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Carbon‐13 NMR spectra of chlorophyll a, chlorophyll a′, pyrochlorophyll a and the corresponding pheophytins
Author(s) -
Lötjönen Simo,
Hynninen Paavo H.
Publication year - 1983
Publication title -
organic magnetic resonance
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0030-4921
DOI - 10.1002/omr.1270211208
Subject(s) - chemistry , chemical shift , steric effects , chlorophyll , solvent , nmr spectra database , chlorophyll b , chlorophyll a , photochemistry , tetrahydrofuran , nuclear magnetic resonance spectroscopy , molecule , stereochemistry , crystallography , spectral line , organic chemistry , biochemistry , physics , astronomy
The 13 C NMR spectra of C‐10 epimeric chlorophylls a and a′, pheophytins a and a′, pyrochlorophyll a and pyropheophytin a have been recorded and assigned by chemical shift comparison, by long‐range selective 1 H decoupling experiments and by the examination of the fully coupled spectra. Various factors influencing the 13 C chemical shifts of the chlorophyll derivatives, e.g. the coordination of magnesium to the chlorin nucleus, the effect of solvent and the steric strain at the periphery of the macrocycle, have been examined. The 13 C NMR spectra of chlorophyll a measured in acetone‐ d 6 and tetrahydrofuran‐ d 8 (THF) were compared, and remarkable solvent effects on the 13 C chemical shifts were observed. These effects were interpreted mostly in terms of specific chlorophyll‐solvent interactions. Different electron donor and steric properties of acetone and THF were considered to cause conformational alterations in the macrocycle, induced by the ligation of the solvent molecule(s) to the axial position(s) of the central magnesium atom of chlorophyll a. These results show that 13 C NMR spectroscopy is a method of high information value for investigations of the unique electron donor acceptor (EDA) properties of the chlorophylls. The structural differences between the C‐10 epimeric chlorophylls and pheophytins were examined in terms of the substituent chemical shift (SCS) parameters for the C‐10 methoxycarbonyl group. The analysis showed that the change from the (10 R ) to the 10( S ) configuration induces conformational alterations in the whole macrocycle which are, however, most prominent in rings IV and V. Owing to the increased steric interaction (repulsion) between the bulky substituents at C‐7 and C‐10, the peripheral strain is larger in the (10 S ) form, and is relieved by more pronounced deviations of rings IV and V from the macrocyclic plane compared with the (10 R ) form. The examination of the SCS parameters also showed that the peripheral steric strain is dissipated to a larger extent over the entire macrocycle in the Mg‐free derivatives. These results confirm the previous conclusions based on 1 H NMR and CD data. The possible function of chlorophyll a′ in photosynthesis is briefly discussed.