Development and Application of (Stable Radical)-substituted Radical Ions

（稳定自由基）取代自由基离子的开发与应用

• 批准号: 17350072
• 负责人: OKADA Keiji
• 金额: $ 4.8万
• 依托单位: Osaka City University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-17350072/
• 关键词: radical ions; stable radicals; ferromagnetic interaction; ferrimagnetic interaction; dihydrophenazines; planar triphenylamine; exchange interaction; ラジカル; 反強磁性相互作用; π電子系化合物; 磁性

Radical-substituted radical ions with strongly ferromagnetic intramolecular interaction are attractive species as spin-building blocks of magnetic materials. In most cases, these species are unstable. We have recently prepared, for the first time, nitronyl nitroxide-substituted dihydrophenazine radical cation, which is a stable compound at room temperature under aerated conditions and has a strongly ferromagnetic intramolecular interaction of J>700K. In order to construct magnetic materials based on the radical-substituted radical ions, we aim at preparing several derivatives of this class of compounds. The following guidelines are taken for the purpose ; 1) the readily oxidizable and reducible π-system which should give stable radical ions are essential, 2) the π-system radical ions should have a large spin density at the carbon atoms on which stable radical is introduced, 3) the π-system radical ions are hoped to have a property giving good quality of crystals. The requirement 2) is … More important to get a strong ferromagnetic nature between the attached radical and radical ion spins. The requirement 3) is critical to develop the magnetic materials.We have examined various radical cations such as p- and m-phenylene bridged dihydrophenazine derivatives, benzoxazinophenoxazines, benzothiazinophenoxazines, and heteroatom-bridged planar triphenylamine derivatives, and radical anions such as thienoqunoid radical anions involving those with 1,4-diazacyclopentadien-2-ylidene terminals and dicyanomethylene terminals. All these compounds are new compounds. We could isolate the radical cation species in all cases. For the radical anions, the thienoqunoids with dicyanomethylene terminals were found to be stable : Thus, the requirements 1) and 2) were satisfied but the requirement 3) was hard to satisfy for most cases. Fortunately, the trisoxytriphenylamine (TOT) radical cation gave good crystals in various conditions. We synthesized nitronyl nitroxide-substituted TOT. Then, we could readily isolate nitronyl nitroxide-substituted TOT radical cations as PF_6, GaCl_4, and FeCl_4 salts. For dihydrophenazine derivatives, we have succeeded to prepare verdazyl-substituted dihydrophenaznines as similar salts. Application of these compounds as purely organic magnetic systems are planned. Less

具有强铁磁分子内相互作用的自由基取代离子是磁性材料的自旋结构单元。在大多数情况下，这些物种是不稳定的。我们最近首次制备了硝酰基氮氧自由基取代的二氢吩嗪自由基阳离子，它在室温和通气条件下是一种稳定的化合物，具有强铁磁分子内相互作用，J> 700 K。为了构建基于自由基取代的自由基离子的磁性材料，我们的目标是制备这类化合物的几种衍生物。为此目的采取以下指导方针：1）应提供稳定自由基离子的易氧化和易还原的π-系统是必要的，2）π-系统自由基离子应在其上引入稳定自由基的碳原子处具有大的自旋密度，3）希望π-系统自由基离子具有提供良好晶体质量的性质。要求2）是 ...更多信息 重要的是在附着的自由基和自由基离子自旋之间获得强铁磁性质。我们已经研究了各种自由基阳离子，如对-和间-亚苯基桥连的二氢吩嗪衍生物、苯并恶嗪吩恶嗪、苯并噻嗪吩恶嗪和杂原子桥连的平面三苯胺衍生物，以及自由基阴离子，如噻吩并喹啉类自由基阴离子，包括那些具有1，4-二氮杂环己烯-2-亚基末端和二氰基亚甲基末端的自由基阴离子。这些化合物均为新化合物。我们可以在所有情况下分离出自由基阳离子。对于自由基阴离子，发现具有二氰基亚甲基末端的噻吩并喹啉类化合物是稳定的：因此，在大多数情况下满足要求1）和2），但难以满足要求3）。幸运的是，三乙氧基三苯胺（TOT）自由基阳离子在各种条件下得到良好的晶体。我们合成了硝酰基氮氧自由基取代的TOT。然后，我们可以很容易地分离硝基氮氧取代TOT自由基阳离子PF_6，GaCl_4，和FeCl_4盐。对于二氢吩嗪衍生物，我们已经成功地制备了verdazyl取代的二氢吩嗪类似的盐。计划将这些化合物作为纯有机磁性系统应用。少

项目成果

Preparation, Properties, and Reduction of a Novel TCNQ-type Thienoquinoid

新型 TCNQ 型噻吩醌的制备、性质及还原

• 发表时间: 2006
• 期刊: Organic Letters 8
• 作者: M.Kozaki;K.Sugimura;H.Ohnishi;K.Okada
• 通讯作者: K.Okada

Preparation and magnetic properties of 4,6-bis(imino nitroxide)-substituted resorcinol and its Cu-complex

• DOI: 10.1016/j.poly.2006.09.058
• 发表时间: 2007-06
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Koichiro Tanaka;K. Furuichi;M. Kozaki;Shuichi Suzuki;D. Shiomi;Kazunobu Sato;T. Takui;K. Okada

Detection of a diradical intermediate in the cis-trans isomerization of 5,5' -bis(4,5-diphenyl-2H-imidazol-2-ylidene)-5,5' -dihydro-Δ^<2,2'> -bithiphene

检测 5,5 -双(4,5-二苯基-2H-咪唑-2-亚基)-5,5 -二氢-Δ^<2,2> 顺反异构化中的双自由基中间体 -比噻吩

• 发表时间: 2006
• 期刊: Tetrahedron Letters 47
• 作者: M.Kozaki;A.Isoyama;K.Okada
• 通讯作者: K.Okada

Exchange Interaction of 5,5'-(m- and p-Phenylene)bis(10-phenyl-5,10-dihydrophenazine) Dication and Related Analogues

5,5-(间-和对-亚苯基)双(10-苯基-5,10-二氢吩嗪)二阳离子及相关类似物的交换相互作用

• 发表时间: 2005
• 期刊: J. Org. Chem. 70
• 作者: E.Terada;T.Okamoto;K.Sato;T.Takui;K.Okada
• 通讯作者: K.Okada