On‐Surface Synthesis of Porphyrin‐Complex Multi‐Block Co‐Oligomers by Defluorinative Coupling
On‐Surface Synthesis of Porphyrin‐Complex Multi‐Block Co‐Oligomers by Defluorinative Coupling
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通过脱氟偶联在表面合成卟啉复合物多嵌段共聚低聚物
DOI：
10.1002/anie.202114697
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Osuka Atsuhiro
中科院分区：
文献类型：
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作者：
Kawai Shigeki;Ishikawa Atsushi;Ishida Shin‐ichiro;Yamakado Takuya;Ma Yujing;Sun Kewei;Tateyama Yoshitaka;Pawlak R?my;Meyer Ernst;Saito Shohei;Osuka Atsuhiro
表面化学反应已经成为一种非常强大的技术，通过自下而上的方法连接小分子来合成纳米结构。考虑到大多数反应物在某些温度下同时活化的事实，以受控方式进行顺序反应仍然具有挑战性。在这里，我们提出了一个表面合成的多嵌段共聚低聚物从三氟甲基（CF3）取代的卟啉金属配合物。结合键分辨扫描探针显微镜和密度泛函理论（DFT）计算证明了Au（111）上的寡聚化。即使在单个单体单元的第一次低聚之后，低聚物的末端仍保留CF 3基团，其可用作反应物以按顺序进行进一步偶联。因此，双蒽稠合卟啉低聚物的铜、钴和钯络合物以设计的顺序彼此连接。
On‐surface chemical reaction has become a very powerful technique to synthesize nanostructures by linking small molecules in the bottom‐up approach. Given the fact that most reactants are simultaneously activated at certain temperatures, a sequential reaction in a controlled way has remained challenging. Here, we present an on‐surface synthesis of multi‐block co‐oligomers from trifluoromethyl (CF3) substituted porphyrin metal complexes. The oligomerization on Au(111) is demonstrated with a combination of bond‐resolved scanning probe microscopy and density functional theory (DFT) calculations. Even after the first oligomerization of single monomer unit, the termini of the oligomer keep the CF3group, which can be used as a reactant for further coupling in a sequential order. Consequently, copper, cobalt, and palladium complexes of bisanthracene‐fused porphyrin oligomers were linked with each other in a designed order.