TY - JOUR
T1 - Molecular tuning in highly fluorescent dithieno[3,2-b:2′,3′-d] pyrrole-based oligomers
T2 - Effects of N-functionalization and terminal aryl unit
AU - Evenson, Sean J.
AU - Pappenfus, Ted M.
AU - Delgado, M. Carmen Ruiz
AU - Radke-Wohlers, Karla R.
AU - Navarrete, J. T.López
AU - Rasmussen, Seth C.
PY - 2012/5/7
Y1 - 2012/5/7
N2 - A series of eight conjugated oligomers consisting of central dithieno[3,2-b:2′,3′-d]pyrroles (DTPs) end-capped with either thienyl or phenyl groups have been prepared from N-alkyl-, N-aryl-, and N-acyl-dithieno[3,2-b:2′,3′-d]pyrroles via Stille and Suzuki cross-coupling. The DTP-based quaterthiophene, N-phenyl-2,6-bis(2-thienyl) dithieno-[3,2-b:2′,3′-d]pyrrole was characterized via X-ray crystallography and was found to crystallize in the orthorhombic space group Pna2 1 with a = 10.8666(3) Å, b = 22.8858(6) Å, c = 7.4246(2) Å, and Z = 4. The full oligomeric series was thoroughly investigated via photophysical, electrochemical, and DFT calculations in order to correlate the cumulative effects of both aryl end-groups and N-functionalization on the resulting optical and electronic properties. Through such molecular tuning, it was found to be possible to modulate the HOMO energy by as much as 0.32 V and to generate highly fluorescent oligomers with solution fluorescence efficiencies as high as 92%. This journal is
AB - A series of eight conjugated oligomers consisting of central dithieno[3,2-b:2′,3′-d]pyrroles (DTPs) end-capped with either thienyl or phenyl groups have been prepared from N-alkyl-, N-aryl-, and N-acyl-dithieno[3,2-b:2′,3′-d]pyrroles via Stille and Suzuki cross-coupling. The DTP-based quaterthiophene, N-phenyl-2,6-bis(2-thienyl) dithieno-[3,2-b:2′,3′-d]pyrrole was characterized via X-ray crystallography and was found to crystallize in the orthorhombic space group Pna2 1 with a = 10.8666(3) Å, b = 22.8858(6) Å, c = 7.4246(2) Å, and Z = 4. The full oligomeric series was thoroughly investigated via photophysical, electrochemical, and DFT calculations in order to correlate the cumulative effects of both aryl end-groups and N-functionalization on the resulting optical and electronic properties. Through such molecular tuning, it was found to be possible to modulate the HOMO energy by as much as 0.32 V and to generate highly fluorescent oligomers with solution fluorescence efficiencies as high as 92%. This journal is
UR - http://www.scopus.com/inward/record.url?scp=84859762037&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84859762037&partnerID=8YFLogxK
U2 - 10.1039/c2cp40161d
DO - 10.1039/c2cp40161d
M3 - Article
C2 - 22453255
AN - SCOPUS:84859762037
SN - 1463-9076
VL - 14
SP - 6101
EP - 6111
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 17
ER -