Synthesis of some mixed seven-coordinate complexes of the type [MI2(CO)3LL′] (M = Mo or W;L = pyridine or substituted pyridines; L′ = PPh3, AsPh3 or SbPh3)

The seven-coordinate bisacetonitrile complexes [MI₂(CO)₃(NCMe)₂] (M = Mo or W) react with L′ (L′ = PPh₃, AsPh₃ or SbPh₃) in CH₂Cl₂ at room temperature to give [MI₂(CO)₃(NCMe)L′] which when reacted in situ with L (L = pyridine or substituted pyridines) affords good yields of 28 mixed seven-coordinate complexes [MI₂(CO)₃LL′]. It is likely these reactions occur via successive dissociative displacements of two acetonitrile ligands.     

Structural variations in dinuclear model hydrolases and hydroxamate inhibitor models: synthetic, spectroscopic and structural studies

Reactions of the structural model hydrolases [M₂(OAc)₄(H₂O)(Im)₄]; M=Mn (E^′); M=Co (D^′); M=Ni (B^′) and [M₂(OPiv)₄(H₂O)(tmen)₂]; M=Mn (E″); M=Co (D″); M=Ni (B″) with a number of hydroxamic acids, RHA (aceto- (R=CH₃), benzo- (R = C₆H₅) and N-phenylacetohydroxamic acid (NPhAHA)) gave a series of hydroxamate dibridged complexes [M₂(OAc)(RA)₂(Im)₄][OTf] and [M₂(OPiv)(RA)₂(tmen)₂][OTf]; M=Co, Ni, in which the bridging hydroxamates exhibit a novel bonding mode in which the deprotonated hydroxamate hydroxyl bridges the two metal centres only. The formation of this type of structure by NPhAHA is the first example involving a secondary hydroxamic acid. These complexes are good structural models of the acetohydroxamate-inhibited C³¹⁹A variant of Klebsiella aerogenes urease (KAU) and their structures are close to those previously reported for complexes containing tmen capping ligands. Reaction with glutarodihydroxamic acid leads to hydroxylamine elimination and formation of a dimer containing deprotonated N-hydroxyglutarimide as bridging ligand but in this case the structure contains pentacoordinated Co(II) and only one bridging acetate in contrast to the tmen-based series where the analogous complex contains hexacoordinated Co(II) and two bridging acetates. Reaction of [Mn₂(OAc)₂(μ-OAc)₂(μ-H₂O)(tmen)₂] with acetohydroxamic acid (AHA) gave the first structurally characterized manganese hydroxamate, [Mn₂(OAc)₃(AA)(tmen)₂] with the same bridging/chelating mode of hydroxamate bonding as in the analogous cobalt and nickel complexes, although only one bridging hydroxamate occurs in the manganese complex in contrast to the two bridging hydroxamates in the cobalt and nickel complexes. The isolation of the dimanganese hydroxamate bridged complex suggests that hydroxamic acids may also inhibit the dimanganese based metallohydrolase, arginase.     

Preparation,structure and properties of dicyano silver complexes of the M(en)3Ag2(CN)4 and M(en)2Ag2(CN)4 type

Complexes of the M(en)₃Ag₂(CN)₄ (M = Ni, Zn, Cd) and M(en)₂Ag₂(CN)₄ (M = Ni, Cu, Zn, Cd) type were prepared and identified by elemental analysis, infrared spectroscopy, measurement of magnetic susceptibility, and X-ray powder diffractometry. The crystal structures of Ni(en)₃Ag₂(CN)₄ (I) and Zn(en)₂Ag₂(CN)₄ (II) were determined by the method of monocrystal structure analysis. Complex I crystallizes in the space group C2/c, a = 1.2639(5), b = 1.3739(4), c = 1.2494(4) nm, β = 113.25(4)°, D_m = 1.86(1), D_c = 1.86 gcm⁻³ Z = 4, R = 0.0429. The crystal structure of I consists of complex cations [Ni(en)₃]²⁺ and complex anions [Ag(CN)₂]⁻. Complex II crystallizes in the space group I2/m, a = 0.9150(3), b = 1.3308(4), c = 0.6442(2) nm, β = 95.80(3)°, D_m = 2.14(1), D_c = 2.15 gcm⁻³, Z = 2, R = 0.0334. Its crystal structure consists of infinite, positively charged chains of the [-NCAgCNZn- (en)₂]_nⁿ⁺ type and isolated [Ag(CN)₂]⁻ anions. The atoms of Ag are positioned parallely to the z axis and the AgAg distance is equal to 0.3221(2) nm.     

Structure and dynamic behaviour of lanthanide nitrate complexes with bis(diphenylphosphorylmethyl)mesitylene in solutions: The nature of unexpected P NMR spectra

The solution structures of the lanthanide complexes, [Ln(L)(NO₃)₃] and [Ln(L)₂(NO₃)₃], where L = bis(diphenylphosphorylmethyl)mesitylene and Ln = La, Ce, Nd, Er, were investigated by ³¹P NMR and IR spectroscopy, conductivity and sedimentation analysis. Variable-temperature ³¹P{¹H} NMR spectroscopy was used to identify species present in solution and to monitor their interconversions. The results indicate that equilibrium between molecular complexes [Ln(L)_n(NO₃)₃]⁰ and cationic species (as ion pairs [Ln(L)_n(NO₃)₂]⁺ · (NO₃)⁻ and as free ions [Ln(L)_n(NO₃)₂]⁺, throughout n = 1, 2) in solutions can be observed by ³¹P{¹H} NMR spectroscopy due to separate detection of the molecular complexes and cationic species. The chelate coordination of the ligand and nitrate ions is retained in all complex species at ambient temperature except for [Er(L)₂(NO₃)₃]. The crystal structure of [Nd(L)(NO₃)₃(MeCN)]MeCN was determined by X-ray diffraction.     

Co (II), Ni(II) and Cu(II) complexes with a new pendant armed macrocyclic ligand showing several π,π-interactions

A new ligand, L, bearing four cyanoethyl pendant groups has been synthesized by reaction of the precursor ligand L¹ with acrylonitrile. The X-ray crystal structure of ligand L reveals the presence of a nanotubular structure in the solid state connected by intermolecular π,π-stacking interactions between adjacent pyridine rings. The coordination capability towards transition metal ions [Co(II), Ni(II) and Cu(II)] has been investigated starting from the hydrated nitrate and perchlorate salts of the metals. The new ligand L and the metal complexes obtained were characterized by elemental analysis, FAB MS, conductivity measurements, magnetic studies, IR and UV-vis spectroscopy. Furthermore, the crystal structure of ligand L and of the complexes [CoL][Co(NO₃)₄] · CH₃CN (1), [NiL](NO₃)₂ (3), [NiL](ClO₄)₂ · CH₃CN · 3H₂O (4), [CuL][Cu(NO₃)₃(H₂O)₂](NO₃) · H₂O (5) and [CuL](ClO₄)₂ · 2CH₃CN (6) were determined. The nitrate ions in the complexes are located near the pyridine rings and π,π-stacking interactions between pyridine rings, nitrate ions and nitrile groups have been found.     

S-allyl-3-(2-pyridyl-methylene)dithiocarbazate ligand and its manganese(II), cobalt(III) and nickel(II) complexes

A new NNS tridentate ligand, S-allyl-3-(2-pyridyl-methylene)dithiocarbazate (HL) has been prepared. Three coordination complexes, Mn(L)₂ (1), [Co(L)₂]NO₃ (2) and Ni(L)₂ (3) (L⁻ is the deprotonated monoanionic form of HL) have been synthesized and characterized by elemental analysis, molar conductivity, FT-IR, ¹H NMR and UV-Vis spectroscopy. 1 and 3 are neutral complexes, while 2 is cationic with nitrate as the counter ion. Single crystal X-ray diffraction analysis shows that bis-chelate complexes have a distorted octahedral geometry in which two ligands in thiolate tautomeric form coordinate to the metal center through N atoms of the pyridine and imino moieties and one S atom. Molecular geometry from X-ray analysis, molecular geometry optimization, atomic charges distribution and bond analysis of the ligand and complexes have been performed using the density functional theory (DFT) with the B3LYP functional.     

Synthesis, structures and magnetic properties of 2-aminomethylpyridine-Ni(II) complexes

A family of complexes of Ni(II), 2-aminomethylpyridine (ampy) and tricyanomethanide (tcm) have been prepared and studied by IR, X-ray crystallography and variable temperature susceptibility. The complexes synthesized include [Ni(ampy)₃](ClO₄)₂ (1), [Ni(ampy)₃](tcm)(PF₆) (2), [Ni(ampy)₃](PF₆)₂ (3), [Ni(ampy)₂(H₂O)₂]Cl₂ (4), and [Ni(ampy)₂(tcm)₂] (5). No coordination polymers of tcm were obtained. The magnetic behavior of the complexes, and the known material [Ni(ampy)(NO₃)₂], is dominated by single-ion anisotropy effects with D-values in the range of −2 to −12 K, although some compounds show a weak antiferromagnetic interaction.     

Palladium(II) complexes containing pyrazole-derived ligands of biological interest. Four,five and six coordinate palladium(II) complexes with 5(3)-methylpyrazole-3(5)-carboxamide and 5(3)-methylpyrazole-3(5)-carbohydrazide

Neutral bis-complexes of palladium(II) with 5(3)- methylpyrazole-3(5)-carboxamide (mpa) and 5(3)- methylpyrazole-3(5)carbohydrazide (mph) of the type PdX₂·2L (where L = mpa, mph; X = Cl, Br, I, SCN, NO₃, ClO₄) have been synthesised and spectroscopically characterised. Available physico-chemical data indicate the mpa complexes of Pd(II) to be trans-square planar species with the primary ligand molecule showing monodentate behavior through the pyrazolyl ring nitrogen only. The Pd(II)—thiocyanate complex of mpa is proposed to have a pseudo-square pyramidal geometry attained through bridging anionic component. The complexes PdX₂·2mph (X = Cl, NO₃) appear to be six-coordinate species at least in the solid state; the corresponding thiocyanato variety has in all probability a five coordinate structure. The species, Pd(ClO₄)₂·2mph is a usual four coordinate one with non-coordinating perchlorate group. The monochelates, PdX₂·mph (X = Br, I), are cis-square planar varieties. The ligand molecule, mph, in all cases is believed to function as (N,N) bidentate ligand in its ‘imidol’ form except in the thiocyanate complex where unusually it exhibits both the monodentate and bidentate functions in the same species.     

Synthesis and characterization of uranyl(VI) and thorium(IV) complexes with phosphine oxides. The crystal structure of UO2(NO3)2(NO2-C6H4Ph2PO)2

Uranyl(VI) and thorium(IV) complexes of the type UO₂(NO₃)₂(L¹)₂, UO₂(NO₃)₂(L²)₂, UO₂(CH₃COO)₂L¹, UO₂(CH₃COO)₂L², Th(NO₃)₄(L¹)₂ and Th(NO₃)₄(L²)₂ (L¹ = (2-nitro)phenyl-bis-phenyl phosphine oxide, L² = triferrocenylphosphine oxide) are reported, together with their physico-chemical properties.The crystal structure of UO₂(NO₃)₂(L¹)₂ is also reported. The crystals are monoclinic, space group P2₁/n with a = 17.78(1), b = 13.88(1), c = 17.37(1) Å, β = 114.8(1)° for Z = 4. The uranium atom is 8-coordinated, the uranyl(VI) group being equatorially surrounded by an irregular hexagon of six oxygen atoms from two trans neutral ligands and two nitrato groups.     

Transition metal complexes with pyrazole derivatives as ligands

Degradation reactions of scorpionates were observed in the presence of transition metal salts MX₂ to give complexes of transition metal and pyrazole derivatives. Otherwise, pyrazolato complexes of transition metals and weakly coordinating anions such as nitrates have been synthesized from transition metal nitrates and 3-phenyl- and 4-phenyldiazo-pyrazole. A number of complexes with pyrazole derivatives as ligands, [Zn(3-tBupzH)₂Cl₂], [Fe₂(3-Phpz)₆Cl₄], [Cu(pzH)₄Br₂], [Ni(py)₂(pzH)₂Cl₂], [Li(THF)₄][Ti₂(μ-pz)₃Cl₄(NMe₂)₂], [Zn₂(μ-3-Phpz)₂(3-PhpzH)₂][(NO₃)₂], [M(3-PhpzH)₄(NO₃)₂] (M = Co, Ni, Cu, Zn, Cd), [Zn(3-PhpzH)₂(NO₃)₂], [Zn(4-PhNNpzH)₂(NO₃)₂](H₂O), and [Cd(4-PhNNpzH)₂(NO₃)₂(H₂O)₂], have been crystallized and characterized by single-crystal X-ray diffraction.     

Magnetic and luminescence characteristics of dinuclear complexes of lanthanides and a phenolic schiff base macrocyclic ligand

The magnetic and luminescence characteristics of trimorphic homodinuclear macrocyclic complexes of lanthanides and a 2:2 phenolate Schiff's base L, derived from 2,6-diformyl-p-cresol and triethylenetetramine were determined. The complexes of Pr³⁺ exhibit non-Curie-Weiss temperature dependent magnetic susceptibilities for which satisfactory fits to an axial relationship depends on crystal field splitting and a weak binuclear Pr³⁺Pr³⁺ antiferromagnetic interaction. The exchange interaction parameters are zJ′ = −2.2, −4.4 and −7.0 cm ⁻¹ for ‘off-white’ Pr₂L(NO₃)₄·2H₂O, ‘yellow’ Pr₂L(NO₃)₄, and ‘orange’ Pr₂L(NO₃)₂(OH)₂, respectively. In contrast, magnetic susceptibilities of the Ln₂L(NO₃)₃(OH) complexes (Ln = Dy, Ho) follow Curie-Weiss behavior over the entire temperature range (6 K to 300 K). The complexes of closed shell ions La³⁺, Lu³⁺, Y³⁺ and those of the half filled shell ion Gd³⁺ exhibit a strong ligand fluorescence in the 450 nm to 650 nm range with decay times at 77 K of 5–8 ns for Ln≠Gd or 2–4 ns for Ln = Gd. The complexes of Gd³⁺ also exhibit a phosphorescence at 600 nm (decay time ∼ 200 μs). The complexes containing Ce³⁺, Eu³⁺, Tb³⁺ and Er³⁺ show very weak ligand luminescence indicative of effective quenching processes. Sensitized emission from the lanthanide ion is observed only with the Eu³⁺ complexes (⁵D_o → ⁷F_j transitions). The emission lifetimes are on the order of 250 μs in the pure Eu³⁺ complexes. The emission decay curves from dilute samples of Eu³⁺ in ‘off-white’ La₂L(NO₃)_4nH₂O show a noticeable rise time as well as a biphasic decay (fast component ∼ 400 μs; slow component ∼ 2500 μs). The luminescing states of L and Eu³⁺ have a common excitation spectrum which is similar to the electronic absorption spectrum of L indicating that ligand-to-metal ion energy transfer processes are dominant. Overall the result if this study suggest that the spectral properties of the complexes are determined by the coordination mode of the lanthanide ions to the Schiff base portion of macrocyclic ligand.     

Diphosphines as bridging ligands in polymeric and dimeric thione-S-ligated Ag(I) nitrate complexes

Reactions of silver(I) nitrate with equimolar amounts of the diphos ligands 1,4-bis(diphenylphosphino)butane (dppb) or 1,2-bis(diphenylphosphino)ethane (dppe) and some heterocyclic thiones (L) in acetonitrile/methanol solvent afforded mixed-ligand complexes, the nature of which was found to be strongly influenced by the backbone length of the diphosphine ligand. The longer chained diphos ligand formed a series of dinuclear complexes of the type [Ag(dppb)(L)]₂(NO₃)₂ with both the diphosphine and thione ligands acting as bridging ligands between the two four-coordinate pseudo-tetrahedrally coordinated metal centers. In the unique case of L=4-methyl-5-trifluoromethyl-4H-1,2,4-triazoline-3(2H)-thione (mftztH), the reaction proceeded under exclusion of the thione ligand from the coordination sphere and coordination of the nitrate anions instead, leading to the diphosphine-doubly bridged dimeric compound [Ag(dppb)(NO₃)]₂. On the other hand, the complexes produced when using the short bite 1,2-bis(diphenylphosphino)ethane (dppe) turned out to be diphosphine-bridged cationic polymers of the type [Ag(dppe)(L)₂]_n(NO₃)_n. The structures of one representative for each of the two aforementioned series of complex compounds, namely [Ag(dppb)(py2SH)]₂(NO₃)₂ · 2H₂O and [Ag(dppe)(pymtH)₂]_n(NO₃)_n, have been established by single-crystal X-ray diffraction.     

Spectroscopic investigation of europium(III) nitrato complexes in anhydrous and aqueous acetonitrile

Electronic absorption and emission spectra, along with lifetime measurements and vibrational spectra, are used to investigate the interaction between nitrate and trivalent europium ions in dilute solutions in anhydrous and aqueous acetonitrile. Upon addition of increasing quantities of nitrate, the complexes [Eu(NO₃)_n]^(3?n)+, with n = 1–5, form quantitatively in anhydrous acetonitrile. In solution, the pentanitrato species is not further solvated and its spectroscopic properties are similar to those of solid samples, indicating a similar structure with five bidentate nitrates bonded to the 10-coordinate Eu(III) ion. The lifetimes of the ⁵D₀ level are 1.35(5) and 1.25(5) ms for Eu(NO₃)₃ and (Me₄N)₂Eu(NO₃)₅ 0.05 M in CH₃CN. The quantum yield of Eu(NO₃)₃ in CH₃CN is 27.4%.The addition of small quantities of water to Eu(NO₃)₃ solutions does not result in the dissociation of the nitrate ions, provided R_w = [H₂O]_t/[Eu³⁺]_t is smaller than 8; the apparent equilibrium rations for [Eu(NO₃)₃(H₂O)_n] are K₃ = 40 ± 15 M^?1 and K₄ = 9 ± 3 M^?1; K₁ and K₂ are too large to be determined. The formation of nitrato complexes is studied in mixtures containing increasing amounts of water and nitrate. Deconvolution of the different components of the ⁵D₀ → ⁷F₀ transition allows a semi-quantitative estimate of the relative concentration of the nitrato complexes. The total number of coordinated nitrate ions per europium ion can be determined on the basis of fluorescence lifetime measurements. The apparent equilibrium ratios for the formation of the mono- and dinitrato species amount to K₁ = 23 ± 3, 15 ± 5 and 5 ± 1 for R_w = 44, 94 and 304, respectively, and to K₂ = 17 ± 8 for R_w = 44 and 94.     

Synthesis, spectroscopy and magnetism of novel metal complexes of 3-aminoflavone (3-af). X-ray crystal structure of 3-af and [Cu(3-af)2(NO3)2]

The synthesis and characterization of four new complexes with the bioactive ligand 3-aminoflavone (3-af) are reported. The complexes of general formula [M(3-af)₂(H₂O)₂](NO₃)₂ · nH₂O], where M = Co(II), Ni(II), and Zn(II), and n = 0, 2, 0, respectively, and [Cu(3-af)₂(NO₃)₂] compound were prepared and studied. In particular, to investigate the binding in detail, the crystal structures of the free ligand (3-af) and [Cu(3-af)₂(NO₃)₂] (1) were determined. The new coordination compounds were identified and characterized by elemental analysis, magnetic measurements, and infrared and ligand-field spectra. The crystal structure of the Cu(II) complex reveals that the ligand acts as a N,O-bidentate chelate ligand forming a five-membered ring with the copper(II) ion. The copper(II) ion is octahedrally surrounded by the two amino nitrogens and two carbonyl oxygens from two chelating organic ligands in trans arrangement. Two molecules of coordinated nitrate anions occupy axial positions. The spectral and magnetic properties are in accordance with the structural data of the copper(II) compound. From X-ray powder-diffraction patterns and IR spectra, the complexes of nickel(II) (2) and cobalt(II) (3) were found to be mutually isomorphous. The results of the spectroscopic studies suggest a mononuclear structure of 2 and 3 complexes. The variable-temperature (1.8-300 K) magnetic susceptibility data of 2 indicate a weak ferromagnetic interaction. The magnetic behavior of complex 3 is characteristic of cobalt(II) systems with an important orbital contribution via spin-orbit-coupling and also suggests a weak ferromagnetic interaction.     

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.     

Cyanide bridged hexanuclear iron complexes

The hexanuclear complexes [Fe₂(NO₃)₂(μ-OR)₂] [NC-Fe(dppe)Cp]₄(PF₆)₂ with OR=OMe or OEt were obtained from Fe(Py)₃(NO₃)₃ and Cp(dppe)Fe-CN in methanol or ethanol. They were identified by a structure determination and by their electrochemical data. Their ν(CN) band positions indicate that the central Fe₂(μ-OR)₂ cores are very strong electron acceptors, which is underlined by strong intervalence transfer bands in the NIR.     

N,N-diisopropylcarboxylic acid amide complexes of thorium(IV) and uranium(IV) N-thiocyanates; the crystal structure of tetraisothiocyanato tetrakis(N,N-diisopropylacetamide-O)uranium(IV)

The complexes M(NCS)₄·xL (x = 2, M = U, L = Me₃CCON(Prⁱ)₂(dippva); x = 3, M = Th, L = Me₂CHCON(Prⁱ)₂(dipiba) and dippva, M = U, L = EtCON(Pr¹)₂(dippa), dipiba and dippva; x = 4, M = Th, L = MeCON(Prⁱ)₂(dipa), dippa and dipiba, M = U, L = dipa, dippa) and the solvates M(NCS)₄·4dipa·CH₂Cl₂ (M = Th, U) have been prepared. Their i.r. and u.v.-visible (M = U only) spectra are reported. The crystal and molecular structure of U(NCS)₄(dipa)₄· CH₂Cl₂ has been determined by the heavy-atom method from X-ray diffractometer data and refined by least squares to R 0.029 for 1135 independent reflections. The crystal is tetragonal, space group P$\text{4}$2₁c, with Z = 2, a = 15.663(4) and c = 10.512(3) Å. The coordination geometry about the 8-coordinate uranium atom is dodecahedral with the N atoms of the NCS groups occupying the dodecahedral A sites and the ‘dipa’ O atoms the B sites. The bonding distances of UO and UN are 2.363(8), and 2.444(11) Å respectively.     

The synthesis and characterisation of Rh(III) complexes with pyridyl triazole ligands

A series of Rh(III) mixed ligand polypyridine type complexes have been prepared. Complexes of the form [Rh(L)₂(L^′)]ⁿ⁺, where n=2/3, L=2,2^′-bipyridine (bpy)/1,10-phenanthroline (phen) and L^′=3-(pyridin-2-yl)-1,2,4-triazole (Hpytr), 1-methyl-3-(pyridin-2-yl)-1,2,4-triazole (1M3pytr), 4-methyl-3-(pyridin-2-yl)-1,2,4-triazole (4Mpytr), 3,5-bis(pyridin-2-yl)-1,2,4-triazole (Hbpt), 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (NH₂bpt) and 3-(pyridin-2-yl)-5-phenyl-1,2,4-triazole (HPhpytr), have been prepared and their synthesis and characterisation are reported. Crystals of [Rh(bpy)₂(Phpytr)](PF₆)₂ and [Rh(phen)₂(NHbpt)](PF₆)₂ were obtained and their structures determined. Analysis of X-ray crystallographic data showed that coordination of the metal centre in [Rh(phen)₂(NHbpt)](PF₆)₂ occurs via the amine moiety and a nitrogen of the pyridine ring. NMR studies illustrated that coordination to the NH₂bpt ligand was also possible via a nitrogen of the triazole ring and the pyridine ring forming the complex [Rh(phen)₂(NH₂bpt)](PF₆)₃. The absorption and emission properties of the complexes studied were found to be π-π^* in nature and preliminary evidence suggests that all complexes with the exception of [Rh(phen)₂(NHbpt)](PF₆)₂ and [Rh(bpy)₂(NHbpt)](PF₆)₂ are dual emitting at 77 K.     

Synthesis and metal complexes of 2,6-bis(1-triazolo)pyridine: X-ray structure of 2,6-bis(1-triazolo)pyridine dihydrochloride

2,6-Bis(1-triazolo)pyridine (1) was synthesized and characterized via IR and NMR. The regiochemistry of the compound was confirmed via single crystal X-ray analysis of the hydrochloride salt. A series of insoluble complexes of the general formulae M(1)₂(X)₂ or M(1)(X)₂ [M=Co(II), Ni(II), Cu(II); X=ClO₄, BF₄, Cl] were prepared and their structures interpreted in light of infrared spectra and composition analysis. The results suggest that first row transition metals are not chelated by 1, but rather form extended coordination polymeric networks. A second family of complexes was prepared using 2,6-bis(1-imidazolo)pyridine to support this interpretation.     

Synthesis,density functional theory calculations and luminescence of lanthanide complexes with 2,6‐bis[(3‐methoxybenzylidene)hydrazinocarbonyl] pyridine Schiff base ligand

A pyridine‐diacylhydrazone Schiff base ligand, L = 2,6‐bis[(3‐methoxy benzylidene)hydrazinocarbonyl]pyridine was prepared and characterized by single crystal X‐ray diffraction. Lanthanide complexes, Ln–L, {[LnL(NO₃)₂]NO₃.xH₂O (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy and Er)} were prepared and characterized by elemental analysis, molar conductance, thermal analysis (TGA/DTGA), mass spectrometry (MS), Fourier transform infra‐red (FT‐IR) and nuclear magnetic resonance (NMR) spectroscopy. Ln–L complexes are isostructural with four binding sites provided by two nitro groups along with four coordination sites for L. Density functional theory (DFT) calculations on L and its cationic [LnL(NO₃)₂]⁺ complexes were carried out at the B3LYP/6–31G(d) level of theory. The FT‐IR vibrational wavenumbers were computed and compared with the experimentally values. The luminescence investigations of L and Ln–L indicated that Tb–L and Eu–L complexes showed the characteristic luminescence of Tb(III) and Eu(III) ions. Ln–L complexes show higher antioxidant activity than the parent L ligand.