Synthesis and properties of π-conjugated donor–acceptor macrocycles derived from phenanthrylene building blocks

• Published in: Tetrahedron Vol. 74; no. 27; pp. 3616 - 3623
• Main Authors: Phulwale, Bhimrao Vaijnath, Mishra, Sushil Kumar, Mazal, Ctibor
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 05.07.2018; Elsevier
• Subjects: Chemistry; Chemistry, Organic; Donor-acceptor; Intramolecular charge transfer; Macrocycles; Phenanthrene; Physical Sciences; Science & Technology; Solvatochromism; Sonogashira cross-coupling; VJCZPAXTUMKXBI-UHFFFAOYSA-N; Phenanthrene; WBUXTZQYQTTXFD-NAQKQKAYSA-N; RIRPXXTWYBARIS-DRISDULESA-N; Solvatochromism; JFHDRRAKDAMSSK-NNJWUXAESA-N; Macrocycles; Intramolecular charge transfer; Donor-acceptor; JHCNARACJULRSO-UHFFFAOYSA-N; AHJSALQNJHHOQF-UHFFFAOYSA-N; NPIKNIRITOFATJ-UHFFFAOYSA-N; VEALCKOTRBVKFD-YNOITZJZSA-N; FJAUPXKDCDHMGP-UHFFFAOYSA-N; OAEVFLWEJFKJGV-UHFFFAOYSA-N; LCMOXVAQWGANIY-WUMRMZDUSA-N; Sonogashira cross-coupling; FSXWMEDUPIZUOI-UHFFFAOYSA-N; DESIGN PRINCIPLES; COMPLEXES; MOLECULES; SHAPE; QUINONE; CHARGE-TRANSFER; DERIVATIVES
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2018.05.025

Phenanthrylene-ethynylidene macrocycles combining electron donor and electron acceptor subunits in their shape-persistent fully conjugated core were synthesized. The donor subunits consisted of two 9,10-dialkoxyphenanthrenes linked either with 1,2-ethynylidene or 2,5-thienylene bridge. The acceptors were 9,10-phenanthroquinone and dibenzoquinoxaline and dibenzophenazines derived from it. Solvatochromic photoluminescence from intramolecular-charge-transfer (ICT) excited state was observed mainly in non-polar solvents. In more polar solvents, the excited states favor non-radiative relaxation. DFT calculated HOMO/LUMO energies of the macrocycles correlate well with spectroscopic and electrochemical data. In the series of substituted dibenzophenazine acceptors a good correlation with Hammett substituent constants σp– was found. [Display omitted]