Torsional angle dependence and switching of inner sphere reorganisation energies for electron and hole transfer processes involving phenyl substituted diketopyrrolopyrroles: a density functional study

Jesus Calvo-Castro, Callum J. McHugh, Andrew J. McLean

Research output: Contribution to journalArticle

Abstract

Determination of inner sphere reorganisation energies is important in the development of organic charge mediating materials and electron transfer reactions. In this study, hole and electron inner sphere reorganisation energies, lambda(h) and lambda(e) respectively, have been computed for the first time for a series of structurally related diketopyrrolopyrrole (DPP) molecular motifs. Inner sphere reorganisation energies for self-exchange electron transfer reactions are calculated as being lower than those associated hole transfer processes in model planar phenyl and thiophenyl substituted DPP systems. It is found that lambda(e) < lambda(h) for all planar ring/DPP core structures examined. The effect on lambda(h/e) of non-planarity between phenyl substituents and DPP core is explored in detail. The relative ordering of lambda(h) and lambda(e) is dependent upon the torsional angle of phenyl rings and reverses at twist angles of greater than 60 degrees such that lambda(e) > lambda(h).
Original languageEnglish
Pages (from-to)609-617
JournalDyes and Pigments
Volume113
DOIs
Publication statusPublished - Feb 2015

Keywords

  • Diketopyrrolopyrroles
  • Reorganisation energies
  • Hole transfer
  • Electron transfer
  • DPP
  • Density functional theory

Cite this

@article{66534048444143eaa3f78fa1b3e4756a,
title = "Torsional angle dependence and switching of inner sphere reorganisation energies for electron and hole transfer processes involving phenyl substituted diketopyrrolopyrroles: a density functional study",
abstract = "Determination of inner sphere reorganisation energies is important in the development of organic charge mediating materials and electron transfer reactions. In this study, hole and electron inner sphere reorganisation energies, lambda(h) and lambda(e) respectively, have been computed for the first time for a series of structurally related diketopyrrolopyrrole (DPP) molecular motifs. Inner sphere reorganisation energies for self-exchange electron transfer reactions are calculated as being lower than those associated hole transfer processes in model planar phenyl and thiophenyl substituted DPP systems. It is found that lambda(e) < lambda(h) for all planar ring/DPP core structures examined. The effect on lambda(h/e) of non-planarity between phenyl substituents and DPP core is explored in detail. The relative ordering of lambda(h) and lambda(e) is dependent upon the torsional angle of phenyl rings and reverses at twist angles of greater than 60 degrees such that lambda(e) > lambda(h).",
keywords = "Diketopyrrolopyrroles, Reorganisation energies, Hole transfer, Electron transfer, DPP, Density functional theory",
author = "Jesus Calvo-Castro and McHugh, {Callum J.} and McLean, {Andrew J.}",
year = "2015",
month = "2",
doi = "10.1016/j.dyepig.2014.09.031",
language = "English",
volume = "113",
pages = "609--617",
journal = "Dyes and Pigments",
issn = "0143-7208",
publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Torsional angle dependence and switching of inner sphere reorganisation energies for electron and hole transfer processes involving phenyl substituted diketopyrrolopyrroles

T2 - a density functional study

AU - Calvo-Castro, Jesus

AU - McHugh, Callum J.

AU - McLean, Andrew J.

PY - 2015/2

Y1 - 2015/2

N2 - Determination of inner sphere reorganisation energies is important in the development of organic charge mediating materials and electron transfer reactions. In this study, hole and electron inner sphere reorganisation energies, lambda(h) and lambda(e) respectively, have been computed for the first time for a series of structurally related diketopyrrolopyrrole (DPP) molecular motifs. Inner sphere reorganisation energies for self-exchange electron transfer reactions are calculated as being lower than those associated hole transfer processes in model planar phenyl and thiophenyl substituted DPP systems. It is found that lambda(e) < lambda(h) for all planar ring/DPP core structures examined. The effect on lambda(h/e) of non-planarity between phenyl substituents and DPP core is explored in detail. The relative ordering of lambda(h) and lambda(e) is dependent upon the torsional angle of phenyl rings and reverses at twist angles of greater than 60 degrees such that lambda(e) > lambda(h).

AB - Determination of inner sphere reorganisation energies is important in the development of organic charge mediating materials and electron transfer reactions. In this study, hole and electron inner sphere reorganisation energies, lambda(h) and lambda(e) respectively, have been computed for the first time for a series of structurally related diketopyrrolopyrrole (DPP) molecular motifs. Inner sphere reorganisation energies for self-exchange electron transfer reactions are calculated as being lower than those associated hole transfer processes in model planar phenyl and thiophenyl substituted DPP systems. It is found that lambda(e) < lambda(h) for all planar ring/DPP core structures examined. The effect on lambda(h/e) of non-planarity between phenyl substituents and DPP core is explored in detail. The relative ordering of lambda(h) and lambda(e) is dependent upon the torsional angle of phenyl rings and reverses at twist angles of greater than 60 degrees such that lambda(e) > lambda(h).

KW - Diketopyrrolopyrroles

KW - Reorganisation energies

KW - Hole transfer

KW - Electron transfer

KW - DPP

KW - Density functional theory

U2 - 10.1016/j.dyepig.2014.09.031

DO - 10.1016/j.dyepig.2014.09.031

M3 - Article

VL - 113

SP - 609

EP - 617

JO - Dyes and Pigments

JF - Dyes and Pigments

SN - 0143-7208

ER -