Cooperative Magnetic Behavior in Metal‐Dicyanamide Complexes

Manson, Jamie L.

doi:10.1002/3527604383.ch3

Cited by 3 publications

(2 citation statements)

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“…In recent years, much attention has been devoted to dicyanamide (dca)-bridged polynuclear systems because of the large variety of topologies and magnetic properties that result from the versatility of dca as a ligand (Scheme ). The α-M(dca) 2 series of compounds, which has isomorphous rutile-like structure, displays ferromagnetism [Co ( T c = 9 K) and Ni ( T c = 20 K)], , spin-canted antiferromagnetism [Cr ( T N = 47 K), Mn ( T N = 16 K), and Fe ( T N =19 K)], and paramagnetism (Cu) . The unusual magnetic properties of these compounds have encouraged the characterization of a large number of new coordination polymers containing the dca ligand and different auxiliary ligands which can be monodentate, polydentate or bridging .…”

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confidence: 99%

Ligand Effects on the Structures of Extended Networks of Dicyanamide-Containing Transition-Metal Ions

et al. 2006

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The structural characterization of a series of complexes of formula [M(dca)2L]n, where dca = dicyanamide, L = 1,10-phenanthroline (phen) [1-4] and 2,9-dimethylphenanthroline (2,9-dmphen) [9-12], and M = Mn (1 and 9), Fe (2 and 10), Co (3 and 11), and Ni (4 and 12), has revealed the effect of the presence of the methyl substituents of L on the resulting network. The structure of [Mn(dca)2(phen)]n (1), which is identical to those of 2-4, together with the investigation of its magnetic properties in the temperature range of 77-300 K were reported elsewhere. The use of the 4,7-dimethylphenanthroline (4,7-dmphen) as the co-ligand yielded a series of compounds of formula [M(dca)2(4,7-dmphen)]n [M = Mn (5), Fe (6), Co (7), and Ni (8)], which are isostructural with 1-4. Compounds containing phen (1-4) and 4,7-dmphen (5-8) are made of two-dimensional grids of metal atoms, each metal atom being linked to three other metal centers through single (three metal atoms involved) and double (two metal atoms involved) dca bridges exhibiting the mu-1,5 coordination mode. The isostructural complexes [M(dca)2(2,9-dmphen)]n (9-12) also have a sheetlike structure, the metal atoms in each layer being linked by two single and one double mu-1,5-dca units, as in 1-8. However, the topology of the network in 9-12 is different from that in 1-8 because of the different arrangement of the two single mu-1,5 dca bridges: cis in 1-8 versus trans in 9-12. The magnetic study of compounds 1-12 in the temperature range of 1.9-290 K has revealed the occurrence of weak ferromagnetic (M = Ni) and antiferromagnetic interactions (M = Mn, Fe, and Co). The different magnetic behavior in 1-12 was analyzed in the light of their structures, and the values of the magnetic interactions were compared to those of related systems.

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Section: Introductionmentioning

confidence: 99%

Ligand Effects on the Structures of Extended Networks of Dicyanamide-Containing Transition-Metal Ions

et al. 2006

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“…The shortest Cu/Cu interactions are between the legs of adjacent triple ladders: the Cu1/ Cu4 distances are 4.003(1) and 6.497(1) A ˚. 4)eN( 5)eC (3) 129.8( 9) The cyano stretching region of the infrared spectrum for (PPh 4 ) 3 [Cu 4 (dca) 11 ] is compared to that of PPh 4 (dca) and Cu(dca) 2 in Fig. 4.…”

Section: Resultsmentioning

confidence: 99%

A novel pseudo-2D structural motif in an anionic copper(II) dicyanamide coordination polymer

Schlueter

Manson

Geiser

2006

Comptes Rendus. Chimie

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Anionic coordination polymers of divalent first-row transition elements are promising components of multifunctional molecular materials in which electronic conduction and magnetism can coexist. We report that a tetraphenylphosphonium salt containing a copper(II) dicyanamide anion has a novel pseudo-two-dimensional anionic structure and may provide a suitable electrolyte for the electrocrystallization of charge transfer salts. This (PPh 4 ) 3 Cu 4 (dca) 11 salt crystallizes in the monoclinic space group P2 1 with lattice parameters, a

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Role of Temperature and Pressure on the Multisensitive Multiferroic Dicyanamide Framework [TPrA][Mn(dca)₃] with Perovskite-like Structure

et al. 2015

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A multistimuli response to temperature and pressure is found in the hybrid inorganic-organic perovskite-like [TPrA][Mn(dca)3] compound, which is related to a first-order structural phase transition near room temperature, Tt ≈ 330 K. This phase transition involves a transformation from room temperature polymorph I, with the noncentrosymmetric space group P4̅21c, to the high temperature polymorph II, with the centrosymmetric space group I4/mcm, and it implies ionic displacements, order-disorder phenomena, and a large and anisotropic thermal expansion (specially along the c-axis). As a consequence, [TPrA][Mn(dca)3] exhibits a dielectric anomaly, associated with the change from a cooperative to a noncooperative electric behavior (antiferroelectric (AFE)-paraelectric (PE) transition). The former implies an AFE distribution of electric dipoles in polymorph I, related to the described off-shift of the apolar TPrA cations and the order-disorder of the polar dca ligands mechanisms, that are different from those reported, up to now, for others perovskite-type hybrid compounds. Such cooperative electric order, below Tt ≈ 330 K, coexisting with long-range antiferromagnetic ordering below T = 2.1 K render the [TPrA][Mn(dca)3] a new type-I multiferroic material. In addition, the obtained experimental results reveal that this compound is also a multistimuli-responsive material, with a very large sensitivity toward temperature and applied external pressure, δTt/δP ≈ 24 K kbar(-1), even for small values of pressure (P < 2 kbar). Therefore, this material opens up a potential interest for future technological applications, such as temperature/pressure sensing.

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Cooperative Magnetic Behavior in Metal‐Dicyanamide Complexes

Cited by 3 publications

References 73 publications

Ligand Effects on the Structures of Extended Networks of Dicyanamide-Containing Transition-Metal Ions

Ligand Effects on the Structures of Extended Networks of Dicyanamide-Containing Transition-Metal Ions

A novel pseudo-2D structural motif in an anionic copper(II) dicyanamide coordination polymer

Role of Temperature and Pressure on the Multisensitive Multiferroic Dicyanamide Framework [TPrA][Mn(dca)₃] with Perovskite-like Structure

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Cooperative Magnetic Behavior in Metal‐Dicyanamide Complexes

Cited by 3 publications

References 73 publications

Ligand Effects on the Structures of Extended Networks of Dicyanamide-Containing Transition-Metal Ions

Ligand Effects on the Structures of Extended Networks of Dicyanamide-Containing Transition-Metal Ions

A novel pseudo-2D structural motif in an anionic copper(II) dicyanamide coordination polymer

Role of Temperature and Pressure on the Multisensitive Multiferroic Dicyanamide Framework [TPrA][Mn(dca)3] with Perovskite-like Structure

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Role of Temperature and Pressure on the Multisensitive Multiferroic Dicyanamide Framework [TPrA][Mn(dca)₃] with Perovskite-like Structure