Synthesis, structure and spectroscopic properties of chloranilate-bridged 4f–4f dinuclear complexes: a comparative study of the emission properties with Cr–Ln complexes

Subhan, Abdus; Kawahata, Ryouji; Nakata, Hajime; Fuyuhiro, Akira; Tsukuda, Toshiaki; Kaizaki, Sumio

doi:10.1016/j.ica.2004.03.032

Cited by 19 publications

(13 citation statements)

References 28 publications

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“…of the corresponding lanthanide chloride salt in water. The subsequent slow diffusion of hexane into a concentrated CH 2 Cl 2 solution of 1 gave purple rod-shaped crystals, with two CH 2 Cl 2 solvates per dinuclear unit, suitable for single-crystal X-ray diffraction studies [27]. On the other hand, reaction of 1 with 1 equiv.…”

Section: Syntheses and Characterizationsmentioning

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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Section: Syntheses and Characterizationsmentioning

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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“…All of the reactions and manipulations were performed under aerobic conditions at an ambient temperature. All the complexes were synthesized according to a previously reported method [21], with modifications. Single crystals suitable for single-crystal X-ray measurements were obtained by recrystallization from CH 2 Cl 2 /hexane.…”

Section: Methodsmentioning

confidence: 99%

“…The series of Cl 2 An 2− bridged neutral dinuclear Ln III complexes 1-5 were prepared by a slight modification of the original method reported by Kaizaki et al [21]; some of these complexes have been previously reported [22][23][24]. All the complexes were isolated as X-ray quality single crystals through several recrystallizations from a concentrated dichloromethane solution layered with hexane.…”

Section: Structural Descriptionsmentioning

confidence: 99%

“…On the other hand, the Kramers systems (complexes 4 and 5) clearly displayed a slow magnetic relaxation under applied dc fields, suggesting field-induced single-molecule magnets that occur through Orbach and Raman relaxation processes. Magnetochemistry 2019, 5, 30 2 of 12 of the representative cluster-type SMM [Mn III 8 Mn IV 4 O 12 (CH 3 COO) 16 (H 2 O) 24 ]·2CH 3 COOH·4H 2 O, which is based on first-row transition metal ions [19,20].Recently, chloralilate (Cl 2 An 2− ) bridged dinuclear Ln III complexes of the formula [{Ln III (Tp) 2 } 2 (µ-Cl 2 An)]·2CH 2 Cl 2 (Tp − = hydrotris(pyrazolyl)borate) have been reported in the literature [21][22][23][24]. In these complexes, the Dy III analogue displays a slow magnetic relaxation under small applied dc magnetic fields, thus behaving as a field-induced SMM [22][23][24].…”

mentioning

confidence: 99%

“…Recently, chloralilate (Cl 2 An 2− ) bridged dinuclear Ln III complexes of the formula [{Ln III (Tp) 2 } 2 (µ-Cl 2 An)]·2CH 2 Cl 2 (Tp − = hydrotris(pyrazolyl)borate) have been reported in the literature [21][22][23][24]. In these complexes, the Dy III analogue displays a slow magnetic relaxation under small applied dc magnetic fields, thus behaving as a field-induced SMM [22][23][24].…”

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confidence: 99%

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Series of Chloranilate-Bridged Dinuclear Lanthanide Complexes: Kramers Systems Showing Field-Induced Slow Magnetic Relaxation

et al. 2019

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A series of chloralilate-bridged dinuclear lanthanide complexes of formula [{Ln III (Tp) 2 } 2 (µ-Cl 2 An)]·2CH 2 Cl 2 , where Cl 2 An 2− and Tp − represent the chloranilate and hydrotris (pyrazolyl)borate ligands, respectively, and Ln = Gd (1), Tb (2), Ho (3), Er (4), and Yb (5) was synthesized. All five complexes were characterized by an elemental analysis, infrared spectroscopy, single crystal X-ray diffraction, and SQUID measurements. The complexes 1-5 in the series were all isostructural. A comparison of the temperature dependence of the dc magnetic susceptibility data of these complexes revealed clear differences depending on the lanthanide center. Ac magnetic susceptibility measurements revealed that none of the five complexes exhibited a slow magnetic relaxation under a zero applied dc field. On the other hand, the Kramers systems (complexes 4 and 5) clearly displayed a slow magnetic relaxation under applied dc fields, suggesting field-induced single-molecule magnets that occur through Orbach and Raman relaxation processes. Magnetochemistry 2019, 5, 30 2 of 12 of the representative cluster-type SMM [Mn III 8 Mn IV 4 O 12 (CH 3 COO) 16 (H 2 O) 24 ]·2CH 3 COOH·4H 2 O, which is based on first-row transition metal ions [19,20].Recently, chloralilate (Cl 2 An 2− ) bridged dinuclear Ln III complexes of the formula [{Ln III (Tp) 2 } 2 (µ-Cl 2 An)]·2CH 2 Cl 2 (Tp − = hydrotris(pyrazolyl)borate) have been reported in the literature [21][22][23][24]. In these complexes, the Dy III analogue displays a slow magnetic relaxation under small applied dc magnetic fields, thus behaving as a field-induced SMM [22][23][24]. This paper reports the syntheses, structures, and magnetic properties of a series of Cl 2 An 2− bridged dinuclear Ln complexes of the formula [{Ln(Tp) 2 } 2 (µ-Cl 2 An)]·2CH 2 Cl 2 [Ln = Gd (1), Tb (2), Ho (3), Er (4), and Yb (5)] to systematically investigate the magnetic properties in other Ln III analogues of [{Ln III (Tp) 2 } 2 (µ-Cl 2 An)]·2CH 2 Cl 2 .

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Synthesis, crystal structure and properties of a new lanthanide‐transition metal carbonyl cluster

Bai

et al. 2008

Applied Organom Chemis

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A new type heterobimetallic complex containing lanthanide and transition metal carbonyl cluster (Ln-M carbonyl cluster), Sm 2 {OOCCCo 3 (CO) 9 } 2 {OOCCF 3 } 4 {(CO) 9 Co 3 CCOOH} 4 , has been synthesized by reaction of (CO) 9 Co 3 CCOOH with Sm(OOCCF 3 ) 3 (H 2 O) 2 , and structurally characterized by single-crystal X-ray diffraction. Application of the complex as a catalyst precursor for hydrogenation of carbon monoxide (Fischer-Tropsch reaction) was explored, and the thermogravimetric behavior and magnetic properties of the compound were examined as well.

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Synthesis, structure and spectroscopic properties of chloranilate-bridged 4f–4f dinuclear complexes: a comparative study of the emission properties with Cr–Ln complexes

Cited by 19 publications

References 28 publications

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

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

Series of Chloranilate-Bridged Dinuclear Lanthanide Complexes: Kramers Systems Showing Field-Induced Slow Magnetic Relaxation

Synthesis, crystal structure and properties of a new lanthanide‐transition metal carbonyl cluster

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