Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials

Nadzeya A. Kukhta; Heather F. Higginbotham; Tomas Matulaitis; Andrew Danos; Aisha N. Bismillah; Nils Haase; Marc K. Etherington; Dmitry S. Yufit; Paul R. McGonigal; Juozas Vidas Gražulevičius; Andrew P. Monkman

doi:10.1039/C9TC02742D

Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials

Nadzeya A. Kukhta
, Heather F. Higginbotham
, Tomas Matulaitis
, Andrew Danos
, Aisha N. Bismillah
, Nils Haase
, Marc K. Etherington
, Dmitry S. Yufit
, Paul R. McGonigal
, Juozas Vidas Gražulevičius
, Andrew P. Monkman

School of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

We report on the properties of the three positional isomers of (2,7-di-tert-butyl-9,9-dimethylacridin-10(9H)-yl)benzonitrile, which are found to have comparable donor steric environments and donor–acceptor dihedral angles. An unexpected intramolecular dipole interaction imparts a unique molecular geometry to the ortho-linked isomer, while comparison of the meta- and para-isomers uncovers how positional differences in acceptor strengths (a consequence of differences in aromatic π-system electron density) lead to very different triplet harvesting and emission properties. These positional-isomer effects on TADF follow the well-known aromatic directing rules from organic synthesis, in keeping with their common origin arising from contributions of multiple electronic resonance structures. Understanding these positional effects and methods of dihedral control is critical to the future design of efficient TADF emitters.

Original language	English
Pages (from-to)	9184-9194
Number of pages	11
Journal	Journal of Materials Chemistry
Volume	7
Issue number	30
Early online date	12 Jul 2019
DOIs	https://doi.org/10.1039/C9TC02742D
Publication status	Published - 14 Aug 2019

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Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials
Kukhta,, N. A. (Creator), Higginbotham, H. F. (Creator), Matulaitis, T. (Creator), Danos, A. (Creator), Bismillah, A. N. (Creator), Haase, N. (Creator), Etherington, M. K. (Creator), Yufit, D. S. (Creator), McGonigal, P. R. (Creator), Gražulevičius, J. V. (Creator) & Monkman, A. P. (Creator), Cambridge Crystallographic Data Centre, 2019
https://dx.doi.org/10.5517/ccdc.csd.cc22by6l and 2 more links, https://dx.doi.org/10.5517/ccdc.csd.cc22by7m, https://dx.doi.org/10.5517/ccdc.csd.cc22by8n (show fewer)
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Kukhta, N. A., Higginbotham, H. F., Matulaitis, T., Danos, A., Bismillah, A. N., Haase, N., Etherington, M. K., Yufit, D. S., McGonigal, P. R., Gražulevičius, J. V., & Monkman, A. P. (2019). Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials. Journal of Materials Chemistry, 7(30), 9184-9194. https://doi.org/10.1039/C9TC02742D

@article{cbfb4c52850f444f83f4029a0f07ce93,

title = "Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials",

abstract = "We report on the properties of the three positional isomers of (2,7-di-tert-butyl-9,9-dimethylacridin-10(9H)-yl)benzonitrile, which are found to have comparable donor steric environments and donor{\textendash}acceptor dihedral angles. An unexpected intramolecular dipole interaction imparts a unique molecular geometry to the ortho-linked isomer, while comparison of the meta- and para-isomers uncovers how positional differences in acceptor strengths (a consequence of differences in aromatic π-system electron density) lead to very different triplet harvesting and emission properties. These positional-isomer effects on TADF follow the well-known aromatic directing rules from organic synthesis, in keeping with their common origin arising from contributions of multiple electronic resonance structures. Understanding these positional effects and methods of dihedral control is critical to the future design of efficient TADF emitters.",

author = "Kukhta, \{Nadzeya A.\} and Higginbotham, \{Heather F.\} and Tomas Matulaitis and Andrew Danos and Bismillah, \{Aisha N.\} and Nils Haase and Etherington, \{Marc K.\} and Yufit, \{Dmitry S.\} and McGonigal, \{Paul R.\} and Gra{\v z}ulevi{\v c}ius, \{Juozas Vidas\} and Monkman, \{Andrew P.\}",

note = "NAK, HFH, MKE, and APM acknowledge the EU{\textquoteright}s Horizon 2020 for funding the PHEBE project under grant no. 641725. NAK, MKE, AD, NH and APM acknowledge the EU{\textquoteright}s Horizon 2020 for funding the HyperOLED project under grant no. 641725. APM thanks EPSRC grant EP/L02621X/1 for funding. ANB acknowledges an EPSRC Doctoral Training Grant.",

year = "2019",

month = aug,

day = "14",

doi = "10.1039/C9TC02742D",

language = "English",

volume = "7",

pages = "9184--9194",

journal = "Journal of Materials Chemistry",

issn = "0959-9428",

publisher = "Royal Society of Chemistry",

number = "30",

}

Kukhta, NA, Higginbotham, HF, Matulaitis, T, Danos, A, Bismillah, AN, Haase, N, Etherington, MK, Yufit, DS, McGonigal, PR, Gražulevičius, JV & Monkman, AP 2019, 'Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials', Journal of Materials Chemistry, vol. 7, no. 30, pp. 9184-9194. https://doi.org/10.1039/C9TC02742D

Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials. / Kukhta, Nadzeya A.; Higginbotham, Heather F.; Matulaitis, Tomas et al.
In: Journal of Materials Chemistry, Vol. 7, No. 30, 14.08.2019, p. 9184-9194.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials

AU - Kukhta, Nadzeya A.

AU - Higginbotham, Heather F.

AU - Matulaitis, Tomas

AU - Danos, Andrew

AU - Bismillah, Aisha N.

AU - Haase, Nils

AU - Etherington, Marc K.

AU - Yufit, Dmitry S.

AU - McGonigal, Paul R.

AU - Gražulevičius, Juozas Vidas

AU - Monkman, Andrew P.

N1 - NAK, HFH, MKE, and APM acknowledge the EU’s Horizon 2020 for funding the PHEBE project under grant no. 641725. NAK, MKE, AD, NH and APM acknowledge the EU’s Horizon 2020 for funding the HyperOLED project under grant no. 641725. APM thanks EPSRC grant EP/L02621X/1 for funding. ANB acknowledges an EPSRC Doctoral Training Grant.

PY - 2019/8/14

Y1 - 2019/8/14

N2 - We report on the properties of the three positional isomers of (2,7-di-tert-butyl-9,9-dimethylacridin-10(9H)-yl)benzonitrile, which are found to have comparable donor steric environments and donor–acceptor dihedral angles. An unexpected intramolecular dipole interaction imparts a unique molecular geometry to the ortho-linked isomer, while comparison of the meta- and para-isomers uncovers how positional differences in acceptor strengths (a consequence of differences in aromatic π-system electron density) lead to very different triplet harvesting and emission properties. These positional-isomer effects on TADF follow the well-known aromatic directing rules from organic synthesis, in keeping with their common origin arising from contributions of multiple electronic resonance structures. Understanding these positional effects and methods of dihedral control is critical to the future design of efficient TADF emitters.

AB - We report on the properties of the three positional isomers of (2,7-di-tert-butyl-9,9-dimethylacridin-10(9H)-yl)benzonitrile, which are found to have comparable donor steric environments and donor–acceptor dihedral angles. An unexpected intramolecular dipole interaction imparts a unique molecular geometry to the ortho-linked isomer, while comparison of the meta- and para-isomers uncovers how positional differences in acceptor strengths (a consequence of differences in aromatic π-system electron density) lead to very different triplet harvesting and emission properties. These positional-isomer effects on TADF follow the well-known aromatic directing rules from organic synthesis, in keeping with their common origin arising from contributions of multiple electronic resonance structures. Understanding these positional effects and methods of dihedral control is critical to the future design of efficient TADF emitters.

U2 - 10.1039/C9TC02742D

DO - 10.1039/C9TC02742D

M3 - Article

SN - 0959-9428

VL - 7

SP - 9184

EP - 9194

JO - Journal of Materials Chemistry

JF - Journal of Materials Chemistry

IS - 30

ER -

Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials

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Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials

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