Structural, spectral, and magnetic properties of end-to-end di-mu-thiocyanato-bridged polymeric complexes of Ni(II) and Co(II). X-ray crystal structure of di-mu-thiocyanatobis(imidazole)nickel(II).

Thiocyanatonickel(II) and thiocyanatocobalt(II) complexes of the composition Ni(NCS)(2)(HIm)(2) (1) and Co(NCS)(2)(HIm)(2) (2), where HIm = imidazole, were prepared and studied. In particular, the crystal structure of Ni(NCS)(2)(HIm)(2) was determined by X-ray methods. This compound crystallizes in the monoclinic system, space group P2(1)/n, with a = 7.720(1) A, b = 5.557(1) A, c = 13.774(3) A, beta = 102.54(3) degrees, and Z = 2. Its structure consists of a one-dimensional polymeric chain in which nickel(II) ions are bridged by two thiocyanate groups bonding in an end-to-end fashion in a trans arrangement. The Ni...Ni distance is 5.557(1) A. The crystal packing is determined by the intermo…

Coligand Effects on the Field-Induced Double Slow Magnetic Relaxation in Six-Coordinate Cobalt(II) Single-Ion Magnets (SIMs) with Positive Magnetic Anisotropy.

Two mononuclear cobalt(II) compounds of formula [Co(dmphen)2(OOCPh)]ClO4·1/2H2O·1/2CH3OH (1) and [Co(dmbipy)2(OOCPh)]ClO4 (2) (dmphen = 2,9-dimethyl-1,10-phenanthroline, dmbipy = 6,6'-dimethyl-2,2'-bipyridine and HOOCPh = benzoic acid) are prepared and magnetostructurally investigated. Each cobalt(II) ion is six-coordinate with a distorted octahedral CoN4O2 environment. The complex cations are interlinked leading to supramolecular chains (1) and pairs (2) that grow along the crystallographic c-axis with racemic mixtures of (Δ,Λ)-Co units. FIRMS allowed us to directly measure the zero-field splitting between the two lowest Kramers doublets, which led to axial anisotropy values of 58.3 cm-1 ≤…

Catecholato complexes of o-phenylenebis(salicylideneiminato)iron(III) and meso-tetra(parasulphonatephenyl)porphyrinatoferrate(III). A comment on the structure of the active site in catechol-1,2-dioxygenase

Abstract Formation of catecholato complexes of Fe(saloph) + and Fe(TPPS) 3− in solution is studied. Fe(saloph)(cat) − contains a cat 2− bidentate ligand. Its formation in solution competes efficiently with the hydrolysis and dimerization of Fe(saloph) + to give Fe 2 (saloph) 2 O. This behaviour shows that the planar saloph 2− ligand, as the analogous salen 2− , is easily distorted, and is not as rigid as generally considered. Iron(III) porphyrin Fe(TPPS) 3− with catechol gives the complex [Fe(TPPS)(Hcat)] 4− . Deprotonation of the unidentate Hcat − ligand cannot be studied because the smaller stability of the complex, and the dimerization of the metalloporphyrin dominates in basic medium. T…

Synthesis, crystal structures and magnetic properties of M(II)Cu(II) chains (M = Mn and Co) with sterically hindered alkyl-substituted phenyloxamate bridging ligands.

A series of neutral oxamato-bridged heterobimetallic chains of general formula [MCu(L(x)2 (S)2] · p S · q H2O [p = 0-1, q = 0-2.5; L1 = N-2,6-dimethylphenyloxamate, S = DMF with M = Mn (1a) and Co (1b); L2 = N-2,6-diethylphenyloxamate, S = DMF with M = Mn (2a) and Co (2b) or S = DMSO with M = Mn (2c) and Co (2 d); L3 = N-2,6-diisopropylphenyloxamate, S = DMF with M = Mn (3a) and Co (3b) or S = DMSO with M = Mn (3c) and Co (3d)] were prepared by treating the corresponding anionic oxamatocopper(II) complexes [Cu(L(x))(2)]2- (x = 1-3) with M(2+) cations (M = Mn and Co) in DMF or DMSO as the solvent. The single-crystal X-ray structures of 2a and 3a reveal the occurrence of well-isolated, zigzag…

Synthesis, crystal structures and magnetic properties of a P-stereogenic ortho-(4-amino-tempo)phosphinic amide radical and its CuII complex

The synthesis of phosphinic amides containing one 4-amino-TEMPO substituent at the ortho position has been achieved through copper(I) catalyzed cross-coupling reactions of ortho-iodophosphinic amides with 4-amino-TEMPO. The method has been extended to the preparation of the first example of a P-stereogenic ortho-(4-amino-tempo)phosphinic amide radical 10. The reaction of 10 with Cu(hfac)2 afforded the P-stereogenic CuII complex 19. The crystal structure of both chiral compounds is reported. The molecular structure of 10 consists of a supramolecular zig-zag chain formed by intermolecular hydrogen bonds between the NH group of the phosphinic amide moiety and the nitroxide oxygen atom. In comp…

Hexanuclear Cu3O–3Cu triazole-based units as novel core motifs for high nuclearity copper(ii) frameworks

The asymmetric 3,5-disubstituted 1,2,4-triazole ligand H2V (5-amino-3-picolinamido-1,2,4-triazole) by reaction with an excess of Cu(II) perchlorate (Cu : H2V being 12 : 1) has produced a novel hexanuclear {Cu6(m3-O/H)(HV/V)3} fragment, with one triangular Cu3(m3-O/H) group connected to three peripheral single Cu(II) ions through a cis–cis–trans bridging mode of the ligand, which is the building block of the three structures described here: one hexanuclear, [Cu6(m3-O)(HV)3(ClO4)7(H2O)9]$8H2O (1), one dodecanuclear, [Cu12(m3-O)2(V)6(ClO4)5(H2O)18](ClO4)3$6H2O (2), and one tetradecanuclear 1D-polymer, {[Cu14(m3-OH)2(V)6(HV)(ClO4)11(H2O)20](ClO4)2$14H2O}n (3), the last two containing hexanuclea…

Synthetically persistent, self assembled [V(IV)2V(V)4] polyoxovanadates: facile synthesis, structure and magnetic analysis.

Slow diffusion in a H-tube at room temperature of a methanolic solution of [VO(acac)(2)] (Hacac = acetylacetone) and 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy) into an aqueous solution of sodium pyrophosphate (Na(4)P(2)O(7)) resulted in the serendipitous formation of X-ray quality crystals of mixed-valent, hexameric oxovanadates of general formula [V(6)O(12)(OCH(3))(4)(L)(4)]·solv [L = 1,10-phenanthroline (phen) for 1· 2CH(3)OH · 4H(2)O (1a), and 2,2'-bipyridine (bipy) for 2· 4H(2)O (2a)]. These were characterized by single-crystal X-ray diffraction, IR, elemental and thermogravimetric analysis (TGA). A facile, rationalized synthetic route for the isolation of 1a and 2a could be e…

CuIIand ZnIICoordination Chemistry of Pyrazole‐Containing Polyamine Receptors − Influence of the Hydrocarbon Side Chain Length on the Metal Coordination

The synthesis of a new macrocyclic receptor (L 4 ) containing two 3,5-dimethylpyrazole units connected by dipropylenetriamine bridges is reported for the first time; pH-metric titrations indicate that L 4 shows six protonation steps in the pH range 2-11. In the absence of metal ions, the pyrazole moieties are not involved in acid-base processes in this pH range. Addition of Cu I I and Zn I I results in deprotonation of the pyrazole moieties which act as bis(monodentate) η 1 :η 1 ligands. This induced deprotonation occurs at higher pH values than in the complexes of the analogous ligand containing diethylenetriamine bridges (L 1 ). The crystal structures of [Cu 2 (H - 2 L 4 )](ClO 4 ) 2 and …

Synthese, Struktur und magnetische Eigenschaften eines achtkernigen Nickel(II)-Komplexes mit einer zentralenhexahedro-Ni8-Einheit

Intermolecular interaction energies and magnetic properties of spin-isolated multinuclear CuII complexes

Dinuclear CuII complexes with 3,5-dinitrobenzoates and 2,2′-bipyridine (2) or 1,10-phenanthroline (3) were synthesized and characterized. A complete energy framework analysis using the HF/3-21G energy model was performed which found that dispersion forces and C—H...O interactions are responsible for the crystal structure features. The magnetic properties of the complexes show a weak magnetic exchange between spins, resulting in low exchange constants of −2.72 (1) cm−1 and −1.10 (1) cm−1 for complexes (2) and (3), respectively. This results from the low overlap between magnetic orbitals induced by 3,5-dinitrobenzoate bridges and the arrangement of the magnetic orbitals. Consequently, the din…

Oxidation of substituted phenols using copper(II) metallatriangles formed through ligand sharing

Reaction of N(2),N(2')-bis-[(1-butyl-benzimidazol-2yl)methyl]biphenyl-2,2'-dicarboxamide (L) with CuX2⋅nH2O in methanol leads to the assembly of four trinuclear Cu(II) complexes with the general formula [Cu3(L)3X3]⋅3X⋅nH2O⋅mMeCN, where X=Cl(-), Br(-), NO3(-) and C6H5COO(-) and n=0-5, m=0-8 (compounds 1-4, respectively). The structure of one of the complex contains three Cu(II) metal ions at the corners of an equilateral triangle. Each of the copper(II) are coordinated through two benzimidazolyl imine N-atoms and two amide carbonyl O-atoms and the apical position is occupied by an anionic nitrate ion, leading to a distorted square pyramidal environment. The magnetic susceptibility data were …

Bioinspired manganese(II) complexes with a clickable ligand for immobilisation on a solid support.

International audience; Clickable ligands like N,N′-bis((pyridin-2-yl)methyl)prop-2-yn-1-amine (L1) and N-((1-methyl-1H-imidazol-2-yl)methyl)-N-(pyridin-2-ylmethyl)prop-2-yn-1-amine (L2) have been used to synthesise a series of manganese(II) complexes for grafting onto appropriate solid supports. These ligands mimic the 2-His-1-carboxylate facial chelation present in the active site of the manganese-dependent dioxygenase (MndD), while the alkyne side function allows grafting of the ligand onto an azido-functionalised support using “click chemistry” methodologies. Such synthetic analogues of the MndD crystallise in the solid state as double halide or pseudohalide-bridged dinuclear manganese(…

BioTIME: A database of biodiversity time series for the Anthropocene

Abstract Motivation The BioTIME database contains raw data on species identities and abundances in ecological assemblages through time. These data enable users to calculate temporal trends in biodiversity within and amongst assemblages using a broad range of metrics. BioTIME is being developed as a community-led open-source database of biodiversity time series. Our goal is to accelerate and facilitate quantitative analysis of temporal patterns of biodiversity in the Anthropocene. Main types of variables included The database contains 8,777,413 species abundance records, from assemblages consistently sampled for a minimum of 2 years, which need not necessarily be consecutive. In addition, th…

Spin canting in Re(IV) complexes: magnetic properties of [ReX4(bpym)] ( X = Cl and Br; bpym = 2,2′-bipyrimidine)

The mononuclear complexes [ReCl4(bpym)] (1) and [ReBr4(bpym)] (2) (bpym = 2,2′-bipyrimidine) are weak ferromagnets. Magnetic ordering occurs below 7.0 (1) and 20.0 K (2) and good hysteresis loops are observed for the two compounds at 2.0 K. A spin-canting phenomenon, i.e., a non-strict linearity of the individual spins aligned in an anti-parallel way by intermolecular antiferromagnetic coupling occurring in many Re(IV) complexes, accounts for these magnetic features which are unusual in molecular solids such as 1 and 2.

Synthesis, structural characterization and electrochemical and magnetic studies of M(hfac)2 (M = CuII, CoII) and Nd(hfac)3 complexes of 4-amino-TEMPO

Three mononuclear complexes [M(hfac)x(ATEMPO)y], where M = Cu (11) and Co (12), x = y = 2; M = Nd (13), x = 4, y = 1, and two polynuclear complexes [{Cu(hfac)2(ATEMPO)}n], where n = 2 (14) and 4 (15), were obtained by the reaction of M(hfac)x (M = CuII, CoII, NdIII; x = 2, 3) with 4-amino-TEMPO (4-amino-2,2,6,6-tetramethylpiperidin-N-oxyl) in good yields and their structural, electrochemical and magnetic properties were examined. In all cases, the radical is coordinated to the metal through the amino group, except 15, and the metal ions have an octahedral geometry, except 13. Different coordination architectures of the copper complexes were obtained as a function of the stoichiometry and so…

Synthesis, Crystal Structure, and Magnetic Properties of an Octanuclear Nickel(II) Complex with ahexahedro-Ni8 Core

Imidazolate bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) complexes of a terpyridinophane azamacrocycle: a solution and solid state study.

The dinuclear Cu2+ and Zn2+ as well as the mixed Cu2+-Zn2+ complexes of a 5,5''-pentaazaterpyridinophane ligand (L) are able to incorporate imidazolate (Im-) as a bridging ligand. The crystal structure of [Cu(2)L(Im)(Br)(H2O)](CF(3)SO(3))(2).3H2O (1) shows one copper coordinated by the three pyridine nitrogens of the terpyridine unit, one nitrogen of the imidazolate bridge (Im-) and one bromide anion occupying the axial position of a distorted square pyramid. The second copper atom is coordinated by the remaining imidazolate nitrogen, the three secondary nitrogens at the centre of the polyamine bridge and one water molecule that occupies the axial position. Magnetic measurements have been p…

Effects of electron donating/withdrawing groups in the 5-substituted-2-hydroxybenzaldehyde on the synthesis of neutral cubanes with a NiII4O4core: synthesis, crystal structures and magnetic properties

Two tetranuclear cubane-like nickel(II) complexes of formula [Ni4(CH3O)4(L1)4(CH3OH)4] (1) and [Ni4(CH3O)4(L2)4(CH3OH)4] (2) (HL1 = 2-hydroxybenzaldehyde and HL2 = 2-hydroxy-5-methylbenzaldehyde) have been prepared by the reaction of NiCl2·6H2O with methanolic solutions of HL1 and HL2 in the presence of triethylamine at room temperature. Complexes 1 and 2 have been characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The X-ray crystal structure analysis revealed that 1 and 2 have a cubane-type structural topology with four Ni(II) ions and four methoxo-oxygen atoms regularly alternating at the corners. Each metal ion in 1 and 2 is six-coordinate in a distorte…

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