Molecule to Supramolecule: Chirality Induction, Inversion, and Amplification in a Mg(II)porphyrin Dimer Templated by Chiral Diols
| Autor: | Himani Malik, Sankar Prasad Rath, Dolly Chandel, Bapan Saha, Avinash Dhamija |
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| Rok vydání: | 2019 |
| Předmět: |
inorganic chemicals
010405 organic chemistry Dimer Intermolecular force macromolecular substances 010402 general chemistry 01 natural sciences Porphyrin 0104 chemical sciences Stereocenter Inorganic Chemistry chemistry.chemical_compound Crystallography Monomer chemistry Intramolecular force Molecule Physical and Theoretical Chemistry Chirality (chemistry) |
| Zdroj: | Inorganic Chemistry. 59:801-809 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | A clear and unambiguous rationalization of chirality induction, amplification, and subsequent inversion processes has been demonstrated using an achiral Mg(II)porphyrin dimer (host) and a series of chiral diols (guests) upon stepwise formation of a 1:1 host-guest polymer and 1:2 host-guest monomer via intermolecular assembling and disassembling processes. Crystallographic characterizations are reported here for both the polymer and the monomeric complexes, which enable us to completely scrutinize the structural and geometrical changes systematically in rationalizing their optical properties. The sign of the CD couplets for both the polymer and monomer are just opposite between R and S guests, which suggests that the chirality is dictated solely by the stereogenic projection of the chiral centers. Stronger intra- and intermolecular coupling in the polymeric complexes is responsible for the highly enhanced CD couplets as compared to the monomer and have only intramolecular coupling as also observed in their X-ray structures. DFT studies clearly support the experimental observations. |
| Databáze: | OpenAIRE |
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