ダウンロード数: 343
このアイテムのファイル:
ファイル | 記述 | サイズ | フォーマット | |
---|---|---|---|---|
asia.201700138.pdf | 2 MB | Adobe PDF | 見る/開く |
タイトル: | Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato(-) Anions and Indium(III) Phthalocyanine Bromide Radical Anions. |
著者: | Konarev, Dmitri V Khasanov, Salavat S Ishikawa, Manabu Nakano, Yoshiaki https://orcid.org/0000-0003-3616-7286 (unconfirmed) Otsuka, Akihiro https://orcid.org/0000-0002-3141-0702 (unconfirmed) Yamochi, Hideki Saito, Gunzi Lyubovskaya, Rimma N |
著者名の別形: | 石川, 学 中野, 義明 大塚, 晃弘 矢持, 秀起 |
キーワード: | aluminum antiferromagnetic coupling gallium indium magnetic properties phthalocyanines radical ions |
発行日: | 18-Apr-2017 |
出版者: | Wiley-Blackwell |
誌名: | Chemistry - an Asian journal |
巻: | 12 |
号: | 8 |
開始ページ: | 910 |
終了ページ: | 919 |
抄録: | Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu4 N(+) )2 [M(III) (HFl-O(-) )(Pc(.3-) )](.-) (Br(-) )⋅1.5 C6 H4 Cl2 [M=Al (1), Ga (2); HFl-O(-) =fluoren-9-olato(-) anion; Pc=phthalocyanine] and (Bu4 N(+) ) [In(III) Br(Pc(.3-) )](.-) ⋅0.875 C6 H4 Cl2 ⋅0.125 C6 H14 (3). The salts were found to contain Pc(.3-) radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc(.3-) in the near-IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl-O(-) anions in 1 and 2 with short Al-O and Ga-O bond lengths of 1.749(2) and 1.836(6) Å, respectively. The C-O bonds [1.402(3) and 1.391(11) Å in 1 and 2, respectively] in the HFl-O(-) anions are longer than the same bond in the fluorenone ketyl (1.27-1.31 Å). Salts 1-3 show effective magnetic moments of 1.72, 1.66, and 1.79 μB at 300 K, respectively, owing to the presence of unpaired S=1/2 spins on Pc(.3-) . These spins are coupled antiferromagnetically with Weiss temperatures of -22, -14, and -30 K for 1-3, respectively. Coupling can occur in the corrugated two-dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J/kB =-0.9 and -1.1 K, respectively, and in the π-stacking {[In(III) Br(Pc(.3-) )](.-) }2 dimers of 3 with an exchange interaction of J/kB =-10.8 K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc(.3-) . It was found that increasing the size of the central metal atom strongly broadened these EPR signals. |
著作権等: | This is the accepted version of the following article: D. V. Konarev, S. S. Khasanov, M. Ishikawa, Y. Nakano, A. Otsuka, H. Yamochi, G. Saito, R. N. Lyubovskaya, Chem. Asian J. 2017, 12, 910., which has been published in final form at http://doi.org/10.1002/asia.201700138. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. The full-text file will be made open to the public on 18 April 2018 in accordance with publisher's 'Terms and Conditions for Self-Archiving'. This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。 |
URI: | http://hdl.handle.net/2433/224817 |
DOI(出版社版): | 10.1002/asia.201700138 |
PubMed ID: | 28205420 |
出現コレクション: | 学術雑誌掲載論文等 |
このリポジトリに保管されているアイテムはすべて著作権により保護されています。