Rapid one-pot synthesis of pyrrole-appended isocorroles
Abstract
Free-base meso-triarylcorroles have been found to undergo oxidative coupling with an excess of pyrrole in dichloromethane in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) affording 5/10-pyrrole-appended isocorroles in reasonable yields (35–60%) and in a matter of seconds. The free-base isocorrole ligands could all be complexed to copper with Cu(OAc)2·H2O in chloroform/methanol in 55–80% yields. Furthermore, single-crystal X-ray structures of two of the new compounds (H2[5-pyr-TpOMePiC] and Cu[10-pyr-TpOMePiC]) revealed planar macrocycles with rms atomic displacements of only 0.02 and 0.06 Å relative to their respective best-fit C19N4 planes. Both free-base and Cu(II)-complexed isocorroles exhibit richly featured UV-vis-NIR spectra with red/NIR absorption maxima at ~650 nm and ~725 nm for the free-bases and ~800–850 nm for the copper complexes, suggesting potential applications in photodynamic therapy. Cyclic voltammetric analyses of five of the Cu complexes revealed fully reversible redox cycles with multiple oxidation and reduction features.
- Authors:
-
[1];
[2];
[1]
- The Arctic Univ. of Norway, Tromsø (Norway)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Research Council of Norway
- OSTI Identifier:
- 1656503
- Grant/Contract Number:
- AC02-05CH11231; 262229
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Organic and Biomolecular Chemistry
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 12; Journal ID: ISSN 1477-0520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Larsen, Simon, McCormick, Laura J., and Ghosh, Abhik. Rapid one-pot synthesis of pyrrole-appended isocorroles. United States: N. p., 2019.
Web. doi:10.1039/c9ob00168a.
Larsen, Simon, McCormick, Laura J., & Ghosh, Abhik. Rapid one-pot synthesis of pyrrole-appended isocorroles. United States. https://doi.org/10.1039/c9ob00168a
Larsen, Simon, McCormick, Laura J., and Ghosh, Abhik. Wed .
"Rapid one-pot synthesis of pyrrole-appended isocorroles". United States. https://doi.org/10.1039/c9ob00168a. https://www.osti.gov/servlets/purl/1656503.
@article{osti_1656503,
title = {Rapid one-pot synthesis of pyrrole-appended isocorroles},
author = {Larsen, Simon and McCormick, Laura J. and Ghosh, Abhik},
abstractNote = {Free-base meso-triarylcorroles have been found to undergo oxidative coupling with an excess of pyrrole in dichloromethane in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) affording 5/10-pyrrole-appended isocorroles in reasonable yields (35–60%) and in a matter of seconds. The free-base isocorrole ligands could all be complexed to copper with Cu(OAc)2·H2O in chloroform/methanol in 55–80% yields. Furthermore, single-crystal X-ray structures of two of the new compounds (H2[5-pyr-TpOMePiC] and Cu[10-pyr-TpOMePiC]) revealed planar macrocycles with rms atomic displacements of only 0.02 and 0.06 Å relative to their respective best-fit C19N4 planes. Both free-base and Cu(II)-complexed isocorroles exhibit richly featured UV-vis-NIR spectra with red/NIR absorption maxima at ~650 nm and ~725 nm for the free-bases and ~800–850 nm for the copper complexes, suggesting potential applications in photodynamic therapy. Cyclic voltammetric analyses of five of the Cu complexes revealed fully reversible redox cycles with multiple oxidation and reduction features.},
doi = {10.1039/c9ob00168a},
journal = {Organic and Biomolecular Chemistry},
number = 12,
volume = 17,
place = {United States},
year = {Wed Mar 06 00:00:00 EST 2019},
month = {Wed Mar 06 00:00:00 EST 2019}
}
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