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J Phys Chem Lett. 2016 Apr 21;7(8):1539-45. doi: 10.1021/acs.jpclett.6b00554. Epub 2016 Apr 12.

Circularly Polarized Persistent Room-Temperature Phosphorescence from Metal-Free Chiral Aromatics in Air.

The journal of physical chemistry letters

Shuzo Hirata, Martin Vacha

Affiliations

  1. Department of Organic and Polymeric Materials, Tokyo Institute of Technology , 2-12-1 Ookayama, Meguro, Tokyo 152-8552, Japan.

PMID: 27058743 DOI: 10.1021/acs.jpclett.6b00554

Abstract

Circularly polarized room-temperature phosphorescence (RTP) with persistent emission characteristics was observed from metal-free chiral binaphthyl structures. Enantiomers of the binaphthyl compounds doped into an amorphous hydroxylated steroid matrix produced blue fluorescence and yellow persistent RTP in air. The lifetime and quantum yield of the yellow persistent RTP were 0.67 s and 2.3%, respectively. The dissymmetry factors of circular dichroism (CD) in the first absorption band, circularly polarized fluorescence (CPF), and circularly polarized persistent RTP were |1.1 × 10(-3)|, |4.5 × 10(-4)|, and |2.3 × 10(-3)|, respectively. A comparison between the experimental data and calculations by time-dependent density functional theory for transient CD spectra confirmed that the binaphthyl conformations in the lowest singlet excited state (S1) and the lowest triplet state (T1) were different. The large difference in the dissymmetry factors for the CPF and the circularly polarized persistent RTP was likely caused by this conformational change between S1 and T1.

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