Intermolecular interactions and energetics in the crystalline π-π stacks and associated model dimer systems of asymmetric halogenated diketopyrrolopyrroles

Jesus Calvo-Castro, Monika Warzecha, Iain D. H. Oswald, Alan R. Kennedy, Graeme Morris, Andrew J. McLean, Callum J. McHugh

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Four novel structurally analogous asymmetric, halogenated N-benzyl substituted diketopyrrolopyrroles (DPP) have been synthesized, and their crystal structures obtained. All four crystal structures exhibit π–π stacks with very small displacements along their short molecular axes, which based upon our previous studies involving symmetrical DPPs is a characteristic of N-benzyl substitution. Intermolecular interaction energies were computed for extracted crystal π–π dimer pairs by means of M06-2X density functional at the 6-311G(d) level to investigate the most energetically favored position of the halogen atoms in FBDPP and ClBDPP structures. In addition, effective stabilization energies arising from both benzyl and halogen substitution in these derivatives and in BrBDPP and IBDPP π–π dimer pairs were determined in order to probe the impact of these groups on the resulting dimer stability. Effects of the intermonomer displacements along the long molecular axis, which have been shown by us previously to significantly influence wavefunction overlap and effective electronic coupling, were investigated in detail using aligned and anti-aligned model systems of ClDPP and BrDPP. The predictions of these model systems are remarkably consistent with the observed displacements in their crystal derived π–π dimer pair equivalents, offering insight into the effective role of intermolecular contacts in crystal structures involving this molecular motif, particularly with a view toward crystal engineering in these systems. As a result, we believe that this study should be of significant interest to the growing DPP based materials community and in general to those investigating the detailed manner by which substituents can be employed in the supramolecular design of crystalline molecular architectures.
LanguageEnglish
Pages1531-1542
Number of pages12
JournalCrystal Growth and Design
Volume16
Issue number3
DOIs
Publication statusPublished - 13 Jan 2016

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Dimers
dimers
Crystalline materials
Halogens
Crystal structure
halogens
crystal structure
Substitution reactions
Crystal engineering
interactions
substitutes
crystals
Crystals
Wave functions
Stabilization
stabilization
engineering
Derivatives
Atoms
energy

Keywords

  • diketopyrrolopyrroles
  • Intermolecular Interactions
  • organic semiconductors
  • Crystal structure
  • solid state

Cite this

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title = "Intermolecular interactions and energetics in the crystalline π-π stacks and associated model dimer systems of asymmetric halogenated diketopyrrolopyrroles",
abstract = "Four novel structurally analogous asymmetric, halogenated N-benzyl substituted diketopyrrolopyrroles (DPP) have been synthesized, and their crystal structures obtained. All four crystal structures exhibit π–π stacks with very small displacements along their short molecular axes, which based upon our previous studies involving symmetrical DPPs is a characteristic of N-benzyl substitution. Intermolecular interaction energies were computed for extracted crystal π–π dimer pairs by means of M06-2X density functional at the 6-311G(d) level to investigate the most energetically favored position of the halogen atoms in FBDPP and ClBDPP structures. In addition, effective stabilization energies arising from both benzyl and halogen substitution in these derivatives and in BrBDPP and IBDPP π–π dimer pairs were determined in order to probe the impact of these groups on the resulting dimer stability. Effects of the intermonomer displacements along the long molecular axis, which have been shown by us previously to significantly influence wavefunction overlap and effective electronic coupling, were investigated in detail using aligned and anti-aligned model systems of ClDPP and BrDPP. The predictions of these model systems are remarkably consistent with the observed displacements in their crystal derived π–π dimer pair equivalents, offering insight into the effective role of intermolecular contacts in crystal structures involving this molecular motif, particularly with a view toward crystal engineering in these systems. As a result, we believe that this study should be of significant interest to the growing DPP based materials community and in general to those investigating the detailed manner by which substituents can be employed in the supramolecular design of crystalline molecular architectures.",
keywords = "diketopyrrolopyrroles, Intermolecular Interactions, organic semiconductors, Crystal structure, solid state",
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Intermolecular interactions and energetics in the crystalline π-π stacks and associated model dimer systems of asymmetric halogenated diketopyrrolopyrroles. / Calvo-Castro, Jesus; Warzecha, Monika; Oswald, Iain D. H.; Kennedy, Alan R.; Morris, Graeme; McLean, Andrew J.; McHugh, Callum J.

In: Crystal Growth and Design, Vol. 16, No. 3, 13.01.2016, p. 1531-1542.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Intermolecular interactions and energetics in the crystalline π-π stacks and associated model dimer systems of asymmetric halogenated diketopyrrolopyrroles

AU - Calvo-Castro, Jesus

AU - Warzecha, Monika

AU - Oswald, Iain D. H.

AU - Kennedy, Alan R.

AU - Morris, Graeme

AU - McLean, Andrew J.

AU - McHugh, Callum J.

N1 - © ACM 2016. This is the author's version of the work. It is posted here for your personal use. Not for redistribution. The definitive Version of Record was published in Crystal Growth & Design, http://dx.doi.org/10.1145/10.1021/acs.cgd.5b01656

PY - 2016/1/13

Y1 - 2016/1/13

N2 - Four novel structurally analogous asymmetric, halogenated N-benzyl substituted diketopyrrolopyrroles (DPP) have been synthesized, and their crystal structures obtained. All four crystal structures exhibit π–π stacks with very small displacements along their short molecular axes, which based upon our previous studies involving symmetrical DPPs is a characteristic of N-benzyl substitution. Intermolecular interaction energies were computed for extracted crystal π–π dimer pairs by means of M06-2X density functional at the 6-311G(d) level to investigate the most energetically favored position of the halogen atoms in FBDPP and ClBDPP structures. In addition, effective stabilization energies arising from both benzyl and halogen substitution in these derivatives and in BrBDPP and IBDPP π–π dimer pairs were determined in order to probe the impact of these groups on the resulting dimer stability. Effects of the intermonomer displacements along the long molecular axis, which have been shown by us previously to significantly influence wavefunction overlap and effective electronic coupling, were investigated in detail using aligned and anti-aligned model systems of ClDPP and BrDPP. The predictions of these model systems are remarkably consistent with the observed displacements in their crystal derived π–π dimer pair equivalents, offering insight into the effective role of intermolecular contacts in crystal structures involving this molecular motif, particularly with a view toward crystal engineering in these systems. As a result, we believe that this study should be of significant interest to the growing DPP based materials community and in general to those investigating the detailed manner by which substituents can be employed in the supramolecular design of crystalline molecular architectures.

AB - Four novel structurally analogous asymmetric, halogenated N-benzyl substituted diketopyrrolopyrroles (DPP) have been synthesized, and their crystal structures obtained. All four crystal structures exhibit π–π stacks with very small displacements along their short molecular axes, which based upon our previous studies involving symmetrical DPPs is a characteristic of N-benzyl substitution. Intermolecular interaction energies were computed for extracted crystal π–π dimer pairs by means of M06-2X density functional at the 6-311G(d) level to investigate the most energetically favored position of the halogen atoms in FBDPP and ClBDPP structures. In addition, effective stabilization energies arising from both benzyl and halogen substitution in these derivatives and in BrBDPP and IBDPP π–π dimer pairs were determined in order to probe the impact of these groups on the resulting dimer stability. Effects of the intermonomer displacements along the long molecular axis, which have been shown by us previously to significantly influence wavefunction overlap and effective electronic coupling, were investigated in detail using aligned and anti-aligned model systems of ClDPP and BrDPP. The predictions of these model systems are remarkably consistent with the observed displacements in their crystal derived π–π dimer pair equivalents, offering insight into the effective role of intermolecular contacts in crystal structures involving this molecular motif, particularly with a view toward crystal engineering in these systems. As a result, we believe that this study should be of significant interest to the growing DPP based materials community and in general to those investigating the detailed manner by which substituents can be employed in the supramolecular design of crystalline molecular architectures.

KW - diketopyrrolopyrroles

KW - Intermolecular Interactions

KW - organic semiconductors

KW - Crystal structure

KW - solid state

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

U2 - 10.1021/acs.cgd.5b01656

DO - 10.1021/acs.cgd.5b01656

M3 - Article

VL - 16

SP - 1531

EP - 1542

JO - Crystal Growth and Design

T2 - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

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ER -