Fernando S. Delgado

Structural versatility of the malonate ligand as a tool for crystal engineering in the design of molecular magnets

The synthesis of ferro- and ferri-magnetic systems with a tunable Tc and three-dimensional (3-D) ordering from molecular precursors implying transition metal ions is one of the active branches of molecular inorganic chemistry. The nature of the interactions between the transition metal ions (or transition metal ions and radicals) is not so easy to grasp by synthetic chemists working in this field since it may be either electrostatic (orbital) or magnetic (mainly dipolar). Therefore, the systems fulfilling the necessary requirements to present the expected magnetic properties are not so easy to design on paper and realize in the beaker. In this work we show how the design of one-, two- and three-dimensional materials can strongly benefit from the use of crystal engineering techniques, which can give rise to structures of different shapes, and how these differences can give rise to different properties. We will focus on the networks constructed by assembling malonate ligands and metal centres. The idea of using malonate (dianion of propanedioic acid, H2mal) is that it can give rise to different coordination modes with the metal ions it binds. Extended magnetic networks of dimensionalities one (1-D), two (2-D) and three (3-D) can be chemically constructed from malonate-bridged metallic complexes. These coordination polymers behave as ferro-, ferri- or canted antiferro-magnets. We are currently trying to obtain analogous compounds using magnetically anisotropic ions, such as cobalt(II), in order to explore how structural differences influence the magnetic properties. In this case the control of the spatial arrangement of the magnetic building blocks is of paramount importance in determining the strength of the magnetic interaction. The possibility of controlling the shape of the networks depends on the coordination bond between the metal ion and the ligands and on supramolecular interactions such as stacking interactions or hydrogen bonding.

Malonate-based copper(II) coordination compounds: ferromagnetic coupling controlled by dicarboxylates

Studies on structural and magnetic properties of polynuclear transition metal complexes, aimed at understanding the structural and chemical factors governing electronic exchange coupling mediated by multiatom bridging ligands, are of continuing interest to design new molecular materials exhibiting unusual magnetic, optical and electrical properties, bound to their molecular nature. Looking at potentially flexible bridging ligands, the malonate group seems a suitable candidate. The occurrence of two carboxylate groups in the 1,3 positions allows this ligand to adopt simultaneously chelating bidentate and different carboxylato bridging modes (syn–syn, anti–anti and syn–anti trough one or two carboxylate groups) In the course of our research we have structurally and magnetically characterized several carboxylato bridged copper(II) complexes. In the present study we start describing briefly the structure and the magnetic behaviour of the compounds, subsequently we analyze the magneto-structural correlations concluding that the parameter that governs, in first order, the magnetic interaction between metal centres is the relative position of the carboxylato bridge of the malonate respect to the copper(II) ions: equatorial–equatorial (strong interaction), equatorial–apical (weak interaction) and apical–apical (negligible interaction). Inside this division another parameters become important such as β (angle between copper(II) basal planes) in the equatorial–equatorial, or the distortion t in the equatorial–apical.

Synthesis, crystal structure and magnetic properties of two-dimensional malonato-bridged cobalt(II) and nickel(II) compounds

Two isostructural malonato-bridged complexes of formula {[M(H2O)2][M(mal)2(H2O)2]}n [M = Co(II) (1), Ni(II) (2); H2mal = malonic acid] have been synthesised and characterized by X-ray diffraction. Their structure consists of corrugated layers of trans-diaquabismalonatemetalate(II) and trans-diaquametal(II) units bridged by carboxylate–malonate groups in the anti–syn conformation. Two crystallographycally independent metal atoms occur in 1 and 2. The malonate anion acts simultaneously as a bidentate and bis-monodentate ligand. Variable-temperature (1.9–295 K) magnetic susceptibility measurements indicate the occurrence of weak antiferro- (1) and ferromagnetic (2) interactions between the cobalt(II) (1) and nickel(II) ions (2) through the anti–syn caboxylate–malonate bridge. A brief discussion on the structural diversity and crystal engineering possibilities of the malonate complexes with divalent first-row transition metal ions other than copper(II) is carried out.

Malonic acid: a multi-modal bridging ligand for new architectures and properties on molecule-based magnets

Abstract In this work, we show how the design of one-, two- and three-dimensional materials can strongly benefit from the use of crystal engineering techniques, which can give rise to structures of different shapes, and how these differences can give rise to different properties. We will focus on the networks constructed by assembling malonate ligands and metal centres. The idea of using malonate (dianion of propanedioic acid, H 2 mal) is that they can give rise to different coordination modes with the metal ions bind. Extended magnetic networks of dimensionalities 1 (1D), 2 (2D) and 3 (3D) can be chemically constructed from malonato-bridged metallic complexes. These coordination polymers behave as ferro-, ferri- or canted antiferromagnets. The control of the spatial arrangement of the magnetic building blocks is of paramount importance in determining the strength of the magnetic interaction. It depends on the coordination bond between the metal ion and the ligands, and on supramolecular interactions such as stacking interactions or hydrogen bonds.

Crystal structure and magnetic properties of two isomeric three-dimensional pyromellitate-containing cobalt(II) complexes.

The hydrothermal preparation, crystal structure determination, and magnetic study of two isomers made up of 1,2,4,5-benzenetetracarboxylate and high-spin Co(II) ions of formula [Co2(bta)(H2O)4]n x 2n H2O (1 and 2; H4bta = 1,2,4,5-benzenetetracarboxylic acid) are reported. 1 and 2 are three-dimensional compounds whose structures can be described as (4,4) rectangular layers of trans-diaquacobalt(II) units with the bta(4-) anion acting as tetrakis-monodentate ligand through the four carboxylate groups, which are further connected through other trans-[Co(H2O)2](2+) (1) and planar [Co(H2O)4](2+) (2) entities, with the bridging units being a carboxylate group in either the anti-syn (1) or syn-syn (2) conformations and a water molecule (2). The study of the magnetic properties of 1 and 2 in the temperature range 1.9-300 K shows the occurrence of weak antiferromagnetic interactions between the high-spin Co(II) ions, with the strong decrease of chi(M)T upon cooling being mainly due to the depopulation of the higher energy Kramers doublets of the six-coordinated Co(II) ions. The computed values of the exchange coupling between the Co(II) ions across anti-syn carboxylate (1) and syn-syn carboxylate/water (2) bridges are J = -0.060 (1) and -1.90 (2) cm(-1) (with the Hamiltonian being defined as H = -Jsigma(i,j)S(i) x S(j)). These values follow the different conformations of the carboxylate bridge in 1 (anti-syn) and 2 (syn-syn) with the occurrence of a double bridge in 2 (water/carboxylate).

The flexibility of molecular components as a suitable tool in designing extended magnetic systems

In this work we show how the design of n-dimensional magnetic compounds (nD with n = 1–3) can strongly benefit from the use crystal engineering techniques, which can give rive to structures of different shapes with different properties. We focus on the networks built by assembling the malonato-bridged tetranuclear copper(II) units Cu4(mal)4 (mal2− is the dianion of propanedioic acid, H2mal) through the potentially bridging 2,4′-bipyridine (2,4′-bpy), 4,4′-bipyridine (4,4′-bpy) and pyrazine (pyz). The magneto-structural study of the complexes of formula [Cu4(mal)4(2,4′-bpy)4(H2O)4]·8H2O (1), [Cu4(mal)4(H2O)4(4,4′-bpy)2] (2) (this compound was the subject of a previous report but it is included here for comparison) and [Cu4(mal)4(pyz)2]·4H2O (3) reveals that the ferromagnetically coupled Cu4(mal)4 unit which occurs in 1–3 is propagated into two- (2) and three-dimensions (3) by using 4,4′-bpy and pyz as linkers, respectively. Whereas in the case of complex 1, this tetranuclear unit is magnetically isolated, significant antiferromagnetic interactions between these units mediated by the bridges 4,4′-bpy and pyz occur in 2 and 3.

Insertion of a spin crossover Fe(III) complex into an oxalate-based layered material: coexistence of spin canting and spin crossover in a hybrid magnet.

The syntheses, structures, and magnetic properties of the compounds of formula [Fe (III)(sal 2trien)] 2[Mn (II) 2(ox) 3].4H 2O.C 3H 7NO ( 1) and [In (III)(sal 2trien)] 2[Mn (II) 2(ox) 3].3H 2O.CH 3OH (2) are reported. The structure presents a homometallic 2D honeycomb anionic layer formed by Mn (II) ions linked through oxalate ligands and a cationic double layer of [Fe(sal 2trien)] (+) or [In(sal 2trien)] (+) complexes intercalated between the 2D oxalate network. The magnetic properties and Mössbauer spectroscopy of 1 indicate the coexistence of a magnetic ordering of the Mn(II) oxalate network that behaves as a weak ferromagnet and a gradual spin crossover of the intercalated [Fe(sal 2trien)] (+) complexes.

Cobalt(II) Sheet-Like Systems Based on Diacetic Ligands: from Subtle Structural Variances to Different Magnetic Behaviors

The preparation, X-ray crystallography, and magnetic investigation of the compounds [Co(H(2)O)(2)(phda)](n) (1), [Co(phda)](n) (2), and [Co(chda)](n) (3) [H(2)phda = 1,4-phenylenediacetic acid and H(2)chda = 1,1-cyclohexanediacetic acid] are described herein. The cobalt atoms in this series are six- (1) and four-coordinated (2 and 3) in distorted octahedral (CoO(6)) and tetrahedral (CoO(4)) environments. The structures of 1-3 consists of rectangular-grids which are built up by sheets of cobalt atoms linked through anti-syn carboxylate bridges, giving rise to either a three-dimensional structure across the phenyl ring (1 and 2) or to regularly stacked layers with the cyclohexyl groups acting as organic separators (3). The magnetic properties of 1-3 were investigated as a function of the temperature and the magnetic field. Ferromagnetic coupling between the six-coordinate cobalt(II) ions across the anti-syn carboxylate bridge occurs in 1 (J = +1.2 cm(-1)) whereas antiferromagnetic coupling among the tetrahedral cobalt(II) centers within the sheets is observed in 2 and 3 [J = -1.63 (2) and -1.70 cm(-1) (3)] together with a spin-canted structure in 3 giving rise a long-range magnetic ordering (T(c) = 7.5 K).

Intramolecular ferro- and antiferromagnetic interactions in oxo-carboxylate bridged digadolinium(III) complexes

Two new digadolinium(III) complexes with monocarboxylate ligands, [Gd2(pac)6(H2O)4] (1) and [Gd2(tpac)6(H2O)4] (2) (Hpac = pentanoic acid and Htpac = 3-thiopheneacetic acid), have been prepared and their structures determined by X-ray diffraction on single crystals. Their structures consist of neutral and isolated digadolinium(III) units, containing six monocarboxylate ligands and four coordinated water molecules, the bridging skeleton being built by a muO(1):kappa2O(1)O(2) framework. This structural pattern has already been observed in the parent acetate-containing compound [Gd2(ac)6(H2O)4] x 4 H2O (3) whose structure and magnetic properties were reported elsewhere (L. Cañadillas-Delgado, O. Fabelo, J. Cano, J. Pasán, F. S. Delgado, M. Julve, F. Lloret and C. Ruiz-Pérez, CrystEngComm, 2009, 11, 2131). Each gadolinium(III) ion in 1 and 2 is nine-coordinated with seven carboxylate-oxygen atoms from four pac (1)/tpac (2) ligands and two water molecules (1 and 2) building a distorted monocapped square antiprism. The values of the intramolecular gadolinium-gadolinium separation are 4.1215(5) (1), 4.1255(6) (2) and 4.1589(3) A (3) and those of the angle at the oxo-carboxylate bridge (theta) are 113.16(13) (1), 112.5(2) (2) and 115.47(7) degrees (3). Magnetic susceptibility measurements in the temperature range 1.9-300 K reveal the occurrence of a weak intramolecular antiferromagnetic interaction [J = -0.032(1) (1) and -0.012(1) cm(-1) (2), the Hamiltonian being defined as H = -JS(A) x S(B)] in contrast with the intramolecular ferromagnetic coupling which occurs in 3 (J = +0.031(1) cm(-1)). The magneto-structural data of 1-3 show the relevance of the geometrical parameters at the muO(1):kappa2O(1)O(2) bridge on the nature of the magnetic coupling between two gadolinium(III) ions.

Dinuclear and two- and three-dimensional gadolinium(III) complexes with mono- and dicarboxylate ligands: synthesis, structure and magnetic properties

Three new gadolinium(III) complexes with carboxylate ligands of formula [Gd2(ac)6(H2O)4]·2H2O (1), [Gd2(ac)2(fum)2(H2O)4]n (2) and [Gd2(ox)(fum)2(H2O)4]n·4nH2O (3) (ac = acetate, fum = fumarate and ox = oxalate) have been prepared and their structures determined by X-ray diffraction on single crystals. The structure of 1 is made up of discrete centrosymmetric di-µ-oxo(carboxylate acetate)digadolinium(III) units with an intramolecular Gd⋯Gd separation of 4.1589(3) A. Each gadolinium atom in 1 is nine-coordinated with two water molecules and seven carboxylate-oxygen atoms from four acetate ligands building a monocapped square antiprism environment. Compound 2 exhibits a sheet-like structure, the repeating intralayer motif being a rectangle of di-µ-oxo(carboxylate acetate)digadolinium(III) units [Gd⋯Gd separation of 3.8659(10) A] where the edges are defined by bridging bis-bidentate and tetrakis-monodentate fumarate groups. Each gadolinium atom in 2 is nine-coordinated with two water molecules and seven carboxylate oxygens from two acetate and three fumarate ligands building a distorted monocapped square antiprism. Compound 3 has a three-dimensional structure where chains of double oxo(carboxylate fumarate)-bridged gadolinium(III) ions are interlinked by bis-bidentate fumarate to afford layers which are further interconnected through bis-bidentate oxalate ligands. The corresponding values of the Gd⋯Gd separation are 4.5816(1), 8.2292(2) and 6.2989(1) A. Each gadolinium atom in 3 is ten-coordinated with two water molecules and eight oxygen atoms from four fumarate ligands and one oxalate group building a distorted bicapped square antiprism. Variable-temperature magnetic susceptibility measurements show the occurrence of weak but significant ferro- (1 and 3) and antiferromagnetic (2) interactions through the double oxo(carboxylate acetate) (1 and 2), double syn-syncarboxylate fumarate (2) and double oxo(carboxylate fumarate) and bis-bidentate oxalate (3) bridges. Monte Carlo calculations were performed in the case of 3 to simulate its magnetic data and to substantiate the best-fit values of the magnetic couplings through the different exchange pathways involved.