High-Resolution Structure and Conformational Dynamics of Rigid, Cofacially Aligned Porphyrin-Bridge-Quinone Systems As Determined by NMR Spectroscopy and ab Initio Simulated Annealing Calculations
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- 作者：Peter M. Iovine ; Gianluigi Veglia ; George Furst ; and Michael J. Therien
- 刊名：Journal of the American Chemical Society
- 出版年：2001
- 出版时间：June 20, 2001
- 年：2001
- 卷：123
- 期：24
- 页码：5668 - 5679
- 全文大小：298K
- 年卷期：v.123,no.24(June 20, 2001)
- ISSN：1520-5126
文摘
The high-resolution solution structure and dynamics of a cofacially aligned porphyrin-phenylene-quinone compound have been determined using 1H NMR spectroscopy and simulated annealing calculations.Members of this class of 
-stacked assemblies feature a 1,8-naphthyl pillaring motif that enforces sub van derWaals interplanar separations between juxtaposed porphyryl, aromatic bridge, and quinonyl components ofthe donor-spacer-acceptor compound; this structural motif gives rise to a comprehensive set of structurallysignificant NOE signatures that can be used as constraints in quantitative structural calculations. Examinationof such data using ab initio simulated annealing analytical methods shows that 5-[8'-(4' '-[8' ''-(2' '' ',5' ''-benzoquinonyl)-1' ''-naphthyl]-1' '-phenyl)-1'-naphthyl]-10,20-diphenylporphyrin displays an unusual degree ofconformational homogeneity in the condensed phase, and represents a rare example where such an analysisdetermines unequivocally a single unique structure in solution.
-stacked assemblies feature a 1,8-naphthyl pillaring motif that enforces sub van derWaals interplanar separations between juxtaposed porphyryl, aromatic bridge, and quinonyl components ofthe donor-spacer-acceptor compound; this structural motif gives rise to a comprehensive set of structurallysignificant NOE signatures that can be used as constraints in quantitative structural calculations. Examinationof such data using ab initio simulated annealing analytical methods shows that 5-[8'-(4' '-[8' ''-(2' '' ',5' ''-benzoquinonyl)-1' ''-naphthyl]-1' '-phenyl)-1'-naphthyl]-10,20-diphenylporphyrin displays an unusual degree ofconformational homogeneity in the condensed phase, and represents a rare example where such an analysisdetermines unequivocally a single unique structure in solution.