2, 9‐Diazadibenzoperylene and 2, 9‐Dimethyldibenzoperylene‐1, 3, 8, 10‐tetratriflates: Key to Functionalized 2, 9‐Diazaperopyrenes. Issue 49 (22nd July 2021)

• Record Type: Journal Article
• Authors: Baal, Eduard; Klein, Marius; Harms, Klaus; Sundermeyer, Jörg
• Is Part Of: Chemistry. Volume 27:Issue 49(2021)
• Page Start: 12610
• Page End: 12618
• Publication Date: 2021-07-22
• Subjects: diazaperopyrenes -- organic dyes -- peropyrenes -- perylene diimide -- reductive aromatization; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202101719
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The synthesis of 2, 9‐diaza‐1, 3, 8, 10‐tetratriflato‐dibenzoperylene (DDP 3 a ) and corresponding 2, 9‐dimethyl‐1, 3, 8, 10‐tetratriflato‐dibenzoperylene (DBP 3 b ) has been developed at multigram scale via reduction of one of the industrially most important high‐performance dyes, perylene‐3, 4, 9, 10‐tetracarboxylic diimide (PTCDI), and of the corresponding dihydroxy peropyrenequinone precursor. The focus of this paper is on the reactivity pattern of 3 a as key intermediate towards highly functionalized 2, 9‐diazadibenzopyrelenes (DDPs) obtained via catalytic substitution of four triflate by aryl, heteroaryl, alkynyl, aminyl, and O‐phosphanyl substituents. The influence of electron‐donating substituents (OSiMe3, OP t ‐Bu2, N‐piperidinyl), electron‐withdrawing (OTf, 3, 5‐bis‐trifluoromethyl‐phenyl), and of electron‐rich π‐conjugated (2‐thienyl, 4‐tert‐butylphenyl, trimethylsilyl‐ethynyl) substituents on optoelectronic and structural properties of these functionalized DDPs has been investigated via XRD analyses, UV/Vis, PL spectroscopy, and by electroanalytical CV. These results were correlated to results of DFT and TD‐DFT calculations. Thus, functionalized DPPs with easily tunable HOMO and LUMO energies and gap became available via a new and reliable synthetic strategy starting from readily available PTCDI. Abstract : A versatile approach towards 2, 9‐diazadibenzoperylenes (DDPs) and related 2, 9‐dimethyldibenzoperylenes (DBPs) with various C, O, and N substituents in 1, 3, 8, 10‐positions is presented. It comprises reductive aromatization of PTCDI via O‐silylation and O‐trifylation steps. DDP‐tetratriflate is the strategic key to (hetero)aryl, alkynyl, aminyl or O‐phosphanyl DDPs characterized by UV/Vis/PL spectra, XRD and CV methods and (TD‐)DFT calculations.