₂-2,6)C(H)}₂CPh]⁻; [L²]⁻ = [{N(C₆H₅)C(H)}₂CPh]⁻) have been synthesized and structurally characterized by X-ray crystallography. In complex 1, the copper(I) atom is in a distorted three-coordinate trigonal planar environment, whereas in complex 2 with the less sterically hindered β-dialdiminato ligand, the copper(I) atom is the centre of a four-coordinate distorted tetrahedron. At room temperature complexes 1 and 2 in a film of PMMA exhibit green emission at 543 and 549 nm with lifetimes of 5.28 and 5.32 ns, respectively.