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.
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.
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https://hdl.handle.net/10161/4070Published Version (Please cite this version)
10.1021/jp102901uPublication Info
Duncan, Timothy V; Frail, Paul R; Miloradovic, Ivan R; & Therien, Michael J (2010). 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. J Phys Chem B, 114(45). pp. 14696-14702. 10.1021/jp102901u. Retrieved from https://hdl.handle.net/10161/4070.This is constructed from limited available data and may be imprecise. To cite this
article, please review & use the official citation provided by the journal.
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Show full item recordScholars@Duke
Michael J. Therien
William R. Kenan, Jr. Distinguished Professor of Chemistry
Our research involves the synthesis of compounds, supramolecular assemblies, nano-scale
objects, and electronic materials with unusual ground-and excited-state characteristics,
and interrogating these structures using state-of-the-art transient optical, spectroscopic,
photophysical, and electrochemical methods. Over chemical dimensions that span molecules
to materials, we probe experimental and theoretical aspects of charge migration reactions
and ultrafast electron transfer processes. Insights

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