A Five‐layer π‐Aromatic Structure Formed through Self‐assembly of a Porphyrin Trimer and Two Aromatic Guests
A Five‐layer π‐Aromatic Structure Formed through Self‐assembly of a Porphyrin Trimer and Two Aromatic Guests
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卟啉三聚体和两种芳香客体自组装形成的五层π芳香结构
DOI：
10.1002/asia.202000452
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Tokunaga Yuji
中科院分区：
文献类型：
--
作者：
Ueda Masahiro;Kimura Masaki;Miyagawa Shinobu;Takaya Hikaru;Naito Masaya;Tokunaga Yuji
在这项研究中，我们合成了两个和四个臂的卟啉-分别在它们的介观位置上含有两个羧基和四个2-氨基喹啉基官能团-作为互补的氢键对，用于AD2对称的卟啉三聚体宿主的自组装。在CH2Cl2和CHCl3中，两个双臂卟啉单元和一个四臂卟啉单元定量地自组装成D2对称的卟啉三聚体，通过氨基-羧酸盐桥形成稳定。卟啉三聚体主体在两个1，3，5-三硝基苯单元之间逐渐结合，形成五层芳香结构。在低于−40 °C的温度下，配合物的缔合和解离速度在核磁共振光谱时间尺度上很慢，使三聚体主体和三硝基苯客体(S)的1 ： 1和1 ： 2络合物能够在三硝基苯的用量小于2eq时独立检测到。VIS滴定实验表明，在室温下，K1和K2在CHCl3中的值分别为2.1±0.4×10 5M−1和2.2±0.0 6×10 4M−1。
In this study we synthesized two‐ and four‐armed porphyrins – bearing two carboxyl and four 2‐aminoquinolino functionalities, respectively, at their meso positions – as a complementary hydrogen bonding pair for the self‐assembly of aD2‐symmetric porphyrin trimer host. Two units of the two‐armed porphyrin and one unit of the four‐armed porphyrin self‐assembled quantitatively into theD2‐symmetric porphyrin trimer, stabilized through ammidinium‐carboxylate salt bridge formation, in CH2Cl2and CHCl3. The porphyrin trimer host gradually bound two units of 1,3,5‐trinitrobenzene between the pair of porphyrin units, forming a five‐layer aromatic structure. At temperatures below −40 °C, the rates of association and dissociation of the complexes were slow on the NMR spectroscopic time scale, allowing the 1 : 1 and 1 : 2 complexes of the trimer host and trinitrobenzene guest(s) to be detected independently when using less than 2 eq of trinitrobenzene. Vis titration experiments revealed the values ofK1(2.1±0.4×105M−1) andK2(2.2±0.06×104M−1) in CHCl3at room temperature.