Subscribe to RSS
DOI: 10.1055/s-0041-1726089
Unusual Zig-Zag Effect in the Electrochemical Oxidation of Phenyl End-Capped α-Oligothiophenes
Abstract
A series of phenyl end-capped α-oligothiophenes containing four to seven thiophene subunits (4T–7T) was synthesized utilizing palladium-catalyzed cross-coupling reactions. UV/Vis spectroscopic analysis revealed one broad absorption band that shifts bathochromically with increasing number of thiophene units. Structured emission spectra are observed with Stokes shift ν~4000 cm−1 and quantum yields of up to 53%. End-capping of the oligothiophene molecules by phenyl units does not only extend the effective conjugation but also prevents from α–α-homocoupling upon electrochemical oxidation. Accordingly, reversible redox waves are observed in cyclic voltammetry with up to four reversible one-electron processes for the two longer congeners. Analyses of the first two oxidation processes in the framework of multiredox systems provide insight into the stabilization or destabilization of polaronic and bipolaronic states. An unusual zig-zag trend for the first (and to a lesser extend second) oxidation process could be explained by the sterical encumbrance of solubilizing hexyl chains in 5T and 7T molecules which counteract the formation of a fully planar quinoidal oligothiophene backbone.
Supporting Information
Supporting information for this article is available online at https://doi.org/10.1055/s-0041-1726089.
Dedicated to Professor Peter Bäuerle on the occasion of his 65th birthday.
Publication History
Received: 16 January 2021
Accepted: 27 January 2021
Article published online:
01 April 2021
© 2021. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes, or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References
- 1 Roncali J. Chem. Rev. 1997; 97: 173
- 2 Anthony JE. Angew. Chem. Int. Ed. 2008; 47: 452
- 3 Mishra A, Ma C.-Q, Bäuerle P. Chem. Rev. 2009; 109: 1141
- 4 Roncali J, Blanchard P, Frere P. J. Mater. Chem. 2005; 15: 1589
- 5 Shi H, Liu CC, Jiang QL, Xu JK. Adv. Electron. Mater. 2015; 1: 1500017
- 6 Ong BS, Wu Y, Li Y, Liu P, Pan H. Chem. Eur. J. 2008; 14: 4766
- 7 Mishra A, Bäuerle P. Angew. Chem. Int. Ed. 2012; 51: 2020
- 8 Bäuerle P, Gaudl K, Würthner F, Sariciftci S, Neugebauer H, Mehring M, Zhong C, Doblhofer K. Adv. Mater. 1990; 2: 490
- 9 Bäuerle P, Würthner F, Götz G, Effenberger F. Synthesis 1993; 1099
- 10 Barbarella G, Zambianchi M, del Fresno I, Marimon M, Antolini L, Bongini A. Adv. Mater. 1993; 5: 834
- 11 Mena-Osteritz E, Meyer A, Langeveld-Voss BM. W, Janssen RA. J, Meijer EW, Bäuerle P. Angew. Chem. Int. Ed. 2000; 39: 2679
- 12 Krömer J, Rios-Carreras I, Fuhrmann G, Musch C, Wunderlin M, Debaerdemaeker T, Mena-Osteritz E, Bäuerle P. Angew. Chem. Int. Ed. 2000; 39: 3481
- 13 Zhang F, Götz G, Winkler HD. F, Schalley CA, Bäuerle P. Angew. Chem. Int. Ed. 2009; 48: 6632
- 14 Facchetti A, Yoon M.-H, Stern CL, Hutchison GR, Ratner MA, Marks TJ. J. Am. Chem. Soc. 2004; 126: 13480
- 15 Diaz-Quijada GA, Weinberg N, Holdcroft S, Pinto BM. J. Phys. Chem. A 2002; 106: 1266
- 16 Azumi R, Mena-Osteritz E, Boese R, Benet-Buchholz J, Bäuerle P. J. Mater. Chem. 2006; 16: 728
- 17 Heinze J, Bilger R, Meerholz K. Ber. Bunsen Ges. Phys. Chem. 1988; 92: 1266
- 18 Zhang F, Götz G, Mena-Osteritz E, Weil M, Sarkar B, Kaim W, Bäuerle P. Chem. Sci. 2011; 2: 781
- 19 Zhang L, Colella NS, Cherniawski BP, Mannsfeld SC. B, Briseno AL. ACS Appl. Mater. Interfaces 2014; 6: 5327
- 20 Bäuerle P, Pfau F, Schlupp H, Würthner F, Gaudl K.-U, Balparda Cara M, Fischer P. J. Chem. Soc., Perkin Trans. 2 1993; 489
- 21 Würthner F, Schmidt R. ChemPhysChem 2006; 7: 793
- 22 Bäuerle P, Segelbacher U, Maier A, Mehring M. J. Am. Chem. Soc. 1993; 115: 10217
- 23 Guyard L, Dumas C, Miomandre F, Pansu R, Renault-Méallet R, Audebert P. New J. Chem. 2003; 27: 1000
- 24 Zheng Y, Ohto T, Liu D, Butt H.-J, Ikeda T. Synth. Met. 2013; 181: 1
- 25 Nikoofard H, Gholami M. C. R. Chim. 2014; 17: 1034
- 26 Bäuerle P, Fischer P, Bidlingmeier B, Stabel A, Rabe JP. Angew. Chem. Int. Ed. Engl. 1995; 34: 303
- 27 Brouwer AM. Pure Appl. Chem. 2011; 83: 2213
- 28 Englman R, Jortner J. Mol. Phys. 1970; 18: 145
- 29 Bäuerle P, Segelbacher U, Gaudl K.-U, Huttenlocher D, Mehring M. Angew. Chem. Int. Ed. Engl. 1993; 32: 76
- 30 Deuchert K, Hünig S. Angew. Chem. Int. Ed. Engl. 1978; 17: 875
- 31 Hünig S. Pure Appl. Chem. 1990; 62: 395
- 32 Heckmann A, Lambert C. Angew. Chem. Int. Ed. 2012; 51: 326
- 33 Hünig S, Schenk W. Liebigs Ann. Chem. 1979; 1523
- 34 Hesse K, Hünig S. Liebigs Ann. Chem. 1985; 708
- 35 Camarada MB, Jaque P, Díaz FR, del Valle MA. J. Polym. Sci., Part B, Polym. Phys. 2011; 49: 1723
- 36 Rausch R, Röhr MI. S, Schmidt D, Krummenacher I, Braunschweig H, Würthner F. Chem. Sci. 2021; 12: 793
- 37 Pun AB, Asadpoordarvish A, Kumarasamy E, Tayebjee MJ. Y, Niesner D, McCamey DR, Sanders SN, Campos LM, Sfeir MY. Nat. Chem. 2019; 11: 821
- 38 Bialas D, Kirchner E, Röhr M, Würthner F. J. Am. Chem. Soc. 2021 , in press
- 39 Takahashi M, Masui K, Sekiguchi H, Kobayashi N, Mori A, Funahashi M, Tamaoki N. J. Am. Chem. Soc. 2006; 128: 10930
- 40 L. Jones, C.; J. Higgins, S. J. Mater. Chem. 1999; 9: 865
- 41 Kiriy N, Kiriy A, Bocharova V, Stamm M, Richter S, Plötner M, Fischer W.-J, Krebs FC, Senkovska I, Adler H.-J. Chem. Mater. 2004; 16: 4757
- 42 Sato M.-A, Fukui K. Synth. Met. 2007; 157: 619