Highly Twisted N,N‑Dialkylamines as a Design Strategy to Tune Simple Aromatic Hydrocarbons as Steric Environment-Sensitive Fluorophores

• Published in: Journal of the American Chemical Society Vol. 138; no. 26; pp. 8194 - 8206
• Main Authors: Sasaki, Shunsuke, Suzuki, Satoshi, Sameera, W. M. C, Igawa, Kazunobu, Morokuma, Keiji, Konishi, Gen-ichi
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 06.07.2016; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; THIOFLAVIN-T; FLUORESCENCE; AGGREGATION-INDUCED EMISSION; ROTORS; CATALYZED AMINATION; CONICAL INTERSECTION; INTERNAL-CONVERSION; INTRAMOLECULAR CHARGE-TRANSFER; MM3 FORCE-FIELD; MOLECULAR-MECHANICS
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.6b03749

The steric-environment sensitivity of fluorescence of 9,10-bis­(N,N-dialkylamino)­anthracenes (BDAAs) was studied experimentally and theoretically. A new design strategy to tune simple aromatic hydrocarbons as efficient aggregation-induced emission (AIE) luminogens and molecular rotors is proposed. For a variety of BDAAs, prominent Stokes shifts and efficient solid-state fluorescence were observed. Calculations on BDAA-methyl suggested that in the ground state (S0) conformations, the pyramidal amine groups are highly twisted, so that their lone-pair orbitals cannot conjugate with the anthracene π orbitals. Fluorescence takes place from the S1 minima, in which one or both amine groups are planarized. The stability of the S1 excited state minima as well as destabilization of the S0 state is the origin of large Stokes shift. Experimental measurement of the nonadiabatic transition rate suggests that para disubstitution by dialkylamino (or strongly electron-donating) groups is a key for fast internal conversion. Minimum energy conical intersection (MECI) between S1 and S0 states was found to have a Dewar-benzene like structure. Although this can be reached efficiently in liquid phase for fast internal conversion, a large amplitude motion is required to reach this MECI, which is prohibited in the solid state and caused efficient AIE. This strategy is used to find experimentally that naphthalene analogues are also efficient AIE luminogens. The flexibility of alkyl chains on amino groups is also found to be important for allowed charge-transfer transition. Thus, three points [(1) highly twisted N,N-dialkylamines, (2) substitution at the para positions, (3) with flexible alkyl groups] were proposed for activation of small aromatic hydrocarbons.