Binuclear Complexes as Building Blocks for Polynuclear Complexes with High-Spin Ground States: Synthesis and Structure of a Tetranuclear Nickel Complex with anS=4 Ground State

Kersting, Berthold; Steinfeld, Gunther; Siebert, D.

doi:10.1002/1521-3765(20011001)7:19<4253::aid-chem4253>3.0.co;2-s

Cited by 45 publications

(19 citation statements)

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“…The Cr . Cr distance is 2.905 (1) Several nickel(II) complexes have also been obtained by employing the N 4 S 2 ligand H 2 L 2 [35,51]. Thus, while treatment of the coordinatively unsaturated complex 23 with pyridazine (pydz) followed by addition of two equivalents of NH 4 SCN affords a dinuclear -pyridazine complex [Ni II 2 (L 2 )(-pydz)(NCS) 2 ] (24), the reaction of 23 with pyridazine/NaN 3 gave a tetranuclear nickel(II) complex [{Ni II 2 (L 2 )(-pydz)(N 3 )} 2 ][BPh 4 ] 2 (25) (Scheme 9).…”

Section: Coordination Chemistry Of Amine-thiophenolates Hl 1 -H 2 Lmentioning

confidence: 99%

“…11 shows the results in the form of m T versus T plots. Least-squares fits of the magnetic susceptibility data by full-matrix diagonalization of the appropriate spin Hamiltonians below provided the J and g values for each compound [51].…”

Section: Structural and Spectroscopic Characterizationmentioning

confidence: 99%

“…Plots of M T against T for 24 and 25. The full line represents the best theoretical fit [51]. plex 25, the best fit to the data yielded two ferromagnetic coupling constants J 1 = 6.47 cm −1 (intradimer coupling constant) and J 2 = +3.59 cm −1 (interdimer coupling constant via the azide bridges), a g value of 2.11 and a zero-field splitting parameter D = −0.068 cm −1 [55].…”

Section: Structural and Spectroscopic Characterizationmentioning

confidence: 99%

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Tetranuclear complexes in molecular magnetism: Targeted synthesis, high-field EPR and pulsed-field magnetization

Chaudhuri

Kataev

Büchner

et al. 2009

Coordination Chemistry Reviews

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Section: Coordination Chemistry Of Amine-thiophenolates Hl 1 -H 2 Lmentioning

confidence: 99%

Section: Structural and Spectroscopic Characterizationmentioning

confidence: 99%

Section: Structural and Spectroscopic Characterizationmentioning

confidence: 99%

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Tetranuclear complexes in molecular magnetism: Targeted synthesis, high-field EPR and pulsed-field magnetization

Chaudhuri

Kataev

Büchner

et al. 2009

Coordination Chemistry Reviews

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“…Concerning polynuclear Ni complexes, only few systems are known to date. [22] (ii) The high crystallographic symmetry reduces the number of magnetic parameters significantly, allowing very accurate determination of the magnetic parameters. (iii) Two species with minimal geometrical differences of one system facilitates an isolation of possible links between ligand-field splitting or magnetic coupling, respectively, and electro-structural properties.…”

Section: Discussionmentioning

confidence: 99%

Ferromagnetic coupling and magnetic anisotropy in molecular Ni(II) squares

et al. 2003

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We investigated the magnetic properties of two isostructural Ni(II) metal complexes [Ni4LIn each molecule the four Ni(II) centers form almost perfect regular squares. Magnetic coupling and anisotropy of single crystals were examined by magnetization measurements and in particular by high-field torque magnetometry at low temperatures. The data were analyzed in terms of an effective spin Hamiltonian appropriate for Ni(II) centers. For both compounds, we found a weak intramolecular ferromagnetic coupling of the four Ni(II) spins and sizable single-ion anisotropies of the easy-axis type. The coupling strengths are roughly identical for both compounds, whereas the zero-field-splitting parameters are significantly different. Possible reasons for this observation are discussed.

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“…In view of the increasing interest in the targeted assembly of molecular-based magnetic materials using high-spin molecules of higher nuclearity [30][31][32][33][34][35][36], we considered it worthwhile to examine the possibility of linking pairs of dinuclear [LNi II 2 ] units by dicarboxylate dianions to form tetranuclear species. In the present contribution we report the synthesis and crystallographic characterization of three tetranuclear nickel (II) complexes of the type [LNi II 2 dicarboxylateNi II 2 L], where "dicarboxylate" stands for acetylenedicarboxylate, terephthalate, or isophthalate dianions.…”

Section: Dicarboxylate Dianions As a Tetradentate Bridged Ligandsmentioning

confidence: 99%

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

Lozan¹

2013

ChemJMold

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A series of novel tri-, tetra-and pentanuclear complexes composed of dinuclear LM 2 units (M=Co, Ni, Zn; L=24-membered macrocyclic hexaaza-dithiophenolate ligand) and ferrocene-carboxylate ([CpFeC 5 H 4 CO 2 ]ˉ), 1,1'-ferro-cenedicarboxylate ([Fe(C 5 Keywords: coordination chemistry, amino-thiophenolate ligands, di-and tetranuclear complexes, ferrocene and naphthalene diimide derivatives, polynuclear complexes IntroductionThe chemistry of container molecules has developed extensively over the past two decades. Many container molecules such as calixarenes, resorcarenes, cyclodextrins, carcerands and glycourils have been invaluable in studying the fundamental principles of inclusion phenomena and consequently their use in separation science or drug delivery, as two examples of application. Importantly, the area has attracted interest in the field of supramolecular chemistry because the properties of such host-guest compounds are often different from those of their constituent components. By adjusting the size and form of the binding cavity it is often possible to complex co-ligands in unusual coordination modes, to activate and transform small molecules, or to stabilize reactive intermediates [1,2]. One subclass are the metallated container molecules, in which metal ions and clusters are used as both a point of recognition and to give the container a well-defined structure. Such compounds also allow for an interplay of molecular recognition and transition-metal catalysis, and for the construction of more effective enzyme mimics. Of interest to the present work is the ability of metallocavitands to recognize and encapsulate difunctionalised molecules towards stabilising or enhancing the optical and electronic properties of redox-and photo-active compounds within a confined environment set up by two hemispheres.The carboxylate group, RCO 2-, can bind to transition metals in a variety of coordination modes giving rise to complexes of great structural diversity [3]. Current activities focus on the coordination chemistry of polycarboxylate ligands, as these offer great potential in the construction of polynuclear aggregates [4] and extended coordination polymers with micro-and mesoporous structures [5][6][7][8] or catalytic properties [9]. In addition, polycarboxylate ligands are of importance as spin-coupling bridging ligands [10][11][12][13][14][15][16][17] in the rapidly expanding fi eld of molecular magnetism [18, 19]. In this context, an enormous amount of literature has been generated concerning the distance dependence of magnetic exchange interactions between metal atoms linked by extended dicarboxylate ligands. Dinuclear copper complexes bridged by oxalate [20, 21] and terephthalate [22][23][24] dianions form, by far, the largest group of such systems, and it appears that the exchange interactions depend on the M···M distance [25], the relative orientation of the magnetic orbitals [26], and the degree of conjugation of the organic spacer unit [27, 28].

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Binuclear Complexes as Building Blocks for Polynuclear Complexes with High-Spin Ground States: Synthesis and Structure of a Tetranuclear Nickel Complex with anS=4 Ground State

Cited by 45 publications

References 51 publications

Tetranuclear complexes in molecular magnetism: Targeted synthesis, high-field EPR and pulsed-field magnetization

Tetranuclear complexes in molecular magnetism: Targeted synthesis, high-field EPR and pulsed-field magnetization

Ferromagnetic coupling and magnetic anisotropy in molecular Ni(II) squares

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

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