期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 16, 期 20, 页码 5976-6005出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200903234
关键词
chiroptical properties; density functional calculations; helical structures; palladium; P,N ligands
资金
- Ministere de l'Education Nationale, de la Recherche et de la Technologie
- Centre National de la Recherche Scientifique (CNRS)
- Region Bretagne
- Agence Nationale de la Recherche (ANR) [PHOSHELIX-137104]
- National Science Foundation [CHE 0447321]
Aza[n]helicene phosphole derivatives have been prepared from aza[n]helicene diynes by the Fagan-Nugent route. Their photophysical properties (UV/Vis absorption and emission behavior) have been evaluated. Their behavior as P,N chelates towards coordination to Pd-II and Cu-I has been investigated: metal-bis(aza[n]helicene phosphole) assemblies are formed by a highly stereoselective coordination process, as demonstrated by X-ray crystallography. An aza[6]helicene phosphole bearing an enantiopure helicene part has been obtained, which allows the preparation of enantiopure Pd-II and Cu-I complexes with original topologies and high molar rotation (MR) and circular dichroism (CD). The structure property relationship established from the experimental data has been studied in detail by theoretical studies (TDDFT calculations of UV/Vis, CD, and MR). Aza[n]helicene phosphole derivatives show pi conjugation extended over the entire molecule, and its influence on the MR of aza[6]helicene phosphole 5c has been demonstrated. Finally, it has been shown that the nature of the metal (coordination geometry and electronic interaction) can have a great impact on the amplitude of the chiroptical properties in metal-bis(aza[n]helicene phosphole) assemblies.
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