Molecular Triangles: Synthesis, Self‐Assembly, and Blue Emission of Cyclo‐7,10‐tris‐triphenylenyl Macrocycles

Abstract

A set of cyclo-7,10-tris-triphenylenyl macrocycles have been prepared by a Yamamoto cyclotrimerization protocol. In these novel macrocycles, three triphenylene units are covalently linked to each other, resulting in the formation of triangular-shaped molecules. The fully planar derivative revealed pronounced self-assembly behavior. NMR spectroscopy was used to determine the association constant in solution. 2D wide-angle X-ray scattering was applied to the study of the liquid crystallinity of this new discotic mesogen in the bulk state. Furthermore, nonplanar, laterally substituted derivatives were successfully tested as blue emitters in organic light-emitting diodes owing to their unique optoelectronic properties and their high stability. In this case, substitution with sterically demanding phenyl groups was efficiently used to suppress intermolecular packing, thus preventing undesired quenching effects.

Conjugated Macrocycles: Concepts and Applications

“…[149] Furthermore, 195e showed liquid crystallinity, and the hexaphenyl derivatives worked as blue emitters in organic light-emitting diodes. [150] Quite recently, Schlüter and co-workers synthesized the fully conjugated, double-stranded cycles 198a-c by the thermolysis of 197a-c.…”

“…Recently, 195d,e were synthesized independently by the research groups of List and Müllen as well as by Iyoda and co-workers by dehydrogenative cyclization of 46d,e or cyclotrimerization of 196e (Scheme 32). [149,150] It is worth noting that the self-association of 195d composed solely of carbon and hydrogen atoms produced oligomers in solution and fibrous material in the solid state, and that 195d afforded with 2,4,7-trinitrofluorenone a 1:3 CT complex with a microball structure and a dendritic interior. [149] Furthermore, 195e showed liquid crystallinity, and the hexaphenyl derivatives worked as blue emitters in organic light-emitting diodes.…”

Konjugierte Makrocyclen: Konzepte und Anwendungen

“…[150] Schlüter und Mitarbeiter synthetisierten erstmals die vollständig konjugierten, doppelsträngigen Cyclen 198 a-c durch die Thermolyse von 197 a-c. [151] Die Bildung von 198 a,b wurde durch massenspektrometrische Analyse und Abfangreaktionen bestätigt.…”

Self-assembled multicolor nanoparticles based on functionalized twistacene dendrimer for cell fluorescent imaging

“…Taking TPPh, TTPy, OTPy and TOPhP into consideration, one do believe that the twisted structures and three-dimensional architectures could effectively suppress π-π interaction, which might be beneficial to decreasing the fluorescent quenching in the selfassembled aggregation to a great extent. Thermal gravimetric analysis was measured under nitrogen atmosphere, and the onset of 5% weight loss of DBPy, DPyT, TPPh, 48 TTPy, OTPy and TOPhP are 386, 467, 232, 325, 246 and 181°C, respectively, indicating that the obtained compounds have high thermal stability (Supplementary Figure S1). …”

“…Note that compounds TPPh, 47 13, 48 16 49 and TOPhP 50 were prepared according to the reported methods. 2,7-Di-tert-butylpyrene-4,5-ketone 51 (1) was first reacted with commercially available 1,3-diphenylacetone (2) in the presence of potassium hydroxide and ethanol to give black solid 3, which was further converted to 6 (DBPy) and 7 in 11% and 28% isolated yield through a Diels-Alder [4+2] cycloaddition reaction by treatment with 2-amino-5-methylbenzoic acid (4), 2-amino-5-bromobenzoic acid (5) and isoamyl nitrile in refluxing DCE.…”