Studies on Preparation and Characterization of Phthalocyanines with the Trithiole Rings

三硫醇环酞菁的制备及表征研究

• 批准号: 15550024
• 负责人: KIMURA Takeshi
• 金额: $ 2.11万
• 依托单位: Iwate University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550024/
• 关键词: Phthalocyanine; Trithiole ring; Organic Heteroatom Chemistry; Redox

1,4,8,11,15,18,22,25-Octalkyl-2,3,9,10,16,17,23,24-tetrakis(o-xylylene-dithio)phthalocyanines (1a,b) [alkyl=butyl and octyl] were prepared in moderate yields on treatment of 3,6-dialkyl-4,5-(o-xylylenedithio)-phthalonitriles with lithium in n-pentanol. Reductive removal of four o-xylylene groups from 1a,b was performed with Li/THF/NH_3,and octathiolate anions generated were then reacted with elemental sulfur to give new phthalocyanines (3a,b) with four trithiole rings, respectively, after partial desulfurization and ring contraction reactions of corresponding phthalocyanines (2a,b). The structures of phthalocyanines were determined with ^1H NMR and MALDI-TOF MS. The absorption of the Q-band of 1a,b was observed at around λ_<max>=770 nm in the UV-vis spectra, while that of 3a,b was found at around a relatively blueshifted region. When the UV-vis spectrum for 3b was measured in concentrated sulfuric acid, the λ_<max> value of the Q-band was 887 nm (log ε=4.5), which suggests that the positive charge generated on 3b strongly affects the π-conjugation of the phthalocyanine skeleton. The ESR spectrum was observed as one broadening signal on treatment of 3b with SbCl_5.

1，4，8，11，15，18，22，25-Octalkyl-2，3，9，10，16，17，23，24-tetrakis(o-xylylene-dithio)phthalocyanines(1a，b)[烷基=丁基和辛基]是用锂在正戊醇中与3，6-dialkyl-4，5-(o-xylylenedithio)-phthalonitriles反应，以中等产率合成的。用Li/THF/NH_3还原脱除1a，b上的4个邻二甲苯基团，生成的八硫杂阴离子与单质硫反应生成含四个三硫醇环的新的三硫基酞菁(3a，b)。用~1H核磁共振和MALDI-TOF MS对其结构进行了表征，在UV-Vis光谱中观察到1a，b的Q带在λ&lt；max&gt；=770 nm附近有吸收，而3a，b的Q带在相对蓝移的区域附近有吸收。当在浓硫酸中测量3b的UV-Vis光谱时，Q带的λ&lt；max&gt；值为887 nm(logε=4.5)，这表明3b上产生的正电荷强烈地影响了酞菁骨架的π共轭。用SbCl5处理3b，观察到ESR谱为一个展宽信号。

项目成果

Preparation and Determination of 4,8-Diethylbenzo[1,2-d:4,5-d]bis[1,2,3]-tritrhiole Dication [DEBBT(2+)]

4,8-二乙基苯并[1,2-d:4,5-d]双[1,2,3]-三硫醇双阳离子[DEBBT(2 )]的制备与测定

• 发表时间: 2005
• 期刊: Phosphorus, Sulfur, and Silicon 180・4/5
• 作者: T.Kimura;T.Sasaki;H.Yamaki;E.Suzuki
• 通讯作者: E.Suzuki

Preparation and Electrochemical properties of 1,4,8,11,15,18,22,25-Octalkylphthalocyanines with Four Trithiole Rings

四三硫醇环1,4,8,11,15,18,22,25-辛烷基酞菁的制备及电化学性能

• 发表时间: 2006
• 期刊: European Journal of Organic Chemistry ・5
• 作者: T.Kimura;T.Suzuki;Y.Takaguchi;A.Yomogita;T.Wakahara;T.Akasaka
• 通讯作者: T.Akasaka

Generation and Structure Determination of 5,6-Bis(methylthio)-4,7-diethyl-benzo[1,2,3]trithiole Dication MBT(2+)

5,6-双(甲硫基)-4,7-二乙基-苯并[1,2,3]三硫醇双阳离子MBT(2)的生成和结构测定

• 期刊: Heteroatom Chemistry (in press)
• 作者: T.Kimura;K.Ito;S.Ogawa;R.Sato;Yasushi Kawai
• 通讯作者: Yasushi Kawai

T.Kimura, T.Sasaki, H.Yamaki, E.Suzuki, S.Niizuma: "Radical Cation and Dication Derived from 4,8-Diethylbenzo[1,2-d:4,5-d']-bis[1,2,3]trithiole [DEBBT]:Change of Electronic State from Singlet-State Dication DEBBT(2+)-S to Triplet-State Dimer 2DEBBT(2+)-T

T.Kimura、T.Sasaki、H.Yamaki、E.Suzuki、S.Niizuma：“源自 4,8-二乙基苯并[1,2-d:4,5-d]-双[1 的自由基阳离子和双阳离子”

Preparation of Phthalocyanines with Eight Benzylchalcogeno Substituents from 5,6-Dibromo-4,7-diethylbenzo[1,2,3] trichalcogenoles

由5,6-二溴-4,7-二乙基苯并[1,2,3]三硫属元素醇制备具有八个苄基硫属元素取代基的酞菁

• 发表时间: 2004
• 期刊: The Journal of Organic Chemistry 69
• 作者: Yasushi Kawai;Yasushi Kawai;Takeshi Kimura;Takeshi Kimura
• 通讯作者: Takeshi Kimura