Synthesis of Hydrophilic Copper(II) Complexes of 5,10,15,20-Tetraaryl-5,15-diazaporphyrins Substituted with Carboxy or (2,3-Dihydroxypropyl)carbamoyl Groups
Synthesis of Hydrophilic Copper(II) Complexes of 5,10,15,20-Tetraaryl-5,15-diazaporphyrins Substituted with Carboxy or (2,3-Dihydroxypropyl)carbamoyl Groups
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羧基或（2,3-二羟丙基）氨基甲酰基取代的 5,10,15,20-四芳基-5,15-二氮杂卟啉亲水性铜（II）配合物的合成
DOI：
10.1142/s1088424621500917
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发表时间：
2021
影响因子：
1.5
通讯作者：
Yuki Shimizu and Yoshihiro Matano
中科院分区：
文献类型：
--
作者：
Ochiai Hikari;Miura Tomoaki;Ikoma Tadaaki;Minoura Mao;Nakano Haruyuki;Matano Yoshihiro;Yuki Shimizu and Yoshihiro Matano
含有亲水性助剂的卟啉类化合物受到了广泛的关注。本文首次报道了由5,10,15,20-四芳基-5,15-重氮卟啉（TADAPs）取代羧基或（2,3-二羟丙基）氨基取代的强亲水性铜（II）配合物。一种常见的二吡啶前驱体与镍（II）或铜（II）醋酸酯进行金属模板化环化反应，得到相应的金属（II）配合物5,10,15,20-四（4-烷氧羰基苯基）-5,15-重氮卟啉（M- tadap - coor; M = Ni, Cu）作为空气稳定的19个自由基阳离子，通过氧化还原反应可与20和18电子态可逆地相互转换。20ni - tadap - coors和18Ni-TADAP-COORs的核磁共振光谱分别显示出抗芳香族和芳香族特征。19Cu-TADAP-COOR经碱性水解得到羧酸Cu-TADAP-COOH，在碱性条件下可自由溶于水，但在中性或酸性条件下难溶。Cu-TADAP-COOH与2,3-双（（叔丁基二甲基硅基）氧）丙烷-1-胺脱水缩合，然后对硅基进行脱保护，得到含有4个（2,3-二羟丙基）氨基的Cu-TADAP-CONHR酰胺。虽然20Cu-TADAP-CONHR不溶于水，但其DAP环的氧化明显改变了其溶解度，从而使其在中性水中均匀分散。循环伏安法表明，在−1.8 ~ +0.2 Vvs范围内存在21/20、20/19和19/18氧化还原对。Fc / Fc。此外，Cu-TADAP-CONHR在中性水中表现出可逆的氧化还原过程。该研究表明，TADAP可能是开发亲水性dap基材料的潜在平台。
Porphyrins containing hydrophilic auxiliaries have received considerable attention. Herein we report the first examples of strongly hydrophilic copper(II) complexes of 5,10,15,20-tetraaryl-5,15-diazaporphyrins (TADAPs) substituted with carboxy or (2,3-dihydroxypropyl)carbamoyl groups. Metal-templated cyclization reactions of a common dipyrrin precursor with nickel(II) or copper(II) acetate afforded the corresponding metal(II) complexes of 5,10,15,20-tetrakis(4-alkoxycarbonylphenyl)-5,15-diazaporphyrin (M-TADAP-COOR; M = Ni, Cu) as air-stable 19radical cations, which were reversibly interconvertible with 20- and 18-electron states by redox reactions. NMR spectroscopy of 20and 18Ni-TADAP-COORs revealed antiaromatic and aromatic characteristics, respectively. Alkaline hydrolysis of the 19Cu-TADAP-COOR afforded a carboxylic acid, Cu-TADAP-COOH, which was freely soluble in water under basic conditions, but poorly soluble under neutral or acidic conditions. Dehydrative condensation of Cu-TADAP-COOH with 2,3-bis((tert-butyldimethylsilyl)oxy)propan-1-amine followed by deprotection of the silyl groups afforded an amide, Cu-TADAP-CONHR, with four (2,3-dihydroxypropyl)carbamoyl groups. Although the 20Cu-TADAP-CONHR was poorly soluble in water, oxidation of its DAP ring notably changed the solubility, and the resulting 18dication was homogeneously dispersed in neutral water. Cyclic voltammetry of the present TADAP derivatives showed the 21/20, 20/19and 19/18redox couples in the range of −1.8 to +0.2 Vvs. Fc/Fc. Furthermore, Cu-TADAP-CONHR exhibited reversible redox processes in neutral water. This study shows that TADAP could be a potential platform for the development of hydrophilic DAP-based materials.