Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons
Type
ArticleAuthors
Diev, Vyacheslav V.Schlenker, Cody W.
Hanson, Kenneth
Zhong, Qiwen
Zimmerman, Jeramy D.
Forrest, Stephen R.
Thompson, Mark E.
KAUST Grant Number
KUS-C1-015-21Date
2011-12-05Online Publication Date
2011-12-05Print Publication Date
2012-01-06Permanent link to this record
http://hdl.handle.net/10754/599342
Metadata
Show full item recordAbstract
A systematic study of the preparation of porphyrins with extended conjugation by meso,β-fusion with polycyclic aromatic hydrocarbons (PAHs) is reported. The meso-positions of 5,15-unsubstituted porphyrins were readily functionalized with PAHs. Ring fusion using standard Scholl reaction conditions (FeCl 3, dichloromethane) occurs for perylene-substituted porphyrins to give a porphyrin β,meso annulated with perylene rings (0.7:1 ratio of syn and anti isomers). The naphthalene, pyrene, and coronene derivatives do not react under Scholl conditions but are fused using thermal cyclodehydrogenation at high temperatures, giving mixtures of syn and anti isomers of the meso,β-fused porphyrins. For pyrenyl-substituted porphyrins, a thermal method gives synthetically acceptable yields (>30%). Absorption spectra of the fused porphyrins undergo a progressive bathochromic shift in a series of naphthyl (λ max = 730 nm), coronenyl (λ max = 780 nm), pyrenyl (λ max = 815 nm), and perylenyl (λ max = 900 nm) annulated porphyrins. Despite being conjugated with unsubstituted fused PAHs, the β,meso-fused porphyrins are more soluble and processable than the parent nonfused precursors. Pyrenyl-fused porphyrins exhibit strong fluorescence in the near-infrared (NIR) spectral region, with a progressive improvement in luminescent efficiency (up to 13% with λ max = 829 nm) with increasing degree of fusion. Fused pyrenyl-porphyrins have been used as broadband absorption donor materials in photovoltaic cells, leading to devices that show comparatively high photovoltaic efficiencies. © 2011 American Chemical Society.Citation
Diev VV, Schlenker CW, Hanson K, Zhong Q, Zimmerman JD, et al. (2012) Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons. J Org Chem 77: 143–159. Available: http://dx.doi.org/10.1021/jo201490y.Sponsors
We acknowledge Drs. Matthew Whited and Peter Djurovich for helpful discussion. The Department of Energy, Office of Basic Energy Sciences as part of Energy Frontier Research Center program, the Center for Energy Nanoscience (DE-SC0001013) are acknowledged for support of the OPV studies of compound 2d (C.W.S. and J.D.Z.). We also acknowledge the NSF SOLAR program (Award ID 0934098, S.R.F and Q.Z.), Universal Display Corporation, Global Photonic Energy Corporation and the Center for Advanced Molecular Photovoltaics (CAMP) (KUS-C1-015-21) of the King Abdullah University of Science and Technology (KAUST) for financial support of the other science presented here.Publisher
American Chemical Society (ACS)Journal
The Journal of Organic ChemistryPubMed ID
22077105ae974a485f413a2113503eed53cd6c53
10.1021/jo201490y
Scopus Count
Collections
Publications Acknowledging KAUST SupportRelated articles
- Thermally Induced Synthesis of Anthracene-, Pyrene- and Naphthalene-Fused Porphyrins.
- Authors: Pijeat J, Chaussy L, Simoës R, Isopi J, Lauret JS, Paolucci F, Marcaccio M, Campidelli S
- Issue date: 2021 Oct
- Synthesis of π-extended porphyrins via intramolecular oxidative coupling.
- Authors: Lewtak JP, Gryko DT
- Issue date: 2012 Oct 18
- N-annulated perylene fused porphyrins with enhanced near-IR absorption and emission.
- Authors: Jiao C, Huang KW, Guan Z, Xu QH, Wu J
- Issue date: 2010 Sep 17
- Synthesis of symmetrical tetraaryltetranaphtho[2,3]porphyrins.
- Authors: Finikova OS, Aleshchenkov SE, Briñas RP, Cheprakov AV, Carroll PJ, Vinogradov SA
- Issue date: 2005 Jun 10
- Structural diversity in expanded porphyrins.
- Authors: Misra R, Chandrashekar TK
- Issue date: 2008 Feb