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Torsional Bias as a Strategy To Tune Single-triplet Gaps in Organic Diradicals

DeFrancisco, Justin R. (författare)
Johns Hopkins Univ, Dept Chem, 3400 North Charles St, Baltimore, MD 21218 USA
Lopez-Espejo, Guzman (författare)
Univ Malaga, Dept Phys Chem, Campus Teatinos S-N, E-29071 Malaga, Spain
Zafra, Jose Luis (författare)
Univ Malaga, Dept Phys Chem, Campus Teatinos S-N, E-29071 Malaga, Spain
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Yadav, Sangeeta (författare)
Uppsala universitet,Molekylär biomimetik
Messersmith, Reid E. (författare)
Johns Hopkins Univ, Dept Chem, 3400 North Charles St, Baltimore, MD 21218 USA
Gomez-Garcia, Carlos J. (författare)
Univ Valencia, Dept Quim Inorgan, Inst Ciencia Mol, Paterna 46980, Spain
Ottosson, Henrik (författare)
Uppsala universitet,Molekylär biomimetik
Casado, Juan (författare)
Univ Malaga, Dept Phys Chem, Campus Teatinos S-N, E-29071 Malaga, Spain
Tovar, John D. (författare)
Johns Hopkins Univ, Dept Chem, 3400 North Charles St, Baltimore, MD 21218 USA;Johns Hopkins Univ, Dept Mat Sci & Engn, 3400 North Charles St, Baltimore, MD 21218 USA
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 (creator_code:org_t)
2018-05-21
2018
Engelska.
Ingår i: The Journal of Physical Chemistry C. - : AMER CHEMICAL SOC. - 1932-7447 .- 1932-7455. ; 122:23, s. 12148-12157
Relaterad länk:
https://urn.kb.se/re...
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https://doi.org/10.1...
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  • Tidskriftsartikel (refereegranskat)
Abstract Ämnesord
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  • Quinoidal compounds with proaromatic structures possess differing degrees of diradical character, where the open-shell diradical resonance form has restored aromaticity throughout the compound. Methods to tune the diradical character of these compounds have traditionally focused on altering the length and the molecular composition of the pi-conjugated backbones. However, other molecular design strategies to tune the singlet-triplet gap of pi-conjugated quinoidal molecules have not been extensively explored. We previously reported a strikingly small energy gap between the quinoidal and diradical states of a quinoidal small molecule containing methano[10]annulene (TMTQ) that was dictated in large part by the unusual aromaticity of the central annulene ring. Here, we report on two alkylated derivatives of TMTQthat present substantially different torsional biases to the planarity of the TMTQ pi-system. Using a combination of electronic and vibrational spectroscopies, magnetic measurements, and quantum chemical calculations, we demonstrate here how a steric effect rather than pi-electron compositional molecular engineering can dramatically narrow the singlet-triplet gap of a quinoidal compound to as small as -0.52 kcal/mol, determined experimentally. This study offers important insight for the continued development of open-shell diradical molecules that need not rely exclusively on the design of synthesis of new and complex conjugated systems.

Ämnesord

NATURVETENSKAP  -- Kemi -- Fysikalisk kemi (hsv//swe)
NATURAL SCIENCES  -- Chemical Sciences -- Physical Chemistry (hsv//eng)

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