Supramolecular coordination chemistry of aromatic polyoxalamide ligands: A metallosupramolecular approach toward functional magnetic materials

The impressive potential of the metallosupramolecular approach in designing new functional magnetic materials constitutes a great scientific challenge for the chemical research community that requires an interdisciplinary collaboration. New fundamental concepts and future applications in nanoscience and nanotechnology will emerge from the study of magnetism as a supramolecular function in metallosupramolecular chemistry. Our recent work on the rich supramolecular coordination chemistry of a novel family of aromatic polyoxalamide (APOXA) ligands with first-row transition metal ions has allowed us to move one step further in the rational design of metallosupramolecular assemblies of increasing structural and magnetic complexity. Thus, we have taken advantage of the new developments of metallosupramolecular chemistry and, in particular, the molecular-programmed self-assembly methods that exploit the coordination preferences of paramagnetic metal ions and suitable designed polytopic ligands. The resulting self-assembled di- and trinuclear metallacyclic complexes with APOXA ligands, either metallacyclophanes or metallacryptands, are indeed ideal model systems for the study of the electron exchange mechanism between paramagnetic metal centers through extended π-conjugated aromatic bridges. So, the influence of different factors such as the topology and conformation of the bridging ligand or the electronic configuration and magnetic anisotropy of the metal ion have been investigated in a systematic way. These oligonuclear metallacyclic complexes can be important in the development of a new class of molecular magnetic devices, such as molecular magnetic wires (MMWs) and switches (MMSs), which are major goals in the field of molecular electronics and spintronics. On the other hand, because of their metal binding capacity through the outer carbonyl-oxygen atoms of the oxamato groups, they can further be used as ligands, referred to as metal–organic ligands (MOLs), toward either coordinatively unsaturated metal complexes or fully solvated metal ions. This well-known “complex-as-ligand” approach affords a wide variety of high-nuclearity metal–organic clusters (MOCs) and high-dimensionality metal–organic polymers (MOPs). The judicious choice of the oligonuclear MOL, ranging from mono- to di- and trinuclear species, has allowed us to control the overall structure and magnetic properties of the final oxamato-bridged multidimensional (nD, n = 0–3) MOCs and MOPs. The intercrossing between short- (nanoscopic) and long-range (macroscopic) magnetic behavior has been investigated in this unique family of oxamato-bridged metallosupramolecular magnetic materials expanding the examples of low-dimensional, single-molecule (SMMs) and single-chain (SCMs) magnets and high-dimensional, open-framework magnets (OFMs), which are brand-new targets in the field of molecular magnetism and materials science

Low-Temperature Properties of Quasi-One-Dimensional Molecule-Based Ferromagnets

Quantum and thermal behaviors of low-dimensional mixed-spin systems are investigated with particular emphasis on the design of molecule-based ferromagnets. One can obtain a molecular ferromagnet by assembling molecular bricks so as to construct a low-dimensional system with a magnetic ground state and then coupling the chains or the layers again in a ferromagnetic fashion. Two of thus-constructed quasi-one-dimensional bimetallic compounds are qualitatively viewed within the spin-wave treatment, one of which successfully grows into a bulk magnet, while the other of which ends in a singlet ground state. Then, concentrating on the ferrimagnetic arrangement on a two-leg ladder which is well indicative of general coupled-chain ferrimagnets, we develop the spin-wave theory and fully reveal its low-energy structure. We inquire further into the ferromagnetic aspect of the ferrimagnetic ladder numerically calculating the sublattice magnetization and the magnetic susceptibility. There exists a moderate coupling strength between the chains in order to obtain the most ferromagnetic ferrimagnet.Comment: 10 pages, 7 figures embedded, to be published in J. Phys. Soc. Jpn. Vol.70, No.5 (2001

K⊂{[FeII^{II}(Tp)(CN)3_{3}]4_{4}[CoIII^{III}(pz^{pz}Tp)]3_{3}[CoII^{II}(pz^{pz}Tp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues

Straightforward access to a new cyanide-bridged {Fe$_{4}$Co$_{4}$} “molecular box” containing a potassium ion, namely K⊂{[Fe$^{II}$(Tp)(CN)$_{3}$]$_{4}$[Co$^{III}$($^{pz}$Tp)]$_{3}$[Co$^{II}$($^{pz}$Tp)]} (1) (with Tp and $^{pz}$Tp = tris- and tetrakis(pyrazolyl)borate, respectively), is provided, alongside its full characterisation. A detailed analysis of the molecular structure (X-ray diffraction, mass spectrometry, NMR spectroscopy) and electronic properties (EPR spectroscopy, SQUID magnetometry, UV/Vis spectroscopy, cyclic voltammetry) reveals that 1 shows slow magnetic relaxation and a remarkable photomagnetic effect at low temperature which is reminiscent of some FeCo Prussian Blue Analogues (PBAs), and is ascribed to a photo-induced electron transfer. However, in contrast with these inorganic polymers, the overall neutral compound 1 is soluble and remarkably stable in organic solvents such as CH2Cl2. Moreover, 1 shows interesting redox versatility, with electrochemical experiments revealing the possible access to six stable redox states

STUDY OF THE MAGNETIC INTERACTIONS IN A BIMETALLIC COMPLEX CuII (salen) NiII (hfa)2 BY POLARISED NEUTRON DIFFRACTION

The long distance magnetic interactions in the complex CuII (salen) NiII (hfa)2 are investigated by polarised neutron diffraction, which permits to determine the magnetisation density. The role of the oxygen bridging ligands in the antiferromagnetic Cu... Ni interaction is demonstrated

CHEMISTRY AND PHYSICS OF MOLECULAR BASED FERROMAGNETS

We propose a strategy to design molecular based ferromagnets, consisting of assembling ferrimagnetic chains within the crystal lattice in a ferromagnetic fashion. The chains may be either regular or alternating. Examples of both situations are presented. The magnetic properties are discussed. One of the compounds orders ferromagnetically at 14 K, which is the highest ordering temperature reported so far for this kind of molecular material

Supramolecular assembly with calix[6]arene and copper ions - Formation of a novel tetranuclear core exhibiting unusual redox properties and catecholase activity

International audienceThe supramolecular biomimetic chemistry based on calix[6]arene N-ligands has been further explored. A tris(imidazole)CuI complex was treated with 1 mol-equiv. of cuprous ion under dioxygen to produce a tetranuclear cupric species, X-ray structural determination of this novel Cu4 complex revealed that the self-inclusion of an imidazolyl coordinating arm into the hydrophobic calixarene cavity provides the base of coordination for a _ClImCu(OH)2CuIm2₂ assembly. The Cu4 core is maintained in solution and is stable even in a coordinating solvent such as acetonitrile. Magnetic susceptibility measurements evidenced a strong antiferromagnetic coupling in each Cu(OH)2Cu subunit with J = -408 cm-1. The complex displayed catecholase activity in the presence of 3,5-di-tert-butylcatechol behaving as a four-electron hole with, however, a sluggish Cu4 I → Cu4 II regeneration through O2 autooxidation. Finally, electrochemical studies revealed two oxidative reversible processes that successively gave rise to a _CuIICuIII__Cu2 II_ and a _CuIICuIII₂ mixed-valence species that could be characterized by UV/Vis and EPR spectroscopy, The overall structure and behavior of this tetranuclear complex is reminiscent of multicopper enzymes. © Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002

Interaction between heterobinuclear molecules and nature of the ground spin states in oximato-bridged [CuIIMII]2 bis-binuclear complexes (M=Cu, NI, Mn): crystal structure of [Cu(pdmg)Ni(Me3[12]N3)(EtOH)](ClO4)2

[EN] Two new heterobimetallic complexes [Cu(pdmg)Ni(Me-3[12]N-3)(CH3CH2OH)](ClO4)(2)(2) and [Cu(pdmg) Mn(bipy)(2)]-ClO4)(2) . H2O (3) (H(2)pdmg = 3,9-dimethyl-4,8-diazaundeca-3,8-diene-2 10-dione dioxime; Me-3[12]N-3 = 2,4,4-trimethyl-1,5,9-triazacyclododeca-1-ene; bipy = 2,2'-bipyridyl) have been prepared and characterized. The structure of 2 has been determined by single-crystal X-ray diffraction methods. It consists of [Cu(pdmg)Ni(Me-3[12]N-3)(CH3CH2OH)](2+) cations and non-coordinated perchlorate anions. The [Cu(pdmg)(CH3CH2OH)] complex coordinates to the [Ni(Me-3[12]N-3)](2+) fragment to afford the binuclear unit doubly-bridged by oximato groups in cis arrangement. The coordination geometry around the copper atom is square-pyramidal, whereas the nickel atom exhibits a trigonal-bipyramidal surrounding The intramolecular Cu-Ni distance is 3.810(6) Angstrom. In the crystal, two [(CuNII)-N-II] dimeric units are related through an inversion center, giving rise to a bis-binuclear entity with a relatively short intermolecular Cu-Cu separation of 4.175(6) Angstrom. Variable-temperature magnetic susceptibility measurements (2.0-300 K) for 2 correspond to an almost isolated Cu(II)Ni(Ir) pair with an intrapair interaction parameter J= -143.6(2) cm(-1). However, the EPR spectrum at 4.2 K is that of a triplet spin state arising from the interaction between the two doublet spin states within the [(CuNiII)-Ni-II](2) bis-binuclear entity. The magnetic properties of 3 unambiguously reveal the bis-binuclear nature of this compound, as is the case for the related homometallic complex [Cu(pdmg)Cu(bipy)(H2O)(2)](ClO4)(2). H2O (1). The intra- (J) and interpair (j) interaction parameters for 3, as deduced from the analysis of its magnetic susceptibility data in the temperature range 2.0-300 K, are - 50.9(2) and 1.50(2) cm(-1), respectively. The field dependence of the magnetization of 3 at 2.0 K corresponds to that of a nonet state arising from the interaction between two quintuplet spin states within the [(CuMnII)-Mn-II](2) bis-binuclear entity. The interaction between the heterobinuclear Cu(II)Mn(II) molecules and its influence on the nature of the ground spin state for 3 are analyzed and discussed in the framework of a spin polarization scheme.This work was supported by the Dirección General de Investigación Cientı́fica y Técnica (DGICYT) (Spain) through Project PB97-1397 the Spanish French Integrated Actions and the TMR program of the European Union through project ERBFMRXCT-980181. B. Cervera and R. Ruiz acknowledge the Conselleria de Cultura, Educació i Ciència de la Generalitat Valenciana and the Ministerio de Educación y Ciencia (Spain) for doctoral and post-doctoral grants, respectively. We are very indebted to Dr Ally Aukauloo for fruitful discussions during the preparation of the manuscript and continuous interest in this work.Cervera, B.; Ruiz, R.; Lloret, F.; Julve, M.; Faus, J.; Muñoz Roca, MDC.; Journaux, Y. (1999). Interaction between heterobinuclear molecules and nature of the ground spin states in oximato-bridged [CuIIMII]2 bis-binuclear complexes (M=Cu, NI, Mn): crystal structure of [Cu(pdmg)Ni(Me3[12]N3)(EtOH)](ClO4)2. Inorganica Chimica Acta. 288(1):57-68. https://doi.org/10.1016/S0020-1693(99)00035-3S5768288

Redox noninnocence of the bridge in copper(II) salophen and bis(oxamato) complexes

Two square-planar copper(II) complexes of 1,2-bis(2-hydroxy-3,5-di-tert-butylbenzimino)-4,5-bis(dimethylamino)benzene (1) and N-[4,5-bis(dimethylamino)-2-(oxalylamino)benzene]oxamate (22-) were prepared. The crystal structures of the proligands H2L1 and Et2H2L2, as well as the corresponding complexes, are reported. The proligands each display a one-electron-oxidation wave, which is assigned to oxidation of the bis(dimethylamino)benzene moiety into a π radical. Complexes 1 and 22- exhibit reversible one-electron-oxidation waves in their cyclic voltammograms (E1/21 = 0.14 and E1/22 = 0.31 V for 1 and E1/21 = -0.47 V vs Fc+/Fc for 22-). The first process corresponds to oxidation of the bis(dimethylamino)benzene central ring into a π radical, while the second process for 1 is ascribed to oxidation of the π radical into an α-diiminoquinone. The one-electron-oxidized species 1+ and 2- exhibit intense visible-near-IR absorptions, which are diagnostic of π radicals. They display a triplet signal in their electron paramagnetic resonance spectra, which stem from magnetic coupling between the ligand-radical spin and the copper(II) spin. The zero-field-splitting parameters are larger for 2- than 1+ because of greater delocalization of the spin density onto the coordinated amidato N atoms. Density functional theory calculations support a π-radical nature of the one-electron-oxidized complexes, as well as S = 1 ground spin states. The electrogenerated 12+ comprises a closed-shell diiminoquinone ligand coordinated to a copper(II) metal center. Both 1 and 2 catalyze the aerobic oxidation of benzyl alcohol, albeit with different yields

Link between Affinity and Cu(II) Binding Sites to Amyloid-β Peptides Evaluated by a New Water-Soluble UV-Visible Ratiometric Dye with a Moderate Cu(II) Affinity

Being able to easily determine the Cu(II) affinity for biomolecules of moderate affinity is important. Such biomolecules include amyloidogenic peptides, such as the well-known amyloid-β peptide involved in Alzheimer's disease. Here, we report the synthesis of a new water-soluble ratiometric Cu(II) dye with a moderate affinity (109 M-1 at pH 7.1) and the characterizations of the Cu(II) corresponding complex by X-ray crystallography, EPR, and XAS spectroscopic methods. UV-vis competition was performed on the Aβ peptide as well as on a wide series of modified peptides, leading to an affinity value of 1.6 × 109 M-1 at pH 7.1 for the Aβ peptide and to a coordination model for the Cu(II) site within the Aβ peptide that agrees with the one mostly accepted currently