Pyrimidine-Substituted Hexaarylbenzenes as Versatile Building Blocks for N–Doped Organic Materials

Abstract

Hexaarylbenzenes (HABs) are valuable precursors for the bottom-up synthesis of (nano-)graphene structures. In this work the synthesis of several bis-pyrimidine substituted HABs furnished with tert-butyl groups at different sites of the four pendant phenyl rings is reported. The synthetic procedure is based on modular [4 + 2]-Diels–Alder cycloaddition reactions followed by decarbonylation. Analysis of the solid-state structures revealed that the newly synthesized HABs feature a propeller-like arrangement of the six arylic substituents around the benzene core. Here, the tilt of the aryl rings with respect to the central ring strongly depends on the intermolecular interactions between the HABs and co-crystallized solvent molecules. Interestingly, by evading the closest proximity of the central ring using an alkyne spacer, the distant pyrimidine ring is oriented in the coplanar geometry with regard to the benzene core, giving rise to a completely different UV-absorption profile.

Key words

carbon materials - cycloadditions - Diels–Alder reactions - doping - ligand design - N-heterocycles

Supporting Information

Supporting Information for this article is available online at https://doi.org/10.1055/a-1482-6190.

Dedicated to Prof. Dr. Peter Bäuerle in occasion of his 65th birthday.

Publikationsverlauf

Eingereicht: 26. Februar 2021

Angenommen: 03. April 2021

Accepted Manuscript online:
14. April 2021

Artikel online veröffentlicht:
26. Mai 2021

• References

• 1 Burnside W. Theory of Groups of Finite Order. Cambridge University Press; Cambridge: 2012
• 2 Pólya G, Read RC. Combinatorial Enumeration of Groups, Graphs, and Chemical Compounds. Springer; New York, NY: 1987
• 3 Vij V, Bhalla V, Kumar M. Chem. Rev. 2016; 116: 9565
• 4 Tomović Z, van Dongen J, George SJ, Xu H, Pisula W, Leclère P, Smulders MM. J, De Feyter S, Meijer EW, Schenning AP. H. J. J. Am. Chem. Soc. 2007; 129: 16190
• 5 Hiraoka S, Hisanaga Y, Shiro M, Shionoya M. Angew. Chem. Int. Ed. 2010; 49: 1669
• 6 Steeger M, Lambert C. Chem. Eur. J. 2012; 18: 11937
• 7 Traber B, Wolff JJ, Rominger F, Oeser T, Gleiter R, Goebel M, Wortmann R. Chem. Eur. J. 2004; 10: 1227
• 8 Shukla R, Lindeman SV, Rathore R. Org. Lett. 2007; 9: 1291
• 9 Yong L, Butenschön H. Chem. Commun. 2002; 2852
• 10 Kotha S, Brahmachary E, Lahiri K. Eur. J. Org. Chem. 2005; 2005: 4741
• 11 Xiang Y, Wang Q, Wang G, Li X, Zhang D, Jin W. Tetrahedron 2016; 72: 2574
• 12 Wijesinghe LP, Perera SD, Larkin E, Máille GM. Ó, Conway-Kenny R, Lankage BS, Wang L, Draper SM. RSC Adv. 2017; 7: 24163
• 13 Gregg DJ, Ollagnier CM. A, Fitchett CM, Draper SM. Chem. Eur. J. 2006; 12: 3043
• 14 Nagarajan S, Barthes C, Gourdon A. Tetrahedron 2009; 65: 3767
• 15 Wijesinghe LP, Lankage BS. Chem. Commun. 2014; 50: 10637
• 16 Suzuki S, Segawa Y, Itami K, Yamaguchi J. Nat. Chem. 2015; 7: 227
• 17 Lungerich D, Reger D, Hölzel H, Riedel R, Martin MM. J. C, Hampel F, Jux N. Angew. Chem. Int. Ed. 2016; 55: 5602
• 18 Draper SM, Gregg DJ, Madathil R. J. Am. Chem. Soc. 2002; 124: 3486
• 19 Meitinger N, Mengele AK, Witas K, Kupfer S, Rau S, Nauroozi D. Eur. J. Org. Chem. 2020; 2020: 6555
• 20 Geng Y, Fechtenkötter A, Müllen K. J. Mater. Chem. 2001; 11: 1634
• 21 Schreck MH, Röhr MI. S, Clark T, Stepanenko V, Würthner F, Lambert C. Chem. Eur. J. 2019; 25: 2831
• 22 Tanaka Y, Akita M. J. Organomet. Chem. 2018; 878: 30
• 23 Khan FA, Wang D, Pemberton B, Talipov MR, Rathore R. J. Photochem. Photobiol., A 2016; 331: 153
• 24 Bhalla V, Vij V, Dhir A, Kumar M. Chem. Eur. J. 2012; 18: 3765
• 25 Thomas KR. J, Velusamy M, Lin JT, Sun S.-S, Tao Y.-T, Chuen C.-H. Chem. Commun. 2004; 20: 2328
• 26 Zou Y, Ye T, Ma D, Qin J, Yang C. J. Mater. Chem. 2012; 22: 23485
• 27 Stępień M, Gońka E, Żyła M, Sprutta N. Chem. Rev. 2017; 117: 3479
• 28 Wang X, Sun G, Routh P, Kim DH, Huang W, Chen P. Chem. Soc. Rev. 2014; 43: 7067
• 29 Gregg DJ, Bothe E, Höfer P, Passaniti P, Draper SM. Inorg. Chem. 2005; 44: 5654
• 30 Draper SM, Gregg DJ, Schofield ER, Browne WR, Duati M, Vos JG, Passaniti P. J. Am. Chem. Soc. 2004; 126: 8694
• 31 Vo TH, Perera UG. E, Shekhirev M, Mehdi Pour M, Kunkel DA, Lu H, Gruverman A, Sutter E, Cotlet M, Nykypanchuk D, Zahl P, Enders A, Sinitskii A, Sutter P. Nano Lett. 2015; 15: 5770
• 32 Cai J, Pignedoli CA, Talirz L, Ruffieux P, Söde H, Liang L, Meunier V, Berger R, Li R, Feng X, Müllen K, Fasel R. Nat. Nanotechnol. 2014; 9: 896
• 33 Leitner TD, Gmeinder Y, Röhricht F, Herges R, Mena-Osteritz E, Bäuerle P. Eur. J. Org. Chem. 2020; 2020: 285
• 34 Pfeffer MG, Pehlken C, Staehle R, Sorsche D, Streb C, Rau S. Dalton Trans. 2014; 43: 13307
• 35 Gregg DJ, Ollagnier CM. A, Fitchett CM, Draper SM. Chem. Eur. J. 2006; 12: 3043
• 36 Chebny VJ, Shukla R, Rathore R. J. Phys. Chem. A 2006; 110: 13003
• 37 Alvarez S. Dalton Trans. 2013; 42: 8617
• 38 Hübscher J, Seichter W, Gruber T, Kortus J, Weber E. J. Heterocycl. Chem. 2015; 52: 1062
• 39 Georgiev I, Bosch E, Barnes CL. J. Chem. Crystallogr. 2004; 34: 859
• 40 Nwachukwu CI, Patton LJ, Bowling NP, Bosch E. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 2020; 76: 458
• 41 Delaney C, Ó Máille G. M. Twamley B, Draper SM. Org. Lett. 2016; 18: 88
• 42 Fort EH, Donovan PM, Scott LT. J. Am. Chem. Soc. 2009; 131: 16006
• 43 Sarkar A, Okada S, Nakanishi H, Matsuda H. Helv. Chim. Acta 1999; 82: 138
• 44 Sheldrick GM. Acta Crystallogr., Sect. A: Found. Crystallogr. 2008; 64: 112
• 45 Sheldrick GM. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 2015; 71: 3
• 46 Macrae CF, Edgington PR, McCabe P, Pidcock E, Shields GP, Taylor R, Towler M, Van De Streek J. J. Appl. Crystallogr. 2006; 39: 453