Structural, spectroscopic and anion binding properties of 5,10-porphodimethenes, an unusual class of calixphyrins
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2010Access:
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Finnigan E.M., Giordani S., Senge M.O. and McCabe T., Structural, spectroscopic and anion binding properties of 5,10-porphodimethenes, an unusual class of calixphyrins, Journal of Physical Chemistry A, 114, 7, 2010, 2464 2470Download Item:
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Abstract:
Complete spectroscopic, structural and anion binding properties are reported for a special class of
calixphyrins, namely 5,10-disubstituted porphodimethenes (PDMs). The crystal structure clearly shows
that PDMs exhibit nonplanar (distorted) structures with both sp2- and sp3-hybridized meso carbon
centres. We were able to obtain and characterize the diacid form [H4(PDM)[[X]2 upon addition of
several acids to PDMs, where X denotes anions of different acids: HCl; HBr; MeSO3H; CF3CO2H and
HClO4. We found that the PDM dications generated were more conjugated and thus more stable than
their corresponding porphyrins. Their potential to coordinate anions was clearly shown using 1H NMR
spectroscopy. In addition, we found that when HClO4 was used to protonate PDMs the conversion occurs through an intermediate species, which has been assigned to the elusive monoacid derivative on
the basis of UV-vis and 1H NMR experiments.
Sponsor
Grant Number
Science Foundation Ireland (SFI)
4/RP1/B482,
Science Foundation Ireland (SFI)
07/YI2/I1052
Science Foundation Ireland (SFI)
07/RFP/CHEF232
Author's Homepage:
http://people.tcd.ie/giordanshttp://people.tcd.ie/sengem
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PUBLISHED
Author: GIORDANI, SILVIA; SENGE, MATHIAS
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Journal of Physical Chemistry A114
7
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http://dx.doi.org/10.1021/jp909573mLicences: