He Haodan, Lee Jiyeon, Zong Zhaohui, Kim Jiwon, Lynch Vincent M, Oh Juwon, Kim Dongho, Sessler Jonathan L, Ke Xian-Sheng
College of Chemistry, Beijing Normal University, Beijing, 100875, China.
School of Integrated Technology, College of Computing, Yonsei University, Incheon, 21983, Korea.
Nat Commun. 2024 Apr 4;15(1):2913. doi: 10.1038/s41467-024-47239-y.
Carbaporphyrin dimers, investigated for their distinctive electronic structures and exceptional properties, have predominantly consisted of systems containing identical subunits. This study addresses the associated knowledge gap by focusing on asymmetric carbaporphyrin dimers with Janus-like characteristics. The synthesis of a Janus-type carbaporphyrin pseudo-dimer 5 is presented. It displays antiaromatic characteristics on the fused side and nonaromatic behavior on the unfused side. A newly synthesized tetraphenylene (TPE) linked bis-dibenzihomoporphyrin 8 and a previously reported dibenzo[g,p]chrysene (DBC) linked bis-dicarbacorrole 9 were prepared as controls. Comprehensive analyses, including H NMR spectral studies, single crystal X-ray diffraction analyses, and DFT calculations, validate the mixed character of 5. A further feature of the Janus pseudo-dimer 5 is that it may be transformed into a heterometallic complex, with one side coordinating a Cu(III) center and the other stabilizing a BODIPY complex. This disparate regiochemical reactivity underscores the potential of carbaporphyrin dimers as versatile frameworks, with electronic features and site-specific coordination chemistry controlled through asymmetry. These findings position carbaporphyrin dimers as promising candidates for advances in electronic structure studies, coordination chemistry, materials science, and beyond.
碳卟啉二聚体因其独特的电子结构和特殊性质而受到研究，主要由包含相同亚基的体系组成。本研究通过聚焦具有类雅努斯特征的不对称碳卟啉二聚体来填补相关知识空白。本文介绍了一种雅努斯型碳卟啉假二聚体5的合成。它在稠合侧表现出反芳香性特征，在未稠合侧表现出非芳香性行为。制备了一种新合成的四亚苯基（TPE）连接的双二苯并高卟啉8和一种先前报道的二苯并[g,p]屈（DBC）连接的双二碳咔咯9作为对照。包括1H NMR光谱研究、单晶X射线衍射分析和DFT计算在内的综合分析验证了5的混合性质。雅努斯假二聚体5的另一个特点是它可以转化为异金属配合物，一侧配位一个Cu(III)中心，另一侧稳定一个BODIPY配合物。这种不同的区域化学反应性强调了碳卟啉二聚体作为通用框架的潜力，其电子特征和位点特异性配位化学通过不对称性来控制。这些发现使碳卟啉二聚体成为电子结构研究、配位化学、材料科学及其他领域进展的有前途候选者。
