Zinc-[7]helicenocyanine and its discrete π-stacked homochiral Dimer
Please always quote using this URN: urn:nbn:de:bvb:20-opus-256534
- In this communication, we demonstrate a novel approach to prepare a discrete dimer of chiral phthalocyanine (Pc) by exploiting the flexible molecular geometry of helicenes, which enables structural interlocking and strong aggregation tendency of Pcs. Synthesized [7]helicene-Pc hybrid molecular structure, zinc-[7]helicenocyanine (Zn-7HPc), exclusively forms a stable dimeric pair consisting of two homochiral molecules. The dimerization constants were estimated to be as high as 8.96×10\(^6\) M\(^{−1}\) and 3.42×107 M\(^{−1}\) in THF and DMSO,In this communication, we demonstrate a novel approach to prepare a discrete dimer of chiral phthalocyanine (Pc) by exploiting the flexible molecular geometry of helicenes, which enables structural interlocking and strong aggregation tendency of Pcs. Synthesized [7]helicene-Pc hybrid molecular structure, zinc-[7]helicenocyanine (Zn-7HPc), exclusively forms a stable dimeric pair consisting of two homochiral molecules. The dimerization constants were estimated to be as high as 8.96×10\(^6\) M\(^{−1}\) and 3.42×107 M\(^{−1}\) in THF and DMSO, respectively, indicating remarkable stability of dimer. In addition, Zn\(^{-7}\)HPc exhibited chiral self-sorting behavior, which resulted in preferential formation of a homochiral dimer also in the racemic sample. Two phthalocyanine subunits in the dimeric form strongly communicate with each other as revealed by a large comproportionation constant and observation of an IV-CT band for the thermodynamically stable mixed-valence state.…
Author: | Fangyuan Zhang, Krzysztof Radacki, Holger Braunschweig, Christoph Lambert, Prince RavatORCiD |
---|---|
URN: | urn:nbn:de:bvb:20-opus-256534 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Fakultät für Chemie und Pharmazie / Institut für Organische Chemie | |
Language: | English |
Parent Title (English): | Angewandte Chemie International Edition |
Year of Completion: | 2021 |
Volume: | 60 |
Article Number: | 44 |
Pagenumber: | 23656-23660 |
Source: | Angewandte Chemie International Edition (2021) 60:44, 23656–23660. DOI: 10.1002/anie.202109380 |
DOI: | https://doi.org/10.1002/anie.202109380 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 547 Organische Chemie |
Tag: | chirality; helicenes; homochiral dimer; organic chemistry; phthalocyanines; supramolecular assembly |
Release Date: | 2022/02/25 |
Licence (German): | ![]() |