Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes

Weber L, Werner V, Fox MA, Marder TB, Schwedler S, Brockhinke A, Stammler H-G, Neumann B (2009)
Journal of the Chemical Society. Dalton Transactions (8): 1339-1351.

Download
Es wurde kein Volltext hochgeladen. Nur Publikationsnachweis!
Zeitschriftenaufsatz | Veröffentlicht | Englisch
Abstract / Bemerkung
A series of π-conjugated systems with two and three 1,3-diethyl-1,3,2-benzodiazaborolyl end-groups was synthesised in 58-91% yields using established 1,3,2-diazaborole methodologies. The bis(diazaborolyl) compounds contain thiophene -2,5-C4H2S- (2a), dithiophene -5,5'-(2,2'-C4H2S)(2)- (2b), phenylene -1,4-C6H4- (2c), biphenylene - 4,4'-(1,1'-(C6H4)(2))- (2d) and dioctylfluorene -2,7-(9,9-(C8H7)(2)C11H6)- (2e) bridges. The three-way linkers in the tris(diazaborolyl) assemblies contain a central phenylene unit - 1,3,5-C6H3- linked to the borolyl end groups via thiophene - 2,5-C4H2S- (3a), directly bonded (3b) or via phenylene - 1,4-C6H4- (3c) units. Molecular structures of 2a, 2b, 2c, 3a, 3b and 3c were determined by X-ray crystallographic studies. These borolylated systems show intense blue/violet luminescence with Stokes shifts of 6200-9500 cm(-1) and quantum yields of 0.33 to 0.98. The absorption maxima (296-351 nm) of these assemblies are reproduced well by TD-DFT computations (B3LYP/6-31G*), and arise from strong, low energy HOMO-LUMO transitions. From molecular orbital computations on optimised geometries of these diazaborolyl systems, the LUMO is located mainly on the thiophene/benzene bridge (66-92%) while the HOMO is largely benzodiazaborolyl in character (53-83%). The S-1 <- S-0 absorption bands are thus assigned to π(diazaborolyl)-π*(thiophene/benzene) transitions. Computations on related bis(boryl) dithiophenes [ with diarylboryl e. g. Ph2B, Mes(2)B, (C6F5)(2)B and FMes(2)B (Mes = 2,4,6-Me3C6H2; FMes = 2,4,6-(CF3)(3)C6H2), dioxaborolyl and other diazaborolyl groups] reveal strong, low energy UV-visible absorption bands arising from π(thiophene)-π*(thiophene) transitions, with increasing boron participation in the LUMO of the diarylboryl and especially the highly fluorinated systems.
Erscheinungsjahr
Zeitschriftentitel
Journal of the Chemical Society. Dalton Transactions
Zeitschriftennummer
8
Seite
1339-1351
ISSN
eISSN
PUB-ID

Zitieren

Weber L, Werner V, Fox MA, et al. Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes. Journal of the Chemical Society. Dalton Transactions. 2009;(8):1339-1351.
Weber, L., Werner, V., Fox, M. A., Marder, T. B., Schwedler, S., Brockhinke, A., Stammler, H. - G., et al. (2009). Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes. Journal of the Chemical Society. Dalton Transactions(8), 1339-1351. doi:10.1039/b815931a
Weber, L., Werner, V., Fox, M. A., Marder, T. B., Schwedler, S., Brockhinke, A., Stammler, H. - G., and Neumann, B. (2009). Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes. Journal of the Chemical Society. Dalton Transactions, 1339-1351.
Weber, L., et al., 2009. Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes. Journal of the Chemical Society. Dalton Transactions, (8), p 1339-1351.
L. Weber, et al., “Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes”, Journal of the Chemical Society. Dalton Transactions, 2009, pp. 1339-1351.
Weber, L., Werner, V., Fox, M.A., Marder, T.B., Schwedler, S., Brockhinke, A., Stammler, H.-G., Neumann, B.: Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes. Journal of the Chemical Society. Dalton Transactions. 1339-1351 (2009).
Weber, Lothar, Werner, Vanessa, Fox, Mark A., Marder, Todd B., Schwedler, Stefanie, Brockhinke, Andreas, Stammler, Hans-Georg, and Neumann, Beate. “Synthetic, structural, photophysical and computational studies of π-conjugated bis- and tris-1,3,2-benzodiazaboroles and related bis(boryl) dithiophenes”. Journal of the Chemical Society. Dalton Transactions 8 (2009): 1339-1351.

16 Zitationen in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

Pyrene Molecular Orbital Shuffle-Controlling Excited State and Redox Properties by Changing the Nature of the Frontier Orbitals.
Merz J, Fink J, Friedrich A, Krummenacher I, Al Mamari HH, Lorenzen S, Haehnel M, Eichhorn A, Moos M, Holzapfel M, Braunschweig H, Lambert C, Steffen A, Ji L, Marder TB., Chemistry 23(53), 2017
PMID: 28718975
Ring Expansion, Photoisomerization, and Retrocyclization of 1,4,2-Diazaboroles.
Su B, Li Y, Ganguly R, Kinjo R., Angew Chem Int Ed Engl 56(46), 2017
PMID: 28906070
A planarized triphenylborane mesogen: discotic liquid crystals with ambipolar charge-carrier transport properties.
Kushida T, Shuto A, Yoshio M, Kato T, Yamaguchi S., Angew Chem Int Ed Engl 54(23), 2015
PMID: 25907576
Highly electron-deficient and air-stable conjugated thienylboranes.
Yin X, Chen J, Lalancette RA, Marder TB, Jäkle F., Angew Chem Int Ed Engl 53(37), 2014
PMID: 25044554
UV-photoelectron spectroscopy of BN indoles: experimental and computational electronic structure analysis.
Chrostowska A, Xu S, Mazière A, Boknevitz K, Li B, Abbey ER, Dargelos A, Graciaa A, Liu SY., J Am Chem Soc 136(33), 2014
PMID: 25089659
Experimental and theoretical studies of quadrupolar oligothiophene-cored chromophores containing dimesitylboryl moieties as π-accepting end-groups: syntheses, structures, fluorescence, and one- and two-photon absorption.
Ji L, Edkins RM, Edkins RM, Sewell LJ, Beeby A, Batsanov AS, Fucke K, Drafz M, Howard JA, Moutounet O, Ibersiene F, Boucekkine A, Furet E, Liu Z, Halet JF, Katan C, Marder TB., Chemistry 20(42), 2014
PMID: 25168267
BN isosteres of indole.
Abbey ER, Liu SY., Org Biomol Chem 11(13), 2013
PMID: 23403937
Multiple reduction of 2,5-bis(borolyl)thiophene: isolation of a negative bipolaron by comproportionation.
Braunschweig H, Dyakonov V, Engels B, Falk Z, Hörl C, Klein JH, Kramer T, Kraus H, Krummenacher I, Lambert C, Walter C., Angew Chem Int Ed Engl 52(49), 2013
PMID: 24123828
Experimental and theoretical studies on organic D-π-A systems containing three-coordinate boron moieties as both π-donor and π-acceptor.
Weber L, Eickhoff D, Marder TB, Fox MA, Low PJ, Dwyer AD, Tozer DJ, Schwedler S, Brockhinke A, Stammler HG, Neumann B., Chemistry 18(5), 2012
PMID: 22213064
Synthesis of 2- and 2,7-functionalized pyrene derivatives: an application of selective C-H borylation.
Crawford AG, Liu Z, Mkhalid IA, Thibault MH, Schwarz N, Alcaraz G, Steffen A, Collings JC, Batsanov AS, Howard JA, Marder TB., Chemistry 18(16), 2012
PMID: 22415854
Luminescence properties of C-diazaborolyl-ortho-carboranes as donor-acceptor systems.
Weber L, Kahlert J, Brockhinke R, Böhling L, Brockhinke A, Stammler HG, Neumann B, Harder RA, Fox MA., Chemistry 18(27), 2012
PMID: 22623079
Boron-doped tri(9,10-anthrylene)s: synthesis, structural characterization, and optoelectronic properties.
Hoffend C, Schödel F, Bolte M, Lerner HW, Wagner M., Chemistry 18(48), 2012
PMID: 23108703
The pentaphenylborole-2,6-lutidine adduct: a system with unusual thermochromic and photochromic properties.
Ansorg K, Braunschweig H, Chiu CW, Engels B, Gamon D, Hügel M, Kupfer T, Radacki K., Angew Chem Int Ed Engl 50(12), 2011
PMID: 21387499

57 References

Daten bereitgestellt von Europe PubMed Central.

Synthese, Struktur, Elektrochemie und optische Eigenschaften von alkinylfunktionalisierten 1,3,2-Diazaborolen und 1,3,2-Diazaborolidinen
Weber, Zeitschrift für anorganische und allgemeine Chemie 633(4), 2007
Synthesis and blue-violet two-photon excited fluorescence of a new organoboron compound
Cao, Journal of Molecular Structure 874(1-3), 2008
Synthesis, photophysics and molecular structures of luminescent 2,5-bis(phenylethynyl)thiophenes (BPETs)
Siddle, New Journal of Chemistry 31(6), 2007
A New Design Strategy for Organic Optoelectronic Materials by Lateral Boryl Substitution
Elbing, Angewandte Chemie International Edition 47(5), 2008
A short history of SHELX.
Sheldrick GM., Acta Crystallogr., A, Found. Crystallogr. 64(Pt 1), 2008
PMID: 18156677
Manipulating Charge-Transfer Character with Electron-Withdrawing Main-Group Moieties for the Color Tuning of Iridium Electrophosphors
Zhou, Advanced Functional Materials 18(3), 2008

Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®

Quellen

PMID: 19462655
PubMed | Europe PMC

Suchen in

Google Scholar