Synthesis and Characterization of Chiral Luminescent Materials Based on Binaphthol Scaffolds

doi:10.6023/A24100296

Abstract

The study of chiroptoelectronic materials that combine stereochemistry and luminescent properties represents one of the frontiers in areas of chirality science. Of particular interest is the access of organic chiral small molecules that can really show well-defined molecular structures and potentially unique structure-function relationships. In this article, we designed and synthesized three new examples of chiral luminescent compounds (M1, M2 and M3), where the axial chirality is derived from the incorporated binaphthyl groups. All these molecules feature an electron donor-acceptor (D-A) charge-transfer (CT) system, and they were prepared by palladium-catalyzed C—N coupling reactions between the electron-donating carbazole or biarylamines and binaphthyls that were further reacted with 2,3,5,6-tetrafluoro-1,4-dicyanoben- zene as a strong electron-accepting moiety. The structures of M1, M2 and M3 have been verified by ¹H, ¹³C NMR and high-resolution mass spectrometry. Their electronic properties were characterized by UV-vis absorption and emission spectra as well as density functional theory (DFT) calculations. The electrochemistry has been performed by cyclic and differential pulse voltammetry, which showed reversible oxidations on the electron donor sites. The enantiomers of these chiral molecules synthesized here were optically resolved through chiral high performance liquid chromatography (HPLC) with a high value of enantiomeric excess (ee>98%), and the chiroptical properties in the ground and excited states were investigated by circular dichroism (CD) and circularly polarized luminescence (CPL) spectra, respectively. Our computations disclosed a small singlet-triplet energy gap (∆E_S-T), and the experimental results gave rise to an enhanced charge-transfer emission behavior with increasing temperature, likely indicating the potential applications in thermally activated delayed fluorescent (TADF) materials. Solvatochromic emissions have been observed for all the molecules as changes in solvent polarity due to the intramolecular charge-transfer effects. Emission color changes were also reversibly induced in solutions in response to changes in temperature, as a result of stabilization of CT states by the temperature-dependent polarity of solvents.

Key words: chiroptics, binaphthol, electron donor-acceptor, triarylamine, carbazole

Cite this article

Niu Zhang, Shuran Han, Hongwei Ma, Pangkuan Chen. Synthesis and Characterization of Chiral Luminescent Materials Based on Binaphthol Scaffolds[J]. Acta Chimica Sinica, 2025, 83(1): 10-16.

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Fig. & Tab. 8

Figure 1. Structures of M1, M2 and M3, Blue: electron donor, Red: electron acceptor

Scheme 1. Synthetic route of M1, M2 and M3

Figure 2. (a) The UV-vis absorption and (b) emission spectra in different solvents (c=1.0×10?5 mol/L) and (c) CIE color coordinates (photographs showing the emission colors under the 365 nm UV lamp) of M1

	λ_abs^a/nm	λ_em^a/nm	Φ_F^b/%	τ^c/ns
M1	375	435/600	8.0	20
M2	351	549	8	97
M3	373	435/576	4.4	12.7

Table 1. Photophysical properties for M1, M2 and M3 in THF solution

Figure 3. (a) DFT-calculated frontier molecular orbital plots with related vertical excitations of M2 (TDDFT-B3LYP/6-31G*). (b) Cyclic voltammogram (CV) curves recorded for the oxidation and reduction potentials of M1, M2 and M3 in CH2Cl2, and referenced by Fc/Fc+ with n-Bu4NPF6 (c=0.1 mol/L) as electrolyte, ν=100 mV/s

Figure 4. Compound M1 in 2-methyltetrahydrofuran solution (c=1.0×10?5 mol/L) at different temperatures: (a) emission spectra; (b) changes in CIE color coordinates; (c) linear dependence of the emission wavelength on temperature

Figure 5. HPLC chromatogram resolution of M1 with n-hexane/ethyl acetate (V/V, 83∶17) as mobile phase, flow rate=0.7 mL/min, at 25 ℃

Figure 6. The CD spectra of enantiomers for M1 in toluene solution (c=1×10?5 mol/L)

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