Year

2017

Type(s)

Journal Article

Author(s)

Etherington, M.K. and Franchello, F. and Gibson, J. and Northey, T. and Santos, J. and Ward, J.S. and Higginbotham, H.F. and Data, P. and Kurowska, A. and Dos Santos, P.L. and Graves, D.R. and Batsanov, A.S. and DIas, F.B. and Bryce, M.R. and Penfold, T.J. and Monkman, A.P.

Source

Nature Communications, 8, 2017

Url

https://www.scopus.com/inward/record.uri?eid=2-s2.0-85017426590&doi=10.1038%2fncomms14987&partnerID=40&md5=5080b2ae721924b7a9fb85616d972566

BibTeX

BibTeX

BibTeX

@ARTICLE{Etherington2017, author={Etherington, M.K. and Franchello, F. and Gibson, J. and Northey, T. and Santos, J. and Ward, J.S. and Higginbotham, H.F. and Data, P. and Kurowska, A. and Dos Santos, P.L. and Graves, D.R. and Batsanov, A.S. and DIas, F.B. and Bryce, M.R. and Penfold, T.J. and Monkman, A.P.}, title={Regio-A nd conformational isomerization critical to design of efficient thermally-activated delayed fluorescence emitters}, journal={Nature Communications}, year={2017}, volume={8}, doi={10.1038/ncomms14987}, art_number={14987}, note={cited By 103}, url={https://www.scopus.com/inward/record.uri?eid=2-s2.0-85017426590&doi=10.1038%2fncomms14987&partnerID=40&md5=5080b2ae721924b7a9fb85616d972566}, affiliation={Department of Physics, Durham University, South Road, Durham, DH13LE, United Kingdom; School of Chemistry, Newcastle University, Newcastle, Tyne, NE17RU, United Kingdom; Department of Chemistry, Durham University, South Road, Durham, DH13LE, United Kingdom; Faculty of Chemistry, Silesian University of Technology, Marcina Strzody 9, Gliwice, 44-100, Poland}, abstract={Regio-A nd conformational isomerization are fundamental in chemistry, with profound effects upon physical properties, however their role in excited state properties is less developed. Here two regioisomers of bis(10H-phenothiazin-10-yl)dibenzo[b,d]thiophene-S,S-dioxide, a donor-acceptor-donor (D-A-D) thermally-activated delayed fluorescence (TADF) emitter, are studied. 2,8-bis(10H-phenothiazin-10-yl)dibenzo[b,d]thiophene-S,S-dioxide exhibits only one quasi-equatorial conformer on both donor sites, with charge-transfer (CT) emission close to the local triplet state leading to efficient TADF via spin-vibronic coupling. However, 3,7-bis(10H-phenothiazin-10-yl)dibenzo[b,d]thiophene-S,S-dioxide displays both a quasi-equatorial CT state and a higher-energy quasi-axial CT state. No TADF is observed in the quasi-axial CT emission. These two CT states link directly to the two folded conformers of phenothiazine. The presence of the low-lying local triplet state of the axial conformer also means that this quasi-axial CT is an effective loss pathway both photophysically and in devices. Importantly, donors or acceptors with more than one conformer have negative repercussions for TADF in organic light-emitting diodes. © 2017 The Author(s).}, keywords={2,8 bis(10h phenothiazin 10 yl)dibenzo[b,d]thiophene dioxide; bis(10h phenothiazin 10 yl)dibenzo[b,d]thiophene dioxide; nitrogen; phenothiazine; unclassified drug, chemical compound; chemistry; design method; electronic equipment; equipment; physical property, absorption; Article; conformation; crystal structure; cyclic potentiometry; donor site; electron spin resonance; fluorescence; isomer; isomerization; light emitting diode; oxidation; phosphorescence; quantum chemistry; quantum yield; temperature dependence}, chemicals_cas={nitrogen, 7727-37-9; phenothiazine, 92-84-2}, references={Wilkinson, F., Horrocks, A.R., (1968) Luminescence in Chemistry, pp. 116-153. , (ed. Bowen, E. J. ) Van Nostrand; Berberan-Santos, M.N., Garcia, J.M.M., Unusually strong delayedfluorescence of C 70 (1996) J. Am. Chem. Soc., 118, pp. 9391-9394; Zhu, Y., Kulkarni, A.P., Jenekhe, S.A., Phenoxazine-based emissive donor-acceptor 77 materials for efficient organic light-emitting diodes (2005) Chem. Mater., 17, pp. 5225-5227; Uoyama, H., Goushi, K., Shizu, K., Nomura, H., Adachi, C., Highly efficientorganic light-emitting diodes from delayed fluorescence (2012) Nature, 492, pp. 234-238; Dias, F.B., Triplet harvesting with 100% efficiency by way of thermallyactivated delayed fluorescence in charge transfer OLED emitters (2013) Adv. Mater., 25, pp. 3707-3714; Gibson, J., Monkman, A.P., Penfold, T.J., The importance of vibroniccoupling for efficient reverse intersystem crossing in thermally activateddelayed fluorescence molecules (2016) ChemPhysChem, 17, pp. 2956-2961; Etherington, M.K., Gibson, J., Higginbotham, H.F., Penfold, T.J., Monkman, A.P., Revealing the spin-vibronic coupling mechanism ofthermally activated delayed fluorescence (2016) Nat. Commun., 7, p. 13680; Olivier, Y., Moral, M., Muccioli, L., Sancho-Garcá, J.-C., Dynamic nature ofexcited states of donor-acceptor TADF materials for OLEDs: How theory canreveal structure-property relationships (2017) J. Mater. Chem. C, , http://dx.doi.org/10.1039/C6TC05075A; Wu, K., Tailoring optoelectronic properties of phenanthroline-basedthermally activated delayed fluorescence emitters through isomer engineering (2016) Adv. Opt. Mater., 4, pp. 1558-1566; Dos Santos, P.L., Engineering the singlet-triplet energy splitting in a TADFmolecule (2016) J. Mater. Chem. C, 4, pp. 3815-3824; Yao, L., Tailoring excited-state properties and electroluminescenceperformance of donor-acceptor molecules through tuning the energy level ofthe charge-transfer state (2015) J. Phys. Chem. C, 119, pp. 17800-17808; Taneda, M., Shizu, K., Tanaka, H., Adachi, C., High efficiency thermallyactivated delayed fluorescence based on 1 3, 5-tris(4-(diphenylamino)phenyl)-2, 4, 6-tricyanobenzene (2015) Chem. Commun., 51, pp. 5028-5031; Dias, F.B., The role of local triplet excited states and D-A relativeorientation in thermally activated delayed fluorescence: Photophysics anddevices (2016) Adv. Sci., 3, p. 1600080; Dos Santos, P.L., Ward, J.S., Bryce, M.R., Monkman, A.P., Using guest-hostinteractions to optimize the efficiency of TADF OLEDs (2016) J. Phys. Chem. Lett., 7, pp. 3341-3346; Malrieu, J.-P., Pullman, B., Sur les propriétés électroniques de la phénothiazineet de son radical (1964) Theor. Chim. Acta, 2, pp. 293-301; Bodea, C., Silberg, I., Recent advances in the chemistry of phenothiazines (1968) Chim. Int. J. Chem., 66, pp. 321-460; Coubeils, J.L., Pullman, B., Molecular orbital study of the conformationalproperties of phenothiazines (1972) Theor. Chim. Acta, 24, pp. 35-41; Daub, J., Competition between conformational relaxation andintramolecular electron transfer within phenothiazine-pyrene dyads (2001) J. Phys. Chem. A, 105, pp. 5655-5665; Stockmann, A., Conformational control of photoinduced chargeseparation within phenothiazine-pyrene dyads (2002) J. Phys. Chem. A, 106, pp. 7958-7970; Acar, N., Phenothiazine-pyrene dyads: Photoinduced charge separationand structural relaxation in the CT state (2003) J. Phys. Chem. A, 107, pp. 9530-9541; Druzhinin, S.I., Two-state intramolecular charge transfer (ICT) with3, 5-dimethyl-4-(dimethylamino)benzonitrile (MMD) and its meta-isomermMMD. Ground state amino twist not essential for ICT (2015) J. Phys. Chem. A, 119, pp. 11820-11836; Tanaka, H., Shizu, K., Nakanotani, H., Adachi, C., Dual intramolecularcharge-transfer fluorescence derived from a phenothiazine-triphenyltriazinederivative (2014) J. Phys. Chem. C, 118, pp. 15985-15994; Marian, C.M., Spin-orbit coupling and intersystem crossing in molecules (2012) WileyInterdiscip. Rev. Comput. Mol. Sci., 2, pp. 187-203; Valeur, B., (2001) Molecular Fluorescence: Principles and Applications. MolecularFluorescence, , Wiley-VCH Verlag GmbH; Penfold, T.J., On predicting the excited-state properties of thermally activateddelayed fluorescence emitters (2015) J. Phys. Chem. C, 119, pp. 13535-13544; Al Attar, H.A., Monkman, A.P., Electric field induce blue shift andintensity enhancement in 2D exciplex organic light emitting diodes; Controllingelectron-hole separation (2016) Adv. Mater., 28, pp. 8014-8020; Ward, J.S., The interplay of thermally activated delayed fluorescence(TADF) and room temperature organic phosphorescence in stericallyconstraineddonor-acceptor charge-transfer molecules (2016) Chem. Commun., 52, pp. 3-6; Vardeny, Z., Tauc, J., Method for direct determination of the effectivecorrelation energy of defects in semiconductors: Optical modulationspectroscopy of dangling bonds (1985) Phys. Rev. Lett., 54, pp. 1844-1847; Ghosh, H.N., Sapre, A.V., Palit, D.K., Mittal, J.P., Picosecond flashphotolysis studies on phenothiazine in organic and micellar solution (1997) J. Phys. Chem. B, 101, pp. 2315-2320; Nath, S., Pal, H., Palit, D.K., Sapre, A.V., Mittal, J.P., Steady-state andtime-resolved studies on photoinduced interaction of phenothiazine and10-methylphenothiazine with chloroalkanes (1998) J. Phys. Chem. A, 102, pp. 5822-5830; Henry, B.R., Lawler, E.A., Triplet-triplet absorption studies on relatedheterocyclic molecules (1974) J. Mol. Spectrosc., 51, pp. 385-393; Jankus, V., Highly efficient TADF OLEDs: How the emitter-hostinteraction controls both the excited state species and electrical properties ofthe devices to achieve near 100% triplet harvesting and high efficiency (2014) Adv. Funct. Mater., 24, pp. 6178-6186; Giebink, N.C., Intrinsic luminance loss in phosphorescent small-moleculeorganic light emitting devices due to bimolecular annihilation reactions (2008) J. Appl. Phys., 103, p. 44509; Malrieu, J.-P., Pullman, B., Configuration spatiale et proprietes electroniquesdu noyau d'isoalloxazine (1964) Theor. Chim. Acta, 2, pp. 302-314; Aizenshtat, Z., Klein, E., Weiler-Feilchenfeld, H., Bergmann, E.D., Conformational studies on xanthene, thioxanthene and acridan (1972) Isr. J. Chem., 10, pp. 753-763; Meyer, H.-D., Worth, G.A., Quantum molecular dynamics:propagating wavepackets and density operators using the multiconfigurationtime-dependent Hartree method (2003) Theor. Chem. Acc., 109, pp. 251-267}, correspondence_address1={Monkman, A.P.; Department of Physics, Durham University, South Road, United Kingdom; email: a.p.monkman@durham.ac.uk}, publisher={Nature Publishing Group}, issn={20411723}, pubmed_id={28406153}, language={English}, abbrev_source_title={Nat. Commun.}, document_type={Article}, source={Scopus},