Anomalous spin crossover of mechanically strained iron(II) complexes, with 1,10-phenanthroline with their counterions, NCS- and PF6/-

Naoko Tsuchiya; Atsushi Tsukamoto; Tadashi Ohshita; Tetsuhiko Isobe; Mamoru Senna; Naoki Yoshioka; Hidenari Inoue

doi:10.1006/jssc.2000.8750

Anomalous spin crossover of mechanically strained iron(II) complexes, with 1,10-phenanthroline with their counterions, NCS^- and PF₆/^-

Naoko Tsuchiya, Atsushi Tsukamoto, Tadashi Ohshita, Tetsuhiko Isobe, Mamoru Senna, Naoki Yoshioka, Hidenari Inoue

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

16 Citations (Scopus)

Abstract

Effects of counterions on the change in the magnetic behavior due to mechanical amorphization have been examined on iron(II) complexes with 1,10-phenanthroline, Fe(phen)₂(NCS)₂, [Fe(phen)₃](NCS)₂·H₂O, and [Fe(phen)₃](PF₆)₂, at temperatures between 2 K and 300 K. Amorphization results in the increase in χ(M)T, where χ(M) is molar magnetic susceptibility and T is temperature, in two modes, i.e., a jump at temperatures below 20 K and a subsequent gradual increase. The first mode is attributed to the mechanically induced high spin state (⁵T(2g)) which is made metastable below 20 K. The second is the thermally induced transition from a low spin (¹A(1g)) to a high spin (⁵T(2g)) state for the distorted complexes with the widened distribution of the ligand field strength. The stabilization of the HS state is mainly due to the ligand field distortion caused by mechanical amorphization. Coordination of ionic species, NCS^- and PF₆/^-, originally serving as counterions, plays a significant role in the ligand field distortion. (C) 2000 Academic Press.

Original language	English
Pages (from-to)	82-91
Number of pages	10
Journal	Journal of Solid State Chemistry
Volume	153
Issue number	1
DOIs	https://doi.org/10.1006/jssc.2000.8750
Publication status	Published - 2000

Keywords

Counterion
Iron(II) complex crystals
Ligand field strength
Mechanical stressing
Spin crossover

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Condensed Matter Physics
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1006/jssc.2000.8750

Cite this

@article{24cd20335054480487db68245f6bba1f,

title = "Anomalous spin crossover of mechanically strained iron(II) complexes, with 1,10-phenanthroline with their counterions, NCS- and PF6/-",

abstract = "Effects of counterions on the change in the magnetic behavior due to mechanical amorphization have been examined on iron(II) complexes with 1,10-phenanthroline, Fe(phen)2(NCS)2, [Fe(phen)3](NCS)2·H2O, and [Fe(phen)3](PF6)2, at temperatures between 2 K and 300 K. Amorphization results in the increase in χ(M)T, where χ(M) is molar magnetic susceptibility and T is temperature, in two modes, i.e., a jump at temperatures below 20 K and a subsequent gradual increase. The first mode is attributed to the mechanically induced high spin state (5T(2g)) which is made metastable below 20 K. The second is the thermally induced transition from a low spin (1A(1g)) to a high spin (5T(2g)) state for the distorted complexes with the widened distribution of the ligand field strength. The stabilization of the HS state is mainly due to the ligand field distortion caused by mechanical amorphization. Coordination of ionic species, NCS- and PF6/-, originally serving as counterions, plays a significant role in the ligand field distortion. (C) 2000 Academic Press.",

keywords = "Counterion, Iron(II) complex crystals, Ligand field strength, Mechanical stressing, Spin crossover",

author = "Naoko Tsuchiya and Atsushi Tsukamoto and Tadashi Ohshita and Tetsuhiko Isobe and Mamoru Senna and Naoki Yoshioka and Hidenari Inoue",

note = "Funding Information: This work was supported by a Grant-in-Aid for Scienti{"}c Research (No. 09490033) from the Ministry of Education, Science, Sports and Culture in Japan.",

year = "2000",

doi = "10.1006/jssc.2000.8750",

language = "English",

volume = "153",

pages = "82--91",

journal = "Journal of Solid State Chemistry",

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publisher = "Academic Press Inc.",

number = "1",

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T1 - Anomalous spin crossover of mechanically strained iron(II) complexes, with 1,10-phenanthroline with their counterions, NCS- and PF6/-

AU - Tsuchiya, Naoko

AU - Tsukamoto, Atsushi

AU - Ohshita, Tadashi

AU - Isobe, Tetsuhiko

AU - Senna, Mamoru

AU - Yoshioka, Naoki

AU - Inoue, Hidenari

N1 - Funding Information: This work was supported by a Grant-in-Aid for Scienti"c Research (No. 09490033) from the Ministry of Education, Science, Sports and Culture in Japan.

PY - 2000

Y1 - 2000

N2 - Effects of counterions on the change in the magnetic behavior due to mechanical amorphization have been examined on iron(II) complexes with 1,10-phenanthroline, Fe(phen)2(NCS)2, [Fe(phen)3](NCS)2·H2O, and [Fe(phen)3](PF6)2, at temperatures between 2 K and 300 K. Amorphization results in the increase in χ(M)T, where χ(M) is molar magnetic susceptibility and T is temperature, in two modes, i.e., a jump at temperatures below 20 K and a subsequent gradual increase. The first mode is attributed to the mechanically induced high spin state (5T(2g)) which is made metastable below 20 K. The second is the thermally induced transition from a low spin (1A(1g)) to a high spin (5T(2g)) state for the distorted complexes with the widened distribution of the ligand field strength. The stabilization of the HS state is mainly due to the ligand field distortion caused by mechanical amorphization. Coordination of ionic species, NCS- and PF6/-, originally serving as counterions, plays a significant role in the ligand field distortion. (C) 2000 Academic Press.

AB - Effects of counterions on the change in the magnetic behavior due to mechanical amorphization have been examined on iron(II) complexes with 1,10-phenanthroline, Fe(phen)2(NCS)2, [Fe(phen)3](NCS)2·H2O, and [Fe(phen)3](PF6)2, at temperatures between 2 K and 300 K. Amorphization results in the increase in χ(M)T, where χ(M) is molar magnetic susceptibility and T is temperature, in two modes, i.e., a jump at temperatures below 20 K and a subsequent gradual increase. The first mode is attributed to the mechanically induced high spin state (5T(2g)) which is made metastable below 20 K. The second is the thermally induced transition from a low spin (1A(1g)) to a high spin (5T(2g)) state for the distorted complexes with the widened distribution of the ligand field strength. The stabilization of the HS state is mainly due to the ligand field distortion caused by mechanical amorphization. Coordination of ionic species, NCS- and PF6/-, originally serving as counterions, plays a significant role in the ligand field distortion. (C) 2000 Academic Press.

KW - Counterion

KW - Iron(II) complex crystals

KW - Ligand field strength

KW - Mechanical stressing

KW - Spin crossover

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