期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 22, 页码 8740-8752出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja202451t
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资金
- NSF [CHE-0517782, CMMI-0730826, 0087210]
- Degussa Stiftung
- Studienstiftung des deutschen Volkes
- Ohio Board of Regents [CAP-491]
- Ferens Educational Trust, University of Hull
- YSU
- EPSRC
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1048717] Funding Source: National Science Foundation
The synthesis and chiral resolution of free-base and Ni(II) complexes of a number of derivatives of meso-tetraphenylmorpholinochlorins, with and without direct beta-carbon-to-o-phenyl linkages to the flanking phenyl groups, is described. The morpholinochlorins, a class of stable chlorin analogues, were synthesized in two to three steps from meso-tetraphenylporphyrin. The conformations and the relative stereo-structures of a variety of free-base and Ni(II) complexes of these morpholinochlorins were elucidated by X-ray diffractometry. Steric and stereoelectronic arguments explain the relative stereoarray of the mor-pholino-substituents, which differ in the free-base and Ni(II) complexes, and in the monoalkoxy, beta-carbon-to-o-phenyl linked morpholinochlorins, and the dialkoxy derivatives. The Ni(II) complexes were all found to be severely ruffled whereas the free-base chromophores are more planar. As a result of the helimeric distortion of their porphyrinoid chromophores, the ruffled macrocycles possess a stable inherent element of chirality. Most significantly, resolution of the racemic mixtures was achieved, both by classical methods via diastereomers and by HPLC on a chiral phase. Full CD spectra were recorded and modeled using quantum-chemical computational methods, permitting, for the first time, an assignment of the absolute configurations of the chromophores. The report expands the range of known pyrrole-modified porphyrins. Beyond this, it introduces large chiral porphyrinoid pi-systems that exist in the form of two enantiomeric, stereochemically stable helimers that can be resolved. This forms the basis for possible future applications, for example, in molecular-recognition systems or in materials with chiroptic properties.
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