Impact of substituent effects on the Raman spectra of structurally related N-substituted diketopyrrolopyrroles

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

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Control over vibrational frequency modes is important in optimising the performance and behaviour of conjugated organic materials employed as charge transfer mediators and optical components in optoelectronic devices. Raman spectroscopy represents a powerful technique that can be employed to determine the structural implications of molecular substitution on photophysical properties in such conjugated organic environments. Herein, we report for the first time, the optimised geometries for a series of eight systematically varied N-substituted diketopyrrolopyrroles as well as their experimental and computed Raman spectra, with special emphasis placed upon their spectral band assignments. Clear out-of-plane structural re-arrangements, including pyramidalisation of the lactam nitrogens arising from intramolecular H-bonding interactions were observed upon N-substitution in the reported systems, leading to significant vibrational frequency shifts for ν(N-C) and ν(C=O) modes. In addition, mode scaling factors were determined and found to be comparable with those reported previously, employed using the same density functional. The following study addresses the implications of structural variation on the progression of those intense Raman modes which play a key role in tuning the photophysical properties of N-substituted diketopyrrolopyrrole systems and as such should be of broad interest to those developing functional materials based upon this molecular motif.

LanguageEnglish
Pages8-16
Number of pages9
JournalVibrational Spectroscopy
Volume83
Early online date22 Dec 2015
DOIs
Publication statusPublished - 1 Mar 2016

Fingerprint

Vibrational spectra
Raman scattering
Substitution reactions
Lactams
Functional materials
Optoelectronic devices
Raman spectroscopy
Charge transfer
Nitrogen
Tuning
Geometry

Keywords

  • density functional theory
  • diketopyrrolopyrroles
  • M06-2X
  • raman
  • scaling factors

Cite this

@article{1693b00dc2554929a8a62bc07d2ea9cd,
title = "Impact of substituent effects on the Raman spectra of structurally related N-substituted diketopyrrolopyrroles",
abstract = "Control over vibrational frequency modes is important in optimising the performance and behaviour of conjugated organic materials employed as charge transfer mediators and optical components in optoelectronic devices. Raman spectroscopy represents a powerful technique that can be employed to determine the structural implications of molecular substitution on photophysical properties in such conjugated organic environments. Herein, we report for the first time, the optimised geometries for a series of eight systematically varied N-substituted diketopyrrolopyrroles as well as their experimental and computed Raman spectra, with special emphasis placed upon their spectral band assignments. Clear out-of-plane structural re-arrangements, including pyramidalisation of the lactam nitrogens arising from intramolecular H-bonding interactions were observed upon N-substitution in the reported systems, leading to significant vibrational frequency shifts for ν(N-C) and ν(C=O) modes. In addition, mode scaling factors were determined and found to be comparable with those reported previously, employed using the same density functional. The following study addresses the implications of structural variation on the progression of those intense Raman modes which play a key role in tuning the photophysical properties of N-substituted diketopyrrolopyrrole systems and as such should be of broad interest to those developing functional materials based upon this molecular motif.",
keywords = "density functional theory, diketopyrrolopyrroles, M06-2X, raman, scaling factors",
author = "Jesus Calvo-Castro and Monika Warzecha and McLean, {Andrew J.} and McHugh, {Callum J.}",
year = "2016",
month = "3",
day = "1",
doi = "10.1016/j.vibspec.2015.12.004",
language = "English",
volume = "83",
pages = "8--16",
journal = "Vibrational Spectroscopy",
issn = "0924-2031",

}

Impact of substituent effects on the Raman spectra of structurally related N-substituted diketopyrrolopyrroles. / Calvo-Castro, Jesus; Warzecha, Monika; McLean, Andrew J.; McHugh, Callum J.

In: Vibrational Spectroscopy, Vol. 83, 01.03.2016, p. 8-16.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Impact of substituent effects on the Raman spectra of structurally related N-substituted diketopyrrolopyrroles

AU - Calvo-Castro, Jesus

AU - Warzecha, Monika

AU - McLean, Andrew J.

AU - McHugh, Callum J.

PY - 2016/3/1

Y1 - 2016/3/1

N2 - Control over vibrational frequency modes is important in optimising the performance and behaviour of conjugated organic materials employed as charge transfer mediators and optical components in optoelectronic devices. Raman spectroscopy represents a powerful technique that can be employed to determine the structural implications of molecular substitution on photophysical properties in such conjugated organic environments. Herein, we report for the first time, the optimised geometries for a series of eight systematically varied N-substituted diketopyrrolopyrroles as well as their experimental and computed Raman spectra, with special emphasis placed upon their spectral band assignments. Clear out-of-plane structural re-arrangements, including pyramidalisation of the lactam nitrogens arising from intramolecular H-bonding interactions were observed upon N-substitution in the reported systems, leading to significant vibrational frequency shifts for ν(N-C) and ν(C=O) modes. In addition, mode scaling factors were determined and found to be comparable with those reported previously, employed using the same density functional. The following study addresses the implications of structural variation on the progression of those intense Raman modes which play a key role in tuning the photophysical properties of N-substituted diketopyrrolopyrrole systems and as such should be of broad interest to those developing functional materials based upon this molecular motif.

AB - Control over vibrational frequency modes is important in optimising the performance and behaviour of conjugated organic materials employed as charge transfer mediators and optical components in optoelectronic devices. Raman spectroscopy represents a powerful technique that can be employed to determine the structural implications of molecular substitution on photophysical properties in such conjugated organic environments. Herein, we report for the first time, the optimised geometries for a series of eight systematically varied N-substituted diketopyrrolopyrroles as well as their experimental and computed Raman spectra, with special emphasis placed upon their spectral band assignments. Clear out-of-plane structural re-arrangements, including pyramidalisation of the lactam nitrogens arising from intramolecular H-bonding interactions were observed upon N-substitution in the reported systems, leading to significant vibrational frequency shifts for ν(N-C) and ν(C=O) modes. In addition, mode scaling factors were determined and found to be comparable with those reported previously, employed using the same density functional. The following study addresses the implications of structural variation on the progression of those intense Raman modes which play a key role in tuning the photophysical properties of N-substituted diketopyrrolopyrrole systems and as such should be of broad interest to those developing functional materials based upon this molecular motif.

KW - density functional theory

KW - diketopyrrolopyrroles

KW - M06-2X

KW - raman

KW - scaling factors

UR - http://www.scopus.com/inward/record.url?scp=84954155631&partnerID=8YFLogxK

U2 - 10.1016/j.vibspec.2015.12.004

DO - 10.1016/j.vibspec.2015.12.004

M3 - Article

VL - 83

SP - 8

EP - 16

JO - Vibrational Spectroscopy

T2 - Vibrational Spectroscopy

JF - Vibrational Spectroscopy

SN - 0924-2031

ER -