Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons

Handle URI:
http://hdl.handle.net/10754/599342
Title:
Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons
Authors:
Diev, Vyacheslav V.; Schlenker, Cody W.; Hanson, Kenneth; Zhong, Qiwen; Zimmerman, Jeramy D.; Forrest, Stephen R.; Thompson, Mark E.
Abstract:
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.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Organic Chemistry
KAUST Grant Number:
KUS-C1-015-21
Issue Date:
6-Jan-2012
DOI:
10.1021/jo201490y
PubMed ID:
22077105
Type:
Article
ISSN:
0022-3263; 1520-6904
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.
Appears in Collections:
Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorDiev, Vyacheslav V.en
dc.contributor.authorSchlenker, Cody W.en
dc.contributor.authorHanson, Kennethen
dc.contributor.authorZhong, Qiwenen
dc.contributor.authorZimmerman, Jeramy D.en
dc.contributor.authorForrest, Stephen R.en
dc.contributor.authorThompson, Mark E.en
dc.date.accessioned2016-02-28T05:49:36Zen
dc.date.available2016-02-28T05:49:36Zen
dc.date.issued2012-01-06en
dc.identifier.citationDiev 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.en
dc.identifier.issn0022-3263en
dc.identifier.issn1520-6904en
dc.identifier.pmid22077105en
dc.identifier.doi10.1021/jo201490yen
dc.identifier.urihttp://hdl.handle.net/10754/599342en
dc.description.abstractA 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.en
dc.description.sponsorshipWe 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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titlePorphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbonsen
dc.typeArticleen
dc.identifier.journalThe Journal of Organic Chemistryen
dc.contributor.institutionUniversity of Southern California, Los Angeles, United Statesen
dc.contributor.institutionUniversity Michigan Ann Arbor, Ann Arbor, United Statesen
kaust.grant.numberKUS-C1-015-21en
kaust.grant.fundedcenterCenter for Advanced Molecular Photovoltaics (CAMP)en

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