Excitation of highly conjugated (porphinato)palladium(II) and (porphinato)platinum(II) oligomers produces long-lived, triplet states at unit quantum yield that absorb strongly over broad spectral domains of the NIR.

dc.contributor.author

Duncan, Timothy V

dc.contributor.author

Frail, Paul R

dc.contributor.author

Miloradovic, Ivan R

dc.contributor.author

Therien, Michael J

dc.coverage.spatial

United States

dc.date.accessioned

2011-06-21T17:26:39Z

dc.date.issued

2010-11-18

dc.description.abstract

Transient dynamical studies of bis[(5,5'-10,20-bis(2,6-bis(3,3-dimethylbutoxy)phenyl)porphinato)palladium(II)]ethyne (PPd(2)), 5,15-bis{[(5'-10,20-bis(2,6-bis(3,3-dimethylbutoxy)phenyl)porphinato)palladium(II)]ethynyl}(10,20-bis(2,6-bis(3,3-dimethylbutoxy)phenyl)porphinato)palladium(II) (PPd(3)), bis[(5,5'-10,20-bis(2,6-bis(3,3-dimethylbutoxy)phenyl)porphinato)platinum(II)]ethyne (PPt(2)), and 5,15-bis{[(5'-10,20-bis(2,6-bis(3,3-dimethylbutoxy)phenyl)porphinato)platinum(II)]ethynyl}(10,20-bis(2,6-bis(3,3-dimethylbutoxy)phenyl)porphinato)platinum(II) (PPt(3)) show that the electronically excited triplet states of these highly conjugated supermolecular chromophores can be produced at unit quantum yield via fast S(1) → T(1) intersystem crossing dynamics (τ(isc): 5.2-49.4 ps). These species manifest high oscillator strength T(1) → T(n) transitions over broad NIR spectral windows. The facts that (i) the electronically excited triplet lifetimes of these PPd(n) and PPt(n) chromophores are long, ranging from 5 to 50 μs, and (ii) the ground and electronically excited absorptive manifolds of these multipigment ensembles can be extensively modulated over broad spectral domains indicate that these structures define a new precedent for conjugated materials featuring low-lying π-π* electronically excited states for NIR optical limiting and related long-wavelength nonlinear optical (NLO) applications.

dc.description.version

Version of Record

dc.identifier

http://www.ncbi.nlm.nih.gov/pubmed/20527945

dc.identifier.eissn

1520-5207

dc.identifier.uri

https://hdl.handle.net/10161/4070

dc.language

eng

dc.language.iso

en_US

dc.publisher

American Chemical Society (ACS)

dc.relation.ispartof

J Phys Chem B

dc.relation.isversionof

10.1021/jp102901u

dc.relation.journal

Journal of Physical Chemistry B

dc.title

Excitation of highly conjugated (porphinato)palladium(II) and (porphinato)platinum(II) oligomers produces long-lived, triplet states at unit quantum yield that absorb strongly over broad spectral domains of the NIR.

dc.title.alternative
dc.type

Journal article

duke.date.pubdate

2010-11-18

duke.description.issue

45

duke.description.volume

114

pubs.author-url

http://www.ncbi.nlm.nih.gov/pubmed/20527945

pubs.begin-page

14696

pubs.end-page

14702

pubs.issue

45

pubs.organisational-group

Biomedical Engineering

pubs.organisational-group

Chemistry

pubs.organisational-group

Duke

pubs.organisational-group

Duke Cancer Institute

pubs.organisational-group

Institutes and Centers

pubs.organisational-group

Pratt School of Engineering

pubs.organisational-group

School of Medicine

pubs.organisational-group

Trinity College of Arts & Sciences

pubs.publication-status

Published

pubs.volume

114

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