Online ISSN: 1884-4111 Print ISSN: 0033-8303
Radioisotopes 66(12): 625-632 (2017)


1,4-ビス(4-ピリジル)ベンゼン架橋配位子を用いた鉄(II)集積型錯体のスピン状態に及ぼすメチル基導入の効果Effect of Methyl Substituent on the Spin State of Iron(II) Assembled Complex Using 1,4-Bis(4-pyridyl)benzene

1広島大学大学院理学研究科Graduate School of Science, Hiroshima University ◇ 739–8526 広島県東広島市鏡山1–3–1 ◇ 1–3–1 Kagamiyama, Higashi-Hiroshima, Hiroshima Pref. 739–8526, Japan

2日本原子力研究開発機構原子力基礎工学研究センターNuclear Science and Engineering Center, Japan Atomic Energy Agency ◇ 319–1184 茨城県那珂郡東海村大字舟石川765–1 ◇ 765–1 Funaishikawa, Tokaimura, Naka, Ibaraki Pref. 319–1184, Japan

3広島大学自然科学研究支援開発センターNatural Science Center for Basic Research and Development, Hiroshima University ◇ 739–8526 広島県東広島市鏡山1–4–2 ◇ 1–4–2 Kagamiyama, Higashi-Hiroshima, Hiroshima Pref. 739–8526, Japan

受付日:2017年2月15日Received: February 15, 2017
受理日:2017年7月10日Accepted: July 10, 2017
発行日:2017年12月15日Published: December 15, 2017


Iron(II) assembled complexes [Fe(NCX)2(L)2] (X=S, Se and BH3; L=2,5-dimethyl-1,4-bis(4-pyridyl)benzene (dmbpb) and 2,3,5,6-tetramethyl-1,4-bis(4-pyridyl)benzene (tmbpb)) were synthesized to investigate the effect of substituent on the spin crossover (SCO) behavior. PXRD revealed that the structure is different between dmbpb and tmbpb complexes, while the structures are independent of anionic ligands. 57Fe Mӧssbauer spectroscopy and magnetic susceptibility measurement revealed that the SCO occurs in the case of [Fe(NCSe)2(dmbpb)2] and [Fe(NCBH3)2(dmbpb)2] but the SCO is not observed in other complexes. The quadrupole splitting (Q.S.) value in high-spin state decreased in the order of S>Se>BH3 for dmbpb complexes but S>BH3>Se for tmbpb complexes. It was suggested that electron distribution is different between dmbpb and tmbpb complexes. Transition temperature for [Fe(NCBH3)2(dmbpb)2] was 128 K, which is lower than that of the corresponding complex bridged with 1,4- bis(4-pyridyl)benzene.

Key words: assembled complex; 1,4-bis(4-pyridyl)benzene; spin crossover; Mӧssbauer spectroscopy

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