TY - JOUR
T1 - A combined theoretical and experimental study of the polymer inter-chain structure in poly(phenylene vinylene) derivatives
AU - Sumpter, B. G.
AU - Drummond, M. L.
AU - Shelton, W. A.
AU - Valeev, E. F.
AU - Barnes, Md
PY - 2008
Y1 - 2008
N2 - The structures and photophysical properties of single molecule MEH-PPV (2-methoxy-5-(2′-ethyl-hexyloxy)-p-phenylenevinylene) and CN-PPV (2,5,2′ ,5′-tetrahexyloxy-7,8′-dicyano-p-phenylenevinylene) nanoparticles are investigated using electronic structure theory and high resolution fluorescence experiments. It is shown that electron withdrawing substituents, such as CN, on the vinyl group of the PPV polymer backbone cause substantial change in the π electronic structure which subsequently decreases the inter-chain distance. Not only does CN-PPV have a smaller inter-chain separation compared to MEH-PPV, but also an increased binding energy and more efficient charge transport (carrier mobility) due to larger electronic coupling (charge transfer integrals). These changes help explain the enhanced luminescence quantum yield, photo-stability, and lifetime for CN-PPV versus MEH-PPV observed in experimental high resolution fluorescence imaging of individual single molecule nanoparticles.
AB - The structures and photophysical properties of single molecule MEH-PPV (2-methoxy-5-(2′-ethyl-hexyloxy)-p-phenylenevinylene) and CN-PPV (2,5,2′ ,5′-tetrahexyloxy-7,8′-dicyano-p-phenylenevinylene) nanoparticles are investigated using electronic structure theory and high resolution fluorescence experiments. It is shown that electron withdrawing substituents, such as CN, on the vinyl group of the PPV polymer backbone cause substantial change in the π electronic structure which subsequently decreases the inter-chain distance. Not only does CN-PPV have a smaller inter-chain separation compared to MEH-PPV, but also an increased binding energy and more efficient charge transport (carrier mobility) due to larger electronic coupling (charge transfer integrals). These changes help explain the enhanced luminescence quantum yield, photo-stability, and lifetime for CN-PPV versus MEH-PPV observed in experimental high resolution fluorescence imaging of individual single molecule nanoparticles.
UR - http://www.scopus.com/inward/record.url?scp=67650693829&partnerID=8YFLogxK
U2 - 10.1088/1749-4699/1/1/015006
DO - 10.1088/1749-4699/1/1/015006
M3 - Article
AN - SCOPUS:67650693829
SN - 1749-4680
VL - 1
JO - Computational Science and Discovery
JF - Computational Science and Discovery
IS - 1
M1 - 015006
ER -