Catalyst‐ and Template‐Free Ultrafast Visible‐Light‐Triggered Dimerization of Vinylpyridine‐Functionalized Tetraarylaminoborane: Intriguing Deep‐Blue Delayed Fluorescence. Issue 51 (16th November 2018)

• Record Type: Journal Article
• Authors: Neena, Kalluvettukuzhy K.; Sudhakar, Pagidi; Thilagar, Pakkirisamy
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 51(2018)
• Page Start: 16806
• Page End: 16810
• Publication Date: 2018-11-16
• Subjects: aminoboranes -- boron -- delayed fluorescence -- photodimerization; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201811353
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A photoredox‐catalyst‐ and template‐free sunlight‐induced molecular dimerization of a vinylpyridine‐functionalized tetraarylaminoborane (TAAB) has been accomplished for the first time. The reaction is quantitative, highly regioselective, and thermally irreversible. The presence of the propeller‐shaped TAAB framework allows selective photodimerization of one of the two vinyl pyridine units. Monomer 1 and photodimer 2 exhibit distinct photophysical properties with delayed fluorescence (DF) both in solution and the solid state, which was confirmed by steady‐state and time‐resolved luminescence studies. Quantum mechanical calculations were performed to support the experimental observations. Our new approach using [2+2] cycloaddition chemistry paves the way for the development of highly sought‐after deep‐blue DF materials. Abstract : True blue : By utilizing BN/CC isosterism and topochemistry, visible‐light‐induced photodimerization of vinylpridine‐appended tetraarylaminoborane (TAAB) was accomplished within a record low reaction time of 1 h without the need for a photoredox catalyst or template. Both the monomer and photodimer exhibit distinctive photophysical properties with deep‐blue delayed fluorescence (DF) features in solution and in the solid state.