Fluorine Directed Two-Dimensional Cruciform π−π Stacking in Diketopyrrolopyrroles

This is the Accepted Manuscript Version of the following article: Jesus Calvo-Castro, Graeme Morris, Alan R. Kennedy, and Callum J. McHugh, “Fluorine Directed Two-Dimensional Cruciform π–π Stacking in Diketopyrrolopyrroles”, Crystal Growth and Design, Vol. 16 (9): 5385–5393, July 2016. Copyright © 2016 American Chemical Society.Enhanced bulk dimensionality in organic materials employed in optoelectronic devices is desirable and can overcome fabrication issues related to structural defects and grain boundaries. Herein, we report a novel fluorinated diketopyrrolopyrrole single crystal structure, which displays a unique, mutually orthogonal, 2-dimensional cruciform π−π stacking arrangement. The crystal structure is characterized by an unusually large number of nearest neighbor dimer pairs which contribute to a greater thermal integrity than structurally analogous equivalents. Binding energies and charge transfer integrals were computed for all of the crystal extracted dimer pairs by means of the M06-2X density functional at the 6- 311G(d) level. Although weak, a number of intermolecular interactions involving organic fluorine (C−F---H, πF---π, and C−F---πF) were identified to influence the supramolecular assembly of these dimer pairs. Charge transfer integrals for the two π−π stacking crystal dimers were determined using the energy splitting in dimer method. Ambipolar charge transport favoring electron transfer approaching that of rubrene is predicted in both of these π−π stacks, with a greater magnitude of coupling observed from those dimers perpetuating along the crystallographic a-axis. Charge transport behavior in the single crystal is greatly influenced by selective fluorination of the N-benzyl substituents and is consistent with the crystal extracted π−π stacking dimer geometries and their overall influence on wave function overlap. The reported structure is an interesting electron transport material that could be exploited, particularly in thin film based optoelectronic devices, where high bulk dimensionality is required.Peer reviewedFinal Accepted Versio

Effects of fluorine substitution on the intermolecular interactions, energetics and packing behaviour of N-benzyl substituted diketopyrrolopyrroles

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Crystal Growth and Design, after peer review and technical editing by the publisher. To access the final edited and published work see doi: 10.1021/acs.cgd.6b00157.Rationalizing the effects of molecular substitution in π-conjugated organic materials arising from well-defined intermolecular interactions, which can influence the formation of predefined packing motifs and control the emergence of π–π stacking represents a current challenge in supramolecular design. Significant effort is potentially required to manage the impact on solid state packing behavior in materials that have been molecularly tuned to carry out specific photophysical and electrochemical functions. In this regard, fluorine substitution in π-conjugated systems has seen a recent surge of interest, primarily aimed toward the development of materials with enhanced optical and optoelectronic behavior. In light of this interest, in the following study, we report the synthesis and single crystal structures from a series of four novel and structurally related, symmetric, fluorinated N-benzyl substituted diketopyrrolopyrroles (DPPs). Two of the investigated series exhibit slipped cofacial π–π dimer pairs, which are consistent with those reported by us previously in halogenated DPPs. Significantly, this characteristic stacking motif of N-benzyl substituted DPPs can be carefully modified via the replacement of hydrogen atoms with trifluoromethyl and isosteric fluorine–hydrogen substituents. In the case of trifluoromethyl substitution, we identify a previously unobserved packing motif exhibiting a framework of well-defined channels propagating along the length of the crystallographic c-axis. In each of the reported systems, all of the nearest neighbor dimer pairs have been identified and their intermolecular interaction energies computed by means of the M06-2X density functional at the 6-311G(d) level. Through a detailed theoretical analysis involving the determination of cropped dimer energetics, organic fluorine is shown to play an active role in the stabilization of the crystal extracted dimer pairs through a number of additive and weak C–F---H, C–F---πF, and C–F---π intermolecular contacts. Contrary to recent reports, we demonstrate that substitution of hydrogen by fluorine can also lead to dramatic changes in solid state packing behavior as a consequence of these weak interactions. Given the importance of organic fluorine substitution in the construction of π-conjugated materials for optoelectronic materials, we feel that this work should be of interest to the wider community involved in supramolecular design of organic conjugated systems, and in particular to those investigating organic fluorine as well as diketopyrrolopyrrole containing architecturesPeer reviewedFinal Accepted Versio

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

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Crystal Growth & Design, copyright © 2014 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see DOI: https://doi.org/10.1021/cg5010165, or ACS Articles on Request http://pubs.acs.org/page/policy/articlesonrequest/index.html/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 ... Novel crystal structures demonstrating long molecular axis, slipped, π−π cofacial stacking motifs and associated semiconductor bands in a series of N-benzylated diketopyrrolopyrroles are reported. Through variation of just 2 atoms from 60, clear crystal structure/(computed) charge transport activity interdependency is observed, with two structures exhibiting hole transport integrals comparable to Rubrene, a highly effective positive charge carrying, organic, crystalline materialPeer reviewedFinal Accepted Versio

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

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Crystal Growth & Design, © 2016 American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see DOI: 10.1021/acs.cgd.5b01656/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.Peer reviewedFinal Accepted Versio

Detection of nitroaromatic vapours with diketopyrrolopyrrole thin films exploring the role of structural order and morphology on thin film properties and fluorescence quenching efficiency

This document is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. The Version of Record is available at: https://doi.org/10.1039/C4CC08468C.Sensitive optical detection of nitroaromatic vapours with diketopyrrolopyrrole thin films is reported for the first time and the impact of thin film crystal structure and morphology on fluorescence quenching behaviour demonstratedPeer reviewedFinal Accepted Versio

Structural and metal-halogen exchange reactivity studies of sodium magnesiate biphenolate complexes

Bimetallic sodium magnesiates have been employed in metal-halogen exchange for the first time. Utilising the racemic phenoxide ligand 5,5´,6,6´-tetramethyl-3,3´-di-tert-butyl-1,1´-biphenyl-2,2´-diol [(rac)-BIPHEN-H2], the dialkyl sodium magnesiates [(rac)-BIPHEN]Na2MgBu2(TMEDA)2 3 and [(rac)-BIPHEN]Na2MgBu2(PMDETA)2 4 have been synthesised. Both 3 and 4 can be easily prepared through co-complexation of di-n-butylmagnesium with the sodiated (rac)-BIPHEN precursor which can be prepared in situ in hydrocarbon solvent. Prior to the main investigation, synthesis of the sodiated precursor [BIPHEN]2Na4(THF)4 1 was explored in order to better understand the formation of sodium magnesiates utilising the dianionic (rac)-BIPHEN ligand as the parent ligand. In addition, a BIPHEN-rich sodium magnesiate [BIPHEN]2Na2Mg(THF)4 2 was prepared and characterised, and its formation was rationalised. Complex 1 and 4 have also been fully characterised in both solid and solution state. In terms of onward reactivity, 3 and 4 have been tested as potential exchange reagents with aryl and heteroaryl iodides to produce aryl and heteroaryl magnesium phenoxides utilising toluene as a non-polar hydrocarbon solvent. Complex 3 reacted smoothly to give a range of aryl and heteroaryl magnesium phenoxides, whilst 4’s reactivity is more sluggish

Twist and shout: a surprising synergy between aryl and N-substituents defines the computed charge transport properties in a series of crystalline diketopyrrolopyrroles

This is the Accepted Manuscript version of an article accepted for publication in CyrstEngComm. Under embargo. Embargo end date: 22 November 2017. Jesus Calvo-Castrp, Sebastian Macza, Connor Thomson, Graeme Morris, Alan R. Kennedy and Callum J. McHugh, ‘Twist and shout: a surprising synergy between aryl and N-substituents defines the computed charge transport properties in a series of crystalline diketopyrrolopyrroles’, CrysEngComm, Vol 18(48): 9382-9390, first published online 22 November 2016, available at doi: 10.1039/C6CE02261HThe influence of systematic variation of aryl and N-substitution on predicted charge transport behaviour in a series of crystalline diketopyrrolopyrroles is evaluated. A correct combination of substituents is revealed to maximise those properties which dictate device performance in organic single crystals based upon this structural motif. For electron transport, furan and N-alkyl substitution emerge as optimal molecular design strategies, whilst phenyl structures bearing N-benzyl substituents are shown to offer the most significant promise as highly sought after crystalline hole transport materials.Peer reviewedFinal Accepted Versio

Reactivation of tectonics, crustal underplating, and uplift after 60 Myr of passive subsidence, Raukumara Basin, Hikurangi-Kermadec fore arc, New Zealand: implications for global growth and recycling of continents

We use seismic reflection and refraction data to determine crustal structure, to map a fore-arc basin containing 12 km of sediment, and to image the subduction thrust at 35 km depth. Seismic reflection megasequences within the basin are correlated with onshore geology: megasequence X, Late Cretaceous and Paleogene marine passive margin sediments; megasequence Y, a similar to 10,000 km(3) submarine landslide emplaced during subduction initiation at 22 Ma; and megasequence Z, a Neogene subduction margin megasequence. The Moho lies at 17 km beneath the basin center and at 35 km at the southern margin. Beneath the western basin margin, we interpret reflective units as deformed Gondwana fore-arc sediment that was thrust in Cretaceous time over oceanic crust 7 km thick. Raukumara Basin has normal faults at its western margin and is uplifted along its eastern and southern margins. Raukumara Basin represents a rigid fore-arc block > 150 km long, which contrasts with widespread faulting and large Neogene vertical axis rotations farther south. Taper of the western edge of allochthonous unit Y and westward thickening and downlap of immediately overlying strata suggest westward or northwestward paleoslope and emplacement direction rather than southwestward, as proposed for the correlative onshore allochthon. Spatial correlation between rock uplift of the eastern and southern basin margins with the intersection between Moho and subduction thrust leads us to suggest that crustal underplating is modulated by fore-arc crustal thickness. The trench slope has many small extensional faults and lacks coherent internal reflections, suggesting collapse of indurated rock, rather than accretion of > 1 km of sediment from the downgoing plate. The lack of volcanic intrusion east of the active arc, and stratigraphic evidence for the broadening of East Cape Ridge with time, suggests net fore-arc accretion since 22 Ma. We propose a cyclical fore-arc kinematic: rock moves down a subduction channel to near the base of the crust, where underplating drives rock uplift, oversteepens the trench slope, and causes collapse toward the trench and subduction channel. Cyclical rock particle paths led to persistent trench slope subsidence during net accretion. Existing global estimates of fore-arc loss are systematically too high because they assume vertical particle paths. Citation: Sutherland, R., et al. (2009), Reactivation of tectonics, crustal underplating, and uplift after 60 Myr of passive subsidence, Raukumara Basin, Hikurangi-Kermadec fore arc, New Zealand: Implications for global growth and recycling of continents, Tectonics, 28, TC5017, doi: 10.1029/2008TC002356