Complexation studies of MX3 (M = Ce, U; X = 1, OTf) with 1,10-phenanthroline (phen), 3,4,7,8-tetramethyl-1,10-phenanthroline (Me(4)phen) and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) in pyridine (py) and acetonitrile reveal the major influence of the counter-ion X and solvent on ligand coordination. By comparison with bipy and terpy analogues (bipy = 2,2'-bipyridine; terpy = 2,2':6',2 ''-terpyridine), the phen and tptz complexes permit to address the effects of the preorganization, basicity and softness of these bi- and terdentate ligands on the coordination behaviour of the trivalent cerium and uranium ions.Addition of phen to MX3 (M = Ce,U; X = I, OTf) in pyridine or acetonitrile led to the formation of the mono-, bis- and tris-phen adducts. The tetrakis-phen derivatives were also obtained except for X = I in the more coordinating solvent pyridine. The greater affinity of phen for M(OTf)(3) than for MI3 reflects the stronger Lewis acidity of the metal centre. The X-ray crystal structures of CeI3(phen)(2)(py)center dot py (1a center dot py), [CeI2(phen)(2) (py)(2)][I] (1b), UI3(phen)(2)(py)-1.5py (1c center dot 1.5py), [CeI2(phen)(3)[I]center dot MeCN (2a center dot MeCN)), [UI2(phen)(3)[I]center dot MeCN (2b center dot MeCN), [M(phen)(4)(MeCN)(2)][I](3)center dot xMeCN [M = Ce (3a center dot 2MeCN) and U (3b center dot 4MeCN)], Ce(OTf)(3)(phen)(2) (py)(2)center dot py (4 center dot py), Ce(OTf)(3)(phen)(3)center dot 2py (5a-2py), Ln(OTf)(3)(phen)(3)center dot py (L = Pr, Nd, Sm) and [M(OTf)(2) (phen)(4)][OTf] [M = Ce (6a) and U (6b)] were determined. The OTf- anion is a better ligand than I- and the complexes are generally less dissociated in ion pairs, as shown by the bis-phen and tris-phen complexes 4 and 5 which are neutral instead of cationic in lb and 2, and the tetrakis-phen complexes 6 which are monocationic instead of tricationic in 3.The bis-Me(4)phen complexes MI3(Me(4)phen)(2)(py) [M = Ce (7a) and U (7b)1 were obtained by treatment of MI3 with Me(4)phen in pyridine, while similar reaction with Ce(OTf)(3) gave Ce(OTf)(3)(Me(4)phen)(2)(py)(2) (8a) in pyridine and [Ce(OTf)(2)(Me(4)phen)(2)(mu(2)-OTf)](2) (8b) in acetonitrile, clearly reflecting the weaker coordinating capacity of MeCN. In contrast to that observed with the MI3/phen system, the tetrakis-Me(4)phen derivatives [MI(Me(4)phen)(4)][I](2) [M = Ce (9a) or U (9b)] could be obtained in pyridine, as well as in acetonitrile, in line with the stronger basicity of Me(4)phen compared to phen. In contrast to CeI3, no difference was observed in the coordination of 4 equiv of phen or Me(4)phen to Ce(OTf)(3) and crystals of [Ce(OTf)(2)(Me(4)phen)(4)] [OTf]center dot 3py (10 center dot 3py) were deposited from a pyridine solution. Solvates of complexes 7-10 have been crystallographically characterized.Treatment of LnX(3) (Ln = Ce, Nd; X = I, OTf) in pyridine or acetonitrile with tptz afforded mono and bis-adducts and the crystal structures of solvates of CeI3(tptz)(MeCN)(2) (11a), Ce(OTf)(3)(tptz)(2) (14), [NdI2(tptz)(2)(py)][I] (15), [CeI2(tptz)(2)(H2O)][I] (16), and 0.8CeI(3)(tptz)(2)center dot 0.2[CeI2(tptz)(2)(MeCN)][1]center dot 0.5MeCN (18) were determined. Addition of 3 equiv of tptz to CeX3 did not afford tris-tptz complexes except in the case of X = I in acetonitrile, affording crystals of [CeI(tptz)(3)][I](2)center dot 2MeCN (20a center dot 2MeCN). By comparison with the terpy analogues, the H-1 NMR spectra and crystal structures of the tptz compounds reveal the weaker basicity and electron donating capacity of tptz. While treatment of CeI3 with tptz or terpy and treatment of UI3 with terpy led to the formation of the corresponding Lewis base adducts, UI3 reacted with 1 equiv of tptz in acetonitrile to give the dinuclear uranium(IV) oxidation compound (UI3(MeCN)}(2)(mu-tptz-tptz) (21a) resulting from electron transfer from the U-III ion to the azine molecule, followed by dimerization of the anion-radical tptz(-). In the presence of 2 equiv of tptz in pyridine, the U-III -> U-IV oxidation did not occur with the less electron rich U(OTf)(3) which was transformed into U(OTf)(3)(tptz)(2)center dot 2py (22.2py) and {U(OTf)(2)(tptz)(2)}(2)(mu-OTf)(2)center dot 2py (23 center dot 2py). Crystal structures of 21-23 have been determined. (C) 2012 Elsevier Ltd. All rights reserved.

Reactions of Ln(OTf)3(Ln = Ce, Nd) or [U(OTf)3(dme)2](OTf = OSO2CF3, dme = dimethoxyethane) with 2 mol equivalents of 2,2':6',2"-terpyridine (terpy) in pyridine or acetonitrile led to the quantitative formation of the bis(terpy) complexes which crystallized as the discrete cation-anion pairs [M(OTf)2(terpy)2(py)][OTf] x 0.5py from pyridine or neutral derivatives [M(OTf)3(terpy)2] x nMeCN from acetonitrile (M = Ce, Nd, U). The crystal structures of these complexes show the differences in the M-O bond lengths to follow the variation of the ionic radii of the metals, while the U-N(terpy) and U-N(py) bonds are shorter than those expected from a purely ionic bonding model. The better affinity of terpy for U(III) over Ce(III) and Nd(III) was evidenced by the thermodynamic parameters (K, DeltaH, DeltaS) corresponding to the equilibrium between the bis- and tris(terpy) complexes in acetonitrile. Hydrolysis of the bis(terpy) compounds followed different courses; whereas the aquo compound [Ce(OTf)2(terpy)2(H2O)][OTf] crystallized readily from pyridine, the uranium complexes [UX2(terpy)2(py)]X (X = I, OTf) were oxidized into the tri- and tetranuclear mu-oxo U(IV) compounds [{UI(terpy)2(mu-O)}2{UI2(terpy)}]I4 x 2MeCN x H2O and [{U(OTf)(terpy)2(mu-O)(mu-OTf)U(terpy)}2(mu-OTf)2(mu-O)][OTf]4 x py x MeCN. The crystal structures of these first examples of uranium(IV) compounds with terpy ligands show the almost linear arrangement of the metal atoms.

Two Mn(II) complexes are isolated and X-ray characterized, namely, cis-[(L(2))Mn(II)(Cl)(2)] (1) and [(L(3))Mn(II)Cl(OH(2))](ClO(4)) (2(ClO(4))), where L(2) and L(3) are the well-known tetradentate N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine and N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)propane-1,3-diamine ligands, respectively. The crystal structure reveals that whereas the ligand L(2) is in the cis-alpha conformation in complex 1, the ligand L(3) is in the more unusual cis-beta conformation in 2. EPR spectra are recorded on frozen solutions for both complexes and are characteristic of Mn(II) species. Electrochemical behaviors are investigated on acetonitrile solution for both complexes and show that cation 2 exists as closely related Mn(II) species in equilibrium. For both complexes exhaustive bulk electrolyses of acetonitrile solution are performed at oxidative potential in various experimental conditions. In the presence of 2,6-lutidine and after elimination of chloride ligands, the formation of the di-mu-oxo mixed-valent complexes [(L(2))Mn(III)(mu-O)(2)Mn(IV)(L(2))](3+) (3a) and [(L(3))Mn(III)(mu-O)(2)Mn(IV)(L(3))](3+) (4) is confirmed by UV-vis and EPR spectroscopies and cyclic voltammetry. In addition crystals of 4(ClO(4))(3) were isolated, and the X-ray structure reveals the cis-alphaconformation of L(3). In the absence of 2,6-lutidine and without elimination of the exogenous chloride ions, the electrochemical oxidation of 1 leads to the formation of the mononuclear Mn(III) complex, namely, [(L(2))Mn(III)(Cl)(2)](+) (5), as confirmed by UV-vis as well as parallel mode EPR spectroscopy and cyclic voltammetry. In the same conditions, the electrochemical oxidation of complex 2 is more intricate, and a thorough analysis of EPR spectra establishes the formation of the binuclear mono-mu-oxo mixed-valent [(L(3))ClMn(III)(mu-O)Mn(IV)Cl(L(3))](3+) (6) complexes. Electrochemical conversion of Mn(II) complexes into mixed-valent Mn(2)(III,IV) oxo-bridged complexes in the presence of 2,6-lutidine is discussed. The role of the chloride ligands as well as that of L(3) in the building of oxo bridges is discussed. Differences in behavior between L(2) and L(3) are commented on.

A new trinuclear (MnMnMnIII)-Mn-III-Mn-II complex has been isolated and X-ray characterised, namely [(py-salpn)Mn-III(mu-OAc)-Mn-II( mu-OAc)Mn-III(py-salpn)](2+) (1), where H2PY-salpn is the new bulky [N3O2] ligand derived from the H(2)salpn Schiff base by the addition of one pyridine arm and the reduction of the imine function. The crystal structure reveals that the complex has a strictly 180 degrees Mn-III... Mn-II... Mn-III, angle, the Mn-II ion being located at an inversion centre. The complex is valence-trapped, with the terminal Mn-III ions showing a JahnTeller elongation along the pyridine-Mn-III-acetate axis. The Mn-II---Mn-III separation is 3.1224(13) angstrom. The EPR spectra recorded on solid and frozen solutions are consistent with an (MnMnMnIII)-Mn-III-Mn-II. species. The electrochemical response of complex 1 in acetonitrile solution exhibits two, one-electron reduction waves at E-1/2 = 0.140 and -0.075 V vs. SCE. Phenolato and acetato -> Mn-III ligand-to-metal charge-transfer transitions are detected by UV/Visible spectroscopy at 359 and 587 nm, respectively, Chemical oxidation of an acetonitrile solution with tert-butyl hydroperoxide leads to mononuclear Mn-IV-hydroxo species, as evidenced by UV/Visible and EPR spectroscopy as well as ESI mass spectrometry. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

Complexes of general formula [(TPA)Fe(R-Cat)]X.nS were synthesised with different catecholate derivatives and anions (TPA = tris(2-pyridylmethyl)amine, R-Cat2- = 4,5-(NO2)2-Cat2- denoted DNC(2-); 3,4,5,6-Cl4-Cat2- denoted TCC2-; 3-OMe-Cat(2-); 4-Me-Cat(2-) and X = BPh4-; NO3-; PF6-; ClO4-; S = solvent molecule). Their magnetic behaviours in the solid state show a general feature along the series, viz., the occurrence of a thermally-induced spin crossover process. The transition curves are continuous with transition temperatures ranging from ca. 84 to 257 K. The crystal structures of [(TPA)Fe(DNC)]X (X = PF6-; BPh4-) and [(TPA)Fe(TCC)]X.nS (X = PF6-; NO3- and n= 1, S = H2O; ClO4- and n= 1, S = H2O; BPh4- and n= 1, S = C3H6O) were solved at 100 (or 123 K) and 293 K. For those two systems, the characteristics of the [FeN(4)O(2)] coordination core and those of the dioxolene ligands appear to be consistent with a prevailing Fe(III)-catecholate formulation. This feature is in contrast with the large quantum mixing between Fe(III)-catecholate and Fe(II)-semiquinonate forms recently observed with the more electron donating simple catecholate dianion. The thermal spin crossover process is accompanied by significant changes of the molecular structures as shown by the average variation of the metal-ligand bond distances which can be extrapolated for a complete spin conversion from ca. 0.123 to 0.156 A. The different space groups were retained in the low- and high-temperature phases.

The title compound, dicaesium sulfate selenate–telluric acid adduct, Cs2(SO4)0.57(SeO4)0.43·Te(OH)6, is a solid solution in the series Cs2(SO4)·Te(OH)6/Cs2(SeO4)·Te(OH)6. It crystallizes in the same structure as the end member Cs2(SeO4)·Te(OH)6 in space group P21/c, whereas the corresponding sulfate adopts another structure type and crystallizes in space group R3. The structure contains planes of statistically distributed SO4/SeO4 tetra­hedra alternating with planes of Te(OH)6 octa­hedra, and with Cs+ cations situated between the planes. Both Te atoms lie on centres of symmetry.

Two new anil molecules exhibiting photochromism in the crystalline state, N-(4-hydroxy)-salicylidene-amino-4-(methylbenzoate) (2) and N-(3,5-di-tert-butylsalicylidene)-4-aminopyridine (3), are obtained. Upon irradiation in the UV, the yellow crystals change color to red, owing to enol-keto intramolecular tautomerism. The red color disappears, when crystals are left in the dark or irradiated with visible light. 3 has the most stable keto form among all anil-type photochromic compounds (tau = 460 days at room temperature). Both exhibit nonlinear optical (NLO) properties and show powder second harmonic generation (SHG) of respectively 10 and 3 times vs urea. X-ray diffraction shows acentric structures where molecules line up "head-to-tail" through hydrogen bonds for 2 (space group Pc), or form a chiral helix 3 (space group P3(2)). Evidence of reversible structural change is given for 3, and we demonstrate the functionality of this crystal as an NLO switching material, as SHG can be photomodulated by about 30%.

Dissolution of [UO2(OTf)(2)] (1) in anhydrous thf, dme or py led to the formation of the complexes [UO2(OTf)(2)(thf)(3)] (2), [UO2(OTf)(2)(dme)] (3) and [UO2(OTf)(2)(py)(3)] (4), respectively. Compounds 2 and 4 are neutral monomers in the solid state as well as the chloride [UO2Cl2(py)(3)] (5) which was prepared in a similar way as for 4 from the dimer [{UO2Cl2(thf)(2)}(2)]. Addition of 4 equivalents of triphenylphosphine oxide (tppo) to 1 afforded, in pyridine, the dicationic species [UO2(tppo)(4)][OTf](2) (6). The bi- or terdentate nitrogen molecules 2,2'-bipy, phen or terpy reacted with 1 in acetonitrile or pyridine to give [UO2(OTf)(2)(bipy)(2)] (7), [UO2(phen)(3)][OTf](2) (8), [UO2(OTf)(2) (terpy)] (9) and [UO2(terpy)(2)][OTf](2) (10), respectively. The hydroxide compound [{UO2(OH)(terpy)}(2)][OTf](2) (11) was obtained by hydrolysis in air of 1 in a mixture of acetonitrile and ethanol in the presence of terpyridine. The X-ray crystal structures of 7, 8 and 10 reveal a novel coordination geometry for the uranyl ion, the uranium atom being in a rhombohedral environment; the six coordinating ligands atoms of the {UO2}(2+) ion are separated into two parallel and staggered equilateral triangles and the UO2 axis is perpendicular to these triangles, passing through their centre. The structures of the mono(terpy) complexes 9 and 11 show the uranium atoms in a distorted pentagonal bipyramidal configuration with the nitrogen atom of the central pyridine ring of the terpy ligand significantly displaced from the equatorial plane.

Treatment of UO2(OTf)2 with pure Me3SiI led to the quantitative formation of UO2I2 (1). This compound dissolved in pyridine and thf to give the red adducts [UO2I2L3][L = py (2) or thf (3)], which were also obtained from the metathetical reaction of UO2(OTf)2 and KI. The crystal structure of has been determined. The uranyl diiodide complexes - are thermally quite stable, providing that strictly anhydrous conditions are employed.

Treatment of UO2(OTf)2 with pure Me3SiI led to the quantitative formation of UO2I2 (1). This compound dissolved in pyridine and thf to give the red adducts [UO2I2L3] {L = py (2) or thf (3)}, which were also obtained from the metathetical reaction of UO2(OTf)2 and KI. The crystal structure of 2 has been determined. The uranyl diiodide complexes 1–3 are thermally quite stable, providing that strictly anhydrous conditions are employed.

Two neutral complexes [(L(6)(3)4M)Fe2Cl4].2H(2)O.2CHCl(3) (1) and [(L(6)(3)4M)Mn2Cl4].CH3CN (2) have been synthesized [L(6)(3)4M = N,N,N',N'-tetrakis[(6-methyl-2-pyridyl)methyl]propane-1,3-diamine] and their molecular structures established by X-ray crystallography. Both structures are similar, with each metal center in a trigonal-bipyramidal environment. No magnetic coupling is observed between the metal centers. UV/Vis spectra and cyclic voltammograms were recorded in CH2Cl2 and CH3CN solutions. Both complexes are stable in CH2Cl2, whereas only 2 is stable in CH3CN. On the contrary, I is in equilibrium with another Fen species in CH3CN. When this last solution is aerated, monocrystals of the neutral linear tetranuclear complex [(L(6)(3)4M)Fe-4(mu-O)(3)Cl-6].2CH(3)CN (3) can be isolated. Its structure is unusual with two Fen, ions penta-coordinate and the two others tetracoordinate with only chloro ligands and oxo bridges. The magnetic properties reveal that two consecutive metal centers are strongly antiferromagnetically coupled. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

-terpyridine (terpy) in pyridine or acetonitrile led to the quantitative formation of the bis(terpy) complexes which crystallized as the discrete cation-anion pairs (M(OTf)2(terpy)2(py))(OTf)·0.5py from pyridine or neutral derivatives (M(OTf)3(terpy)2)·nMeCN from acetonitrile (M = Ce, Nd, U). The crystal structures of these complexes show the differences in the M-O bond lengths to follow the variation of the ionic radii of the metals, while the U-N(terpy) and U-N(py) bonds are shorter than those expected from a purely ionic bonding model. The better affinity of terpy for U

The dinuclear phenolato-bridged complex [(mL)Mn(II)Mn(II)(mL)](ClO(4))(2) (1(ClO(4))(2)) has been obtained with the new [N(4)O] pentadentate ligand mL(-) (mLH=N,N'-bis-(2-pyridylmethyl)-N-(2-hydroxybenzyl)-N'-methyl-ethane-1,2-diamine) and has been characterised by X-ray crystallography. X- and Q-band EPR spectra were recorded and their variation with temperature was examined. All spectra exhibit features extending over 0-800 mT at the X band and over 100-1450 mT at the Q band, features that are usually observed for dinuclear Mn(II) complexes. Cyclic voltammetry of 1 exhibits two irreversible oxidation waves at E(1)(p)=0.89 V and E(2)(p)=1.02 V, accompanied on the reverse scan by an ill-defined cathodic wave at E(1')(p)=0.56 V (all measured versus the saturated calomel electrode (SCE)). Upon chemical oxidation with tBuOOH (10 equiv) at 20 degrees C, 1 is transformed into the mono-mu-oxo species [(mL)Mn(III)-(mu-O)-Mn(III)(mL)](2+) (2), which eventually partially evolves into the di-mu-oxo species [(mL)Mn(III)-(mu-O)(2)-Mn(IV)(mL)](n+) (3) in which one of the aromatic rings of the ligand is decoordinated. The UV/Vis spectrum of 2 displays a large absorption band at 507 nm, which is attributed to a phenolate-->Mn(III) charge-transfer transition. The cyclovoltammogram of 2 exhibits two reversible oxidation waves, at 0.65 and 1.16 V versus the SCE, corresponding to the Mn(III)Mn(III)/Mn(III)Mn(IV) and Mn(III)Mn(IV)/Mn(IV)Mn(IV) oxidation processes, respectively. The one-electron electrochemical oxidation of 2 leads to the mono-mu-oxo mixed-valent species [(mL)Mn(III)-(mu-O)-Mn(IV)(mL)](3+) (2 ox). The UV/Vis spectrum of 2 ox exhibits one large band at 643 nm, which is attributed to the phenolate-->Mn(IV) charge-transfer transition. 2 ox can also be obtained by the direct electrochemical oxidation of 1 in the presence of an external base. The 2 ox and 3 species exhibit a 16-line EPR signal with first peak to last trough widths of 125 and 111 mT, respectively. Both spectra have been simulated by using colinear rhombic Mn-hyperfine tensors. Mechanisms for the chemical formation of 2 and the electrochemical oxidation of 1 into 2 ox are proposed.

Two heptacoordinated Mn(II) complexes are isolated and X-ray characterized using the well-known tpen ligand (tpen = N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethanediamine): [(tpen)Mn(OH(2))](ClO(4))(2) (1(ClO(4))(2)) and [(tpen)Mn(micro-OAc)Mn(tpen)](ClO(4))(3).2H(2)O (2(ClO(4))(3).2H(2)O). Crystallographic data for 1(ClO(4))(2) at 110(2) K (respectively at 293(2) K): monoclinic, space group C2/c, a = 15.049(3) A (15.096(3) A), b = 9.932(2) A (10.105(2) A), c = 19.246(4) A (19.443(4) A), beta = 94.21(3) degrees (94.50(3) degrees ), Z = 4. Crystallographic data for 2(ClO(4))(3).0.5(C(2)H(5))(2)O at 123(2) K: triclinic, space group P, a = 12.707(3) A, b = 12.824(3) A, c = 19.052(4) A, alpha = 102.71(3) degrees, beta = 97.83(3) degrees, gamma = 98.15(3) degrees, Z = 2. Investigation of the variation upon temperature of the molar magnetic susceptibility of compound 2(ClO(4))(3).2H(2)O reveals a weak antiferromagnetic exchange interaction between the two high-spin Mn(II) ions (J = -0.65 +/- 0.05 cm(-)(1), H = -JS(1).S(2)). EPR spectra are recorded on powder samples and on frozen acetonitrile solutions, demonstrating the maintenance upon dissolution of the heptacoordination of Mn in complex 1 while complex 2 partially dissociates. Electrochemical responses of complexes 1 and 2 are investigated in acetonitrile, and bulk electrolyses are performed at oxidative potential in the presence of various amounts of 2,6-lutidine (0-2.65 equiv per Mn ion). The formation from either 1 or 2 of the mixed-valent complex [(tpen)Mn(III)(micro-O)(2)Mn(IV)(tpen)](3+) (3) is established from mass spectrometry and EPR and IR spectroscopy measurements. When reaction is started from 2, formation of [(tpen)Mn(IV)(micro-O)(2)(micro-OAc)Mn(IV)](3+) (4) is evidenced from cyclic voltammetry, EPR, and UV-vis data. The Mn vs tpen ratio in the electrogenerated complexes is accurately controlled by the quantity of additional 2,6-lutidine. The role of tpen as a base is discussed.

Angewandte Chemie International EditionVolume 43, Issue 7 p. 850-852 Communication Rational Design of an Enneanuclear Copper(II) Complex with a Metallacyclophane Core† Xavier Ottenwaelder Dr., Xavier Ottenwaelder Dr. Laboratoire de Chimie Inorganique, CNRS UMR 8613, Université Paris-Sud, 91405 Orsay, France, Fax: (+33) 169-154-754Search for more papers by this authorJoan Cano Dr., Joan Cano Dr. Laboratoire de Chimie Inorganique, CNRS UMR 8613, Université Paris-Sud, 91405 Orsay, France, Fax: (+33) 169-154-754Search for more papers by this authorYves Journaux Dr., Yves Journaux Dr. jour@icmo.u-psud.fr Laboratoire de Chimie Inorganique, CNRS UMR 8613, Université Paris-Sud, 91405 Orsay, France, Fax: (+33) 169-154-754Search for more papers by this authorEric Rivière Dr., Eric Rivière Dr. Laboratoire de Chimie Inorganique, CNRS UMR 8613, Université Paris-Sud, 91405 Orsay, France, Fax: (+33) 169-154-754Search for more papers by this authorConor Brennan Dr., Conor Brennan Dr. Laboratoire de Chimie Inorganique, CNRS UMR 8613, Université Paris-Sud, 91405 Orsay, France, Fax: (+33) 169-154-754Search for more papers by this authorMartine Nierlich Dr., Martine Nierlich Dr. CEA, Service de Chimie Moléculaire DSM/DRECAM, Centre d'Etudes de Saclay Bât. 125, 91191 Gif sur Yvette Cedex (France)Search for more papers by this authorRafael Ruiz-García Dr., Rafael Ruiz-García Dr. Departament de Química Orgànica, Facultat de Química, Universitat de València, 46100 Burjassot, València, SpainSearch for more papers by this author Xavier Ottenwaelder Dr., Xavier Ottenwaelder Dr. Laboratoire de Chimie Inorganique, CNRS UMR 8613, Université Paris-Sud, 91405 Orsay, France, Fax: (+33) 169-154-754Search for more papers by this authorJoan Cano Dr., Joan Cano Dr. Laboratoire de Chimie Inorganique, CNRS UMR 8613, Université Paris-Sud, 91405 Orsay, France, Fax: (+33) 169-154-754Search for more papers by this authorYves Journaux Dr., Yves Journaux Dr. jour@icmo.u-psud.fr Laboratoire de Chimie Inorganique, CNRS UMR 8613, Université Paris-Sud, 91405 Orsay, France, Fax: (+33) 169-154-754Search for more papers by this authorEric Rivière Dr., Eric Rivière Dr. Laboratoire de Chimie Inorganique, CNRS UMR 8613, Université Paris-Sud, 91405 Orsay, France, Fax: (+33) 169-154-754Search for more papers by this authorConor Brennan Dr., Conor Brennan Dr. Laboratoire de Chimie Inorganique, CNRS UMR 8613, Université Paris-Sud, 91405 Orsay, France, Fax: (+33) 169-154-754Search for more papers by this authorMartine Nierlich Dr., Martine Nierlich Dr. CEA, Service de Chimie Moléculaire DSM/DRECAM, Centre d'Etudes de Saclay Bât. 125, 91191 Gif sur Yvette Cedex (France)Search for more papers by this authorRafael Ruiz-García Dr., Rafael Ruiz-García Dr. Departament de Química Orgànica, Facultat de Química, Universitat de València, 46100 Burjassot, València, SpainSearch for more papers by this author First published: 02 February 2004 https://doi.org/10.1002/anie.200352851Citations: 53 † This work was supported by the European Community (contract HPRN-CT-1999-00012/TMR network “MolNanoMag”). Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Abstract A hexakis-bidentate building block: Tricopper(II) and enneacopper(II) 1,3,5-metallacyclophanes were synthesized by a combination of self-assembly and a rational approach (see scheme). Both complexes exhibit ferromagnetic coupling in the core, through a spin-polarization mechanism. Citing Literature Volume43, Issue7February 6, 2004Pages 850-852 RelatedInformation

A new mu-phenoxo-bis-mu-acetato di-Mn(II) complex using the BpmpH ligand was isolated as a perchlorate salt (BpmpH = 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methyl-phenol). The X-ray structure has been solved showing that the two Mn(II) ions are in a distorted octahedral environment. Investigation of the variation of the molar magnetic susceptibility upon temperature reveals an antiferromagnetic exchange interaction between the two high-spin Mn(II) ions. Fitting of the experimental data led to g = 1.99 and J = 9.6 cm(-1) (H(HDvV) = JS(A).S(B)). EPR spectra recorded on a powder sample of [(Bpmp)Mn(2)(mu-OAc)(2)](ClO(4)).0.5H(2)O at X-band between 4.3 K and room temperature and at Q-band between 5 and 298 K are presented. A new method based on a scrupulous examination of the variation upon temperature of these experimental spectra is developed here to first assign the transitions to the relevant spin states and second to determine the associated spin parameters. This approach is compared to the deconvolution process that has been previously applied to dinuclear Mn(II) complexes or metalloenzyme active sites. Crystallographic data is as follows: triclinic, space group P one macro, a = 10.154(2) A, b = 12.0454(2) A, c = 17.743(4) A, alpha = 101.69(3) degrees, beta = 93.62(3) degrees, gamma = 94.67(3) degrees, Z = 2.

The crystal structure of the complex 12.calix-[4]-arene dihydroxyphosphonic acid, 12.propane diammonium, 12.ethanol and 40.water molecules is based on dimeric units of the calix, assembled via trigonal units into a hexameric tube of 15 A radius and 16 A depth, further assemby via spanning propane diammonium cations and ethanol molecules forms a channel (40 A), selectively containing all the water molecules.