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 | ||
dc.identifier.eissn | 1520-5207 | |
dc.identifier.uri | ||
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 | ||
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 |