Self-assembly of porphyrins is a fascinating topic, not only for mimicking chlorophyll assemblies in photosynthetic organisms, but also for the potential of creating molecular-level devices. Herein, zinc porphyrin derivatives bearing a meta-pyridyl group at the meso position were prepared and their assemblies studied in chloroform. Among the porphyrins studied, one with a carbamoylpyridyl moiety gave a distinct 1H NMR spectrum in CDCl3, which allowed the supramolecular structure in solution to be probed in detail. Ring-current-induced chemical-shift changes in the 1H NMR spectrum, together with vapor-pressure osmometry and diffusion-ordered NMR spectroscopy, among other evidence, suggested that the porphyrin molecules form a trimer with a triangular cone structure. Incorporation of a directly linked porphyrin–ferrocene dyad with the same assembling properties in the assemblies led to a rare example of a light-harvesting/charge-separation system in which an energy gradient is incorporated and reductive quenching occurs.
|Number of pages||11|
|Journal||Chemistry - A European Journal|
|Publication status||Published - 2021 Feb 24|
Bibliographical noteFunding Information:
We thank K. Wada and M. Kudo of Center for Creative Materials Research, Research Institute of College of Science and Technology, Nihon University for low‐temperature NMR and precise‐weight sampling, respectively. We also thank Y. Kida for experimental help. J.O. acknowledges financial support from Kakenhi (18K05156), MEXT, Japan for part of the work. The work at Yonsei University (transient absorption) was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. 2020R1A5A1019141).
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All Science Journal Classification (ASJC) codes
- Organic Chemistry