Recent Advances on Anilato-Based Molecular Materials with Magnetic and/or Conducting Properties

Mercuri, Maria Laura; Congiu, Francesco; Concas, Giulio; Sahadevan, Suchithra Ashoka

doi:10.3390/magnetochemistry3020017

Cited by 81 publications

(76 citation statements)

References 212 publications

(255 reference statements)

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“…The magnetic properties of chloranilate‐bridged framework materials are currently of great interest– not only for those containing diamagnetic can 2− bridges but also, particularly, those containing radical can 3− bridges of the semiquinone type found in d‐block anilato families such as [Fe 2 (can) 3 ] 2− , the latter forming a 6,3‐ hexagonal network structure ,. The present 2D 4,4‐network is an attractive system to explore magnetic properties, including magnetic exchange, as each Ln III centre is bridged by four can 2− groups to neighbouring Ln III centres.…”

Section: Resultsmentioning

confidence: 99%

Square Grid Metal–Chloranilate Networks as Robust Host Systems for Guest Sorption

Kingsbury

Abrahams

Auckett

et al. 2019

Chemistry A European J

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Reaction of the chloranilate dianion with Y(NO3)3 in the presence of Et4N+ in the appropriate proportions results in the formation of (Et4N)[Y(can)2], which consists of anionic square‐grid coordination polymer sheets with interleaved layers of counter‐cations. These counter‐cations, which serve as squat pillars between [Y(can)2] sheets, lead to alignment of the square grid sheets and the subsequent generation of square channels running perpendicular to the sheets. The crystals are found to be porous and retain crystallinity following cycles of adsorption and desorption. This compound exhibits a high affinity for volatile guest molecules, which could be identified within the framework by crystallographic methods. In situ neutron powder diffraction indicates a size‐shape complementarity leading to a strong interaction between host and guest for CO2 and CH4. Single‐crystal X‐ray diffraction experiments indicate significant interactions between the host framework and discrete I2 or Br2 molecules. A series of isostructural compounds (cat)[MIII(X‐an)2] with M=Sc, Gd, Tb, Dy, Ho, Er, Yb, Lu, Bi or In, cat=Et4N, Me4N and X‐an=chloranilate, bromanilate or cyanochloranilate bridging ligands have been generated. The magnetic properties of representative examples (Et4N)[Gd(can)2] and (Et4N)[Dy(can)2] are reported with normal DC susceptibility but unusual AC susceptibility data noted for (Et4N)[Gd(can)2].

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Section: Resultsmentioning

confidence: 99%

Square Grid Metal–Chloranilate Networks as Robust Host Systems for Guest Sorption

Kingsbury

Abrahams

Auckett

et al. 2019

Chemistry A European J

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“…We noticed that chloranilate (Cl2An 2− ) is a promising organic ligand for investigating the above-mentioned Ln III -based SMMs or SIMs. The dianionic form of Cl2An 2− has a delocalized π system with resonance structures that are represented by p-quinone, o-quinone, tetraquinone, and bi-separated delocalized forms (Scheme 1) [24,25]. The coordination geometry and the ligand-field strength of the central Ln III ion can be fine-tuned by combining Cl2An 2− with a suitable ancillary ligand, while maintaining a similar coordination environment.…”

Section: Introductionmentioning

confidence: 99%

Field-Induced Slow Magnetic Relaxation of Mono- and Dinuclear Dysprosium(III) Complexes Coordinated by a Chloranilate with Different Resonance Forms

et al. 2017

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Abstract:We synthesized the dinuclear and mononuclear dysprosium(III) complexes [{Dy(Tp) 2 } 2 (Cl 2 An)]·2CH 2 Cl 2 (1) and [Co(Cp) 2 ][Dy(Tp) 2 (Cl 2 An)] (3), where Cl 2 An 2− and Tp − are the chloranilate and hydrotris(pyrazolyl)borate ligand, respectively. In addition, the magnitude of the magnetic coupling between the lanthanide centers through the Cl 2 An 2− bridge has been probed through the synthesis of [{Gd(Tp) 2 } 2 (Cl 2 An)]·2CH 2 Cl 2 (2), which is a gadolinium(III) analogue of 1. Complexes 1-3 were characterized by infrared (IR) spectroscopy, elemental analysis, single-crystal X-ray diffraction, and SQUID measurements. IR and single-crystal X-ray structural analyses confirm that the coordination environments of the lanthanide(III) centers in 1 and 3 are similar to each other; i.e., eight-coordinated metal centers, each occupied by an N 6 O 2 donor set from two Tp − ligands and one Cl 2 An 2− ligand. The coordination geometries of the lanthanide(III) centers in 1 and 2 are distorted triangular dodecahedral, while that in the mononuclear complex 3 is square antiprismatic, where the Cl 2 An 2− ligand takes the bi-separated delocalized form in 1 and 2, and the o-quinone form in 3. Alternating-current (AC) magnetic studies clearly reveal that both 1 and 3 exhibit field-induced slow relaxations of magnetization that occur via Raman and direct processes. Complexes 1 and 3 exhibit different spin relaxation behavior, which reflects the coordination geometry around each Dy III center and its nuclearity, as well as the molecular packing in the crystal lattice. Although the magnetic analysis of 2 revealed negligible magnetic coupling, Cl 2 An 2− bridges with small biases may form in the dinuclear complexes, which play roles in the spin relaxation dynamics through dipolar interactions.

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“…The similarities of oxalato and anilato-type ligands can be clearly seen in the classical chiral [M(L)3] 3− monomers [24,25], as well as in the extended 2D and 3D lattices observed for both ligands [22,[26][27][28][29][30]. a b Although anilato-type ligands have been mainly used with transition metal ions [22,23], there are also several examples of anilato-based compounds with lanthanoids (Tables 1-4). These compounds can be formulated as [Ln2(C6O4X2)3(G)n]•mG, and can be grouped into different series depending on X (the anilato-type ligand) and G (the solvent used).…”

Section: Introductionmentioning

confidence: 99%

“…Other ligands include aromatic amines and quinones, such as the 2,5-dihydroxy-1,4-benzoquinone dianion (C6O4H2) 2− = dhbq, and the corresponding 3,6-disubstituted dianions (C6O4X2) 2− , with X = Cl, Br, NO2, CN, ... (Figure 1) [22,23]. These derivatives of 2,5-dihydroxy-1,4-benzoquinone (anilato-type ligands) are becoming popular ligands, since they resemble the oxalato ligand (Figure 1), although with some advantages.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, for X = H (i.e., with the ligand C6O4H2 2− = dhbq 2− ) and G = H2O (Table 1), all the Ln(III) ions form isostructural compounds (phase I) formulated as [Ln2(C6O4H2)3(H2O)6]•18H2O, whose structure consists in a (6,3)-2D honeycomb lattice formed by regular (although not planar) hexagons, and where the Ln(III) ions are nona-coordinated with a tri-capped trigonal prismatic geometry [31][32][33]. [31] When X = Cl (i.e., with the ligand C6O4Cl2 2− = chloranilato) and G = H2O (Table 2), up to four different phases, formulated as [Ln2(C6O4Cl2)3(H2O)6]•nH2O, could be prepared, depending Although anilato-type ligands have been mainly used with transition metal ions [22,23], there are also several examples of anilato-based compounds with lanthanoids (Tables 1-4). These compounds can be formulated as [Ln 2 (C 6 O 4 X 2 ) 3 (G) n ]·mG, and can be grouped into different series depending on X (the anilato-type ligand) and G (the solvent used).…”

Section: Introductionmentioning

confidence: 99%

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Tuning the Structure and Properties of Lanthanoid Coordination Polymers with an Asymmetric Anilato Ligand

et al. 2018

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Recent Advances on Anilato-Based Molecular Materials with Magnetic and/or Conducting Properties

Cited by 81 publications

References 212 publications

Square Grid Metal–Chloranilate Networks as Robust Host Systems for Guest Sorption

Square Grid Metal–Chloranilate Networks as Robust Host Systems for Guest Sorption

Field-Induced Slow Magnetic Relaxation of Mono- and Dinuclear Dysprosium(III) Complexes Coordinated by a Chloranilate with Different Resonance Forms

Tuning the Structure and Properties of Lanthanoid Coordination Polymers with an Asymmetric Anilato Ligand

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