Impact of systematic structural variation on the energetics of π−π stacking interactions and associated computed charge transfer integrals of crystalline diketopyrrolopyrroles

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

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Control over solid state structure is critical for effective performance in optoelectronic devices bearing π-conjugated charge mediating organic materials. A series of five structurally related N-benzyl-substituted diketopyrrolopyrroles (DPPs) differing solely in 2 out their 60 atoms were synthesized and crystal structures obtained. Systematic variation of the long axis aligned, π−π stacks has been identified within the single crystal structure series and intermolecular interaction energies and charge transfer integrals for the π−π stacks have been computed by means of density functional theory (M06-2X/6-311G(d)). The computed intermolecular interaction energies as well as charge transfer integrals were further investigated utilizing a series of systematically cropped dimer pairs, highlighting the crucial role of the benzyl/halo substitution on stabilization of these π−π dimers. Two of the DPPs, including a new polymorph of a previously reported structure exhibit twice the intermolecular interaction energy and comparable hole transfer integrals to Rubrene, one of the most efficient hole conducting materials known. The computed properties for all of the π−π dimer systems reported herein are consistent with trends predicted by a model system. As such these materials show great promise as charge mediators in organic electronic applications and may be exploited in systematic structure activity based investigations of charge transfer theory.
LanguageEnglish
Pages4849-4858
Number of pages10
JournalCrystal Growth and Design
Volume14
Issue number9
Early online date28 Jul 2014
DOIs
Publication statusPublished - 2014

Fingerprint

Dimers
Charge transfer
dimers
charge transfer
Crystalline materials
Bearings (structural)
Crystal structure
energy transfer
crystal structure
interactions
organic materials
optoelectronic devices
Polymorphism
Optoelectronic devices
Energy transfer
Density functional theory
halos
Substitution reactions
Stabilization
stabilization

Keywords

  • solid state
  • structural variation
  • crystalline diketopyrrolopyrroles
  • charge transport activity
  • crystal structure
  • Rubrene

Cite this

@article{4afaeb33c0da4b4fa60d16fb3699c23e,
title = "Impact of systematic structural variation on the energetics of π−π stacking interactions and associated computed charge transfer integrals of crystalline diketopyrrolopyrroles",
abstract = "Control over solid state structure is critical for effective performance in optoelectronic devices bearing π-conjugated charge mediating organic materials. A series of five structurally related N-benzyl-substituted diketopyrrolopyrroles (DPPs) differing solely in 2 out their 60 atoms were synthesized and crystal structures obtained. Systematic variation of the long axis aligned, π−π stacks has been identified within the single crystal structure series and intermolecular interaction energies and charge transfer integrals for the π−π stacks have been computed by means of density functional theory (M06-2X/6-311G(d)). The computed intermolecular interaction energies as well as charge transfer integrals were further investigated utilizing a series of systematically cropped dimer pairs, highlighting the crucial role of the benzyl/halo substitution on stabilization of these π−π dimers. Two of the DPPs, including a new polymorph of a previously reported structure exhibit twice the intermolecular interaction energy and comparable hole transfer integrals to Rubrene, one of the most efficient hole conducting materials known. The computed properties for all of the π−π dimer systems reported herein are consistent with trends predicted by a model system. As such these materials show great promise as charge mediators in organic electronic applications and may be exploited in systematic structure activity based investigations of charge transfer theory.",
keywords = "solid state, structural variation, crystalline diketopyrrolopyrroles, charge transport activity , crystal structure, Rubrene",
author = "Jesus Calvo-Castro and Monika Warzecha and Alan Kennedy and Callum McHugh and McLean, {Andrew J.}",
year = "2014",
doi = "10.1021/cg5010165",
language = "English",
volume = "14",
pages = "4849--4858",
journal = "Crystal Growth and Design",
issn = "1528-7483",
publisher = "American Chemical Society",
number = "9",

}

TY - JOUR

T1 - Impact of systematic structural variation on the energetics of π−π stacking interactions and associated computed charge transfer integrals of crystalline diketopyrrolopyrroles

AU - Calvo-Castro, Jesus

AU - Warzecha, Monika

AU - Kennedy, Alan

AU - McHugh, Callum

AU - McLean, Andrew J.

PY - 2014

Y1 - 2014

N2 - Control over solid state structure is critical for effective performance in optoelectronic devices bearing π-conjugated charge mediating organic materials. A series of five structurally related N-benzyl-substituted diketopyrrolopyrroles (DPPs) differing solely in 2 out their 60 atoms were synthesized and crystal structures obtained. Systematic variation of the long axis aligned, π−π stacks has been identified within the single crystal structure series and intermolecular interaction energies and charge transfer integrals for the π−π stacks have been computed by means of density functional theory (M06-2X/6-311G(d)). The computed intermolecular interaction energies as well as charge transfer integrals were further investigated utilizing a series of systematically cropped dimer pairs, highlighting the crucial role of the benzyl/halo substitution on stabilization of these π−π dimers. Two of the DPPs, including a new polymorph of a previously reported structure exhibit twice the intermolecular interaction energy and comparable hole transfer integrals to Rubrene, one of the most efficient hole conducting materials known. The computed properties for all of the π−π dimer systems reported herein are consistent with trends predicted by a model system. As such these materials show great promise as charge mediators in organic electronic applications and may be exploited in systematic structure activity based investigations of charge transfer theory.

AB - Control over solid state structure is critical for effective performance in optoelectronic devices bearing π-conjugated charge mediating organic materials. A series of five structurally related N-benzyl-substituted diketopyrrolopyrroles (DPPs) differing solely in 2 out their 60 atoms were synthesized and crystal structures obtained. Systematic variation of the long axis aligned, π−π stacks has been identified within the single crystal structure series and intermolecular interaction energies and charge transfer integrals for the π−π stacks have been computed by means of density functional theory (M06-2X/6-311G(d)). The computed intermolecular interaction energies as well as charge transfer integrals were further investigated utilizing a series of systematically cropped dimer pairs, highlighting the crucial role of the benzyl/halo substitution on stabilization of these π−π dimers. Two of the DPPs, including a new polymorph of a previously reported structure exhibit twice the intermolecular interaction energy and comparable hole transfer integrals to Rubrene, one of the most efficient hole conducting materials known. The computed properties for all of the π−π dimer systems reported herein are consistent with trends predicted by a model system. As such these materials show great promise as charge mediators in organic electronic applications and may be exploited in systematic structure activity based investigations of charge transfer theory.

KW - solid state

KW - structural variation

KW - crystalline diketopyrrolopyrroles

KW - charge transport activity

KW - crystal structure

KW - Rubrene

UR - http://pubs.acs.org/journal/cgdefu

U2 - 10.1021/cg5010165

DO - 10.1021/cg5010165

M3 - Article

VL - 14

SP - 4849

EP - 4858

JO - Crystal Growth and Design

T2 - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 9

ER -