Multifunctional one-dimensional rhodium(I)-semiquinonato complex: Substituent effects on crystal structures and solid-state properties

Minoru Mitsumi, Shoji Ohtake, Yuki Kakuno, Yuuki Komatsu, Yoshiki Ozawa, Koshiro Toriumi, Nobuhiro Yasuda, Nobuaki Azuma, Yuji Miyazaki

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Two new one-dimensional (1D) rhodium(I)-semiquinonato complexes formulated as [Rh(3,6-DBSQ-4,5-PDO)(CO)2]- (4; 3,6-DBSQ-4,5-PDO•- = 3,6-di-tert-butyl-4,5-(1,3-propanedioxy)-1,2-benzosemiquinonato) and [Rh(3,6-DBSQ-4,5-(N,N′-DEN))(CO)2]- (5; 3,6-DBSQ-4,5-(N,N′-DEN)•- = 3,6-di-tert-butyl-4,5-(N,N′-diethylenediamine)-1,2-benzosemiquinonato) were synthesized to explore the nature of the unusual structural phase transition and magnetic and conductive properties recently reported for [Rh(3,6-DBSQ-4,5-(MeO)2)(CO)2]- (3; 3,6-DBSQ-4,5-(MeO)2•- = 3,6-di-tert-butyl-4,5-dimethoxy-1,2-benzosemiquinonato). Their crystal structures and magnetic and conductive properties were investigated. Compounds 4 and 5 comprise neutral 1D chains of complex molecules stacked in a staggered arrangement with fairly short average Rh-Rh distances of 3.06 Å for 4 and 3.10 Å for 5. These distances are similar to those for 3 (3.09 Å); however, the molecules of 5 are strongly dimerized in the 1D chain. Compound 4 undergoes a first-order phase transition at Ttrs = 229.1 K, and its magnetic properties drastically change from antiferromagnetic coupling in the roomerature (RT) phase to strong ferromagnetic coupling in the lowerature (LT) phase. In addition, compound 4 exhibits a long-range ordering of net magnetic moments originating from the imperfect cancellation of antiferromagnetically coupled spins between the ferromagnetic 1D chains at TN = 10.9 K. Furthermore, this compound exhibits an interesting crossover from a semiconductor with a small activation energy (Ea = 31 meV) in the RT phase to a semiconductor with a large activation energy (Ea = 199 meV) in the LT phase. These behaviors are commonly observed for 3. Alternating current susceptibility measurements of 4, however, revealed a frequency-dependent phenomenon below 5.2 K, which was not observed for 3, thus indicating a slow spin relaxation process that possibly arises from the movements of domain walls. In contrast, compound 5, which possesses a strongly dimerized structure in its 1D chain, shows no sign of strong ferromagnetic interactions and is an insulator, with a resistivity greater than 7 × 107 ω cm.

Original languageEnglish
Pages (from-to)11710-11720
Number of pages11
JournalInorganic Chemistry
Volume53
Issue number21
DOIs
Publication statusPublished - Nov 3 2014
Externally publishedYes

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Rhodium
Carbon Monoxide
rhodium
Crystal structure
solid state
crystal structure
Activation energy
magnetic properties
Phase transitions
Semiconductor materials
Molecules
Domain walls
Relaxation processes
activation energy
Magnetic moments
Magnetic properties
cancellation
domain wall
molecules
alternating current

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Mitsumi, M., Ohtake, S., Kakuno, Y., Komatsu, Y., Ozawa, Y., Toriumi, K., ... Miyazaki, Y. (2014). Multifunctional one-dimensional rhodium(I)-semiquinonato complex: Substituent effects on crystal structures and solid-state properties. Inorganic Chemistry, 53(21), 11710-11720. https://doi.org/10.1021/ic5019532

Multifunctional one-dimensional rhodium(I)-semiquinonato complex : Substituent effects on crystal structures and solid-state properties. / Mitsumi, Minoru; Ohtake, Shoji; Kakuno, Yuki; Komatsu, Yuuki; Ozawa, Yoshiki; Toriumi, Koshiro; Yasuda, Nobuhiro; Azuma, Nobuaki; Miyazaki, Yuji.

In: Inorganic Chemistry, Vol. 53, No. 21, 03.11.2014, p. 11710-11720.

Research output: Contribution to journalArticle

Mitsumi, M, Ohtake, S, Kakuno, Y, Komatsu, Y, Ozawa, Y, Toriumi, K, Yasuda, N, Azuma, N & Miyazaki, Y 2014, 'Multifunctional one-dimensional rhodium(I)-semiquinonato complex: Substituent effects on crystal structures and solid-state properties', Inorganic Chemistry, vol. 53, no. 21, pp. 11710-11720. https://doi.org/10.1021/ic5019532
Mitsumi, Minoru ; Ohtake, Shoji ; Kakuno, Yuki ; Komatsu, Yuuki ; Ozawa, Yoshiki ; Toriumi, Koshiro ; Yasuda, Nobuhiro ; Azuma, Nobuaki ; Miyazaki, Yuji. / Multifunctional one-dimensional rhodium(I)-semiquinonato complex : Substituent effects on crystal structures and solid-state properties. In: Inorganic Chemistry. 2014 ; Vol. 53, No. 21. pp. 11710-11720.
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abstract = "Two new one-dimensional (1D) rhodium(I)-semiquinonato complexes formulated as [Rh(3,6-DBSQ-4,5-PDO)(CO)2]- (4; 3,6-DBSQ-4,5-PDO•- = 3,6-di-tert-butyl-4,5-(1,3-propanedioxy)-1,2-benzosemiquinonato) and [Rh(3,6-DBSQ-4,5-(N,N′-DEN))(CO)2]- (5; 3,6-DBSQ-4,5-(N,N′-DEN)•- = 3,6-di-tert-butyl-4,5-(N,N′-diethylenediamine)-1,2-benzosemiquinonato) were synthesized to explore the nature of the unusual structural phase transition and magnetic and conductive properties recently reported for [Rh(3,6-DBSQ-4,5-(MeO)2)(CO)2]- (3; 3,6-DBSQ-4,5-(MeO)2•- = 3,6-di-tert-butyl-4,5-dimethoxy-1,2-benzosemiquinonato). Their crystal structures and magnetic and conductive properties were investigated. Compounds 4 and 5 comprise neutral 1D chains of complex molecules stacked in a staggered arrangement with fairly short average Rh-Rh distances of 3.06 {\AA} for 4 and 3.10 {\AA} for 5. These distances are similar to those for 3 (3.09 {\AA}); however, the molecules of 5 are strongly dimerized in the 1D chain. Compound 4 undergoes a first-order phase transition at Ttrs = 229.1 K, and its magnetic properties drastically change from antiferromagnetic coupling in the roomerature (RT) phase to strong ferromagnetic coupling in the lowerature (LT) phase. In addition, compound 4 exhibits a long-range ordering of net magnetic moments originating from the imperfect cancellation of antiferromagnetically coupled spins between the ferromagnetic 1D chains at TN = 10.9 K. Furthermore, this compound exhibits an interesting crossover from a semiconductor with a small activation energy (Ea = 31 meV) in the RT phase to a semiconductor with a large activation energy (Ea = 199 meV) in the LT phase. These behaviors are commonly observed for 3. Alternating current susceptibility measurements of 4, however, revealed a frequency-dependent phenomenon below 5.2 K, which was not observed for 3, thus indicating a slow spin relaxation process that possibly arises from the movements of domain walls. In contrast, compound 5, which possesses a strongly dimerized structure in its 1D chain, shows no sign of strong ferromagnetic interactions and is an insulator, with a resistivity greater than 7 × 107 ω cm.",
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T2 - Substituent effects on crystal structures and solid-state properties

AU - Mitsumi, Minoru

AU - Ohtake, Shoji

AU - Kakuno, Yuki

AU - Komatsu, Yuuki

AU - Ozawa, Yoshiki

AU - Toriumi, Koshiro

AU - Yasuda, Nobuhiro

AU - Azuma, Nobuaki

AU - Miyazaki, Yuji

PY - 2014/11/3

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N2 - Two new one-dimensional (1D) rhodium(I)-semiquinonato complexes formulated as [Rh(3,6-DBSQ-4,5-PDO)(CO)2]- (4; 3,6-DBSQ-4,5-PDO•- = 3,6-di-tert-butyl-4,5-(1,3-propanedioxy)-1,2-benzosemiquinonato) and [Rh(3,6-DBSQ-4,5-(N,N′-DEN))(CO)2]- (5; 3,6-DBSQ-4,5-(N,N′-DEN)•- = 3,6-di-tert-butyl-4,5-(N,N′-diethylenediamine)-1,2-benzosemiquinonato) were synthesized to explore the nature of the unusual structural phase transition and magnetic and conductive properties recently reported for [Rh(3,6-DBSQ-4,5-(MeO)2)(CO)2]- (3; 3,6-DBSQ-4,5-(MeO)2•- = 3,6-di-tert-butyl-4,5-dimethoxy-1,2-benzosemiquinonato). Their crystal structures and magnetic and conductive properties were investigated. Compounds 4 and 5 comprise neutral 1D chains of complex molecules stacked in a staggered arrangement with fairly short average Rh-Rh distances of 3.06 Å for 4 and 3.10 Å for 5. These distances are similar to those for 3 (3.09 Å); however, the molecules of 5 are strongly dimerized in the 1D chain. Compound 4 undergoes a first-order phase transition at Ttrs = 229.1 K, and its magnetic properties drastically change from antiferromagnetic coupling in the roomerature (RT) phase to strong ferromagnetic coupling in the lowerature (LT) phase. In addition, compound 4 exhibits a long-range ordering of net magnetic moments originating from the imperfect cancellation of antiferromagnetically coupled spins between the ferromagnetic 1D chains at TN = 10.9 K. Furthermore, this compound exhibits an interesting crossover from a semiconductor with a small activation energy (Ea = 31 meV) in the RT phase to a semiconductor with a large activation energy (Ea = 199 meV) in the LT phase. These behaviors are commonly observed for 3. Alternating current susceptibility measurements of 4, however, revealed a frequency-dependent phenomenon below 5.2 K, which was not observed for 3, thus indicating a slow spin relaxation process that possibly arises from the movements of domain walls. In contrast, compound 5, which possesses a strongly dimerized structure in its 1D chain, shows no sign of strong ferromagnetic interactions and is an insulator, with a resistivity greater than 7 × 107 ω cm.

AB - Two new one-dimensional (1D) rhodium(I)-semiquinonato complexes formulated as [Rh(3,6-DBSQ-4,5-PDO)(CO)2]- (4; 3,6-DBSQ-4,5-PDO•- = 3,6-di-tert-butyl-4,5-(1,3-propanedioxy)-1,2-benzosemiquinonato) and [Rh(3,6-DBSQ-4,5-(N,N′-DEN))(CO)2]- (5; 3,6-DBSQ-4,5-(N,N′-DEN)•- = 3,6-di-tert-butyl-4,5-(N,N′-diethylenediamine)-1,2-benzosemiquinonato) were synthesized to explore the nature of the unusual structural phase transition and magnetic and conductive properties recently reported for [Rh(3,6-DBSQ-4,5-(MeO)2)(CO)2]- (3; 3,6-DBSQ-4,5-(MeO)2•- = 3,6-di-tert-butyl-4,5-dimethoxy-1,2-benzosemiquinonato). Their crystal structures and magnetic and conductive properties were investigated. Compounds 4 and 5 comprise neutral 1D chains of complex molecules stacked in a staggered arrangement with fairly short average Rh-Rh distances of 3.06 Å for 4 and 3.10 Å for 5. These distances are similar to those for 3 (3.09 Å); however, the molecules of 5 are strongly dimerized in the 1D chain. Compound 4 undergoes a first-order phase transition at Ttrs = 229.1 K, and its magnetic properties drastically change from antiferromagnetic coupling in the roomerature (RT) phase to strong ferromagnetic coupling in the lowerature (LT) phase. In addition, compound 4 exhibits a long-range ordering of net magnetic moments originating from the imperfect cancellation of antiferromagnetically coupled spins between the ferromagnetic 1D chains at TN = 10.9 K. Furthermore, this compound exhibits an interesting crossover from a semiconductor with a small activation energy (Ea = 31 meV) in the RT phase to a semiconductor with a large activation energy (Ea = 199 meV) in the LT phase. These behaviors are commonly observed for 3. Alternating current susceptibility measurements of 4, however, revealed a frequency-dependent phenomenon below 5.2 K, which was not observed for 3, thus indicating a slow spin relaxation process that possibly arises from the movements of domain walls. In contrast, compound 5, which possesses a strongly dimerized structure in its 1D chain, shows no sign of strong ferromagnetic interactions and is an insulator, with a resistivity greater than 7 × 107 ω cm.

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