Tetra-N-silylated Bis(borylene)tetraaminoperylenes (“DIBOTAPs”)

• Verfasst von: Martens-Kruck, Susanne [VerfasserIn]
• Verfasst von: Riehm, Till [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Gade, Lutz H. [VerfasserIn]
• Titel: Tetra-N-silylated Bis(borylene)tetraaminoperylenes (“DIBOTAPs”)
• Titelzusatz: synthesis, structures and photophysics
• Verf.angabe: Susanne C. Martens, Till Riehm, Hubert Wadepohl and Lutz H. Gade
• E-Jahr: 2012
• Jahr: June 2012
• Umfang: 8 S.
• Fussnoten: First published: 08 May 2012 ; Gesehen am 10.10.2018
• Titel Quelle: Enthalten in: European journal of inorganic chemistry
• Ort Quelle: Weinheim : Wiley-VCH, 1998
• Jahr Quelle: 2012
• Band/Heft Quelle: (2012), 18, Seite 3039-3046
• ISSN Quelle: 1099-0682
• DOI: doi:10.1002/ejic.201200210
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: Boron-nitrogen compounds
• Sach-SW: Fluorescence
• Sach-SW: Perylenes
• Sach-SW: Photophysics
• Sach-SW: X-ray diffraction
• K10plus-PPN: 1581725973

Abstract

Silylated N,N′;N″,N″′-diborylene-3,4,9,10-tetraaminoperylenes (DIBOTAPs, compounds 1-4) were synthesized by treating 4,9-diaminoperylenequinone-3,10-diimine (DPDI, 1 equiv.) with BH3-THF (2 equiv.), lithiation with n-butyllithium (4 equiv.), and subsequent addition of the corresponding silyl chloride (4 equiv.). The structures of all compounds were determined by single-crystal X-ray diffraction analysis. In all cases, the perylene backbones are not completely planar. In general, local deviations from planarity are smallest within the central C6 ring [root-mean-square deviations (rmsd) range from 0.002 Å for 4 to 0.027 Å for 2·C6D6] and largest within the C3N2B rings [rmsd range from 0.05 Å for 4 to 0.096 Å for 2·C6D6]. The emission spectra of the DIBOTAP derivatives 1-4 in hexane as well as in THF are mirror images of the absorption spectra with Stokes shifts of about 10 nm. By variation of the steric demand of the silyl groups, the luminescence quantum yields could be further influenced. The exchange of all three methyl groups with ethyl (compound 1) or isopropyl (compound 2) substituents resulted in a significant increase in quantum yields with values of 92 % and 89 %, respectively. The observed fluorescence decay is monoexponential for all dyes with typical lifetimes of 5.5-6.6 ns.