Synthesis and Properties of Novel Circularly Polarized Luminescence Materials Based on Binaphthol Skeleton

doi:10.6023/A22030122

Abstract

A series of chiral luminescent molecules based on binaphthol skeleton and having electron donor diarylamine (NN), electron donor/acceptor diarylamine and diarylboron (BN), electron donor/acceptor diarylamine and cyano (4N2CN) were synthesized. The properties of several molecules were compared by introducing different acceptor groups and extended molecular chiral skeletons. Compounds BN and 4N2CN exhibit significant thermochromic shift of the emission due to the intramolecular charge transfer (ICT) character. The emission wavelength was linearly enhanced with a high correlation coefficient of 0.991 for BN between 345 K and 150 K, 0.996 for 4N2CN between 345 K and 180 K. Furthermore, a fully reversible emission response was corroborated by an excellent fatigue resistance without emission degradation upon its exposure to 5 cycles of temperature change over a range of 195 K and 165 K for BN and 4N2CN. Optical resolution of the racemic mixtures have been performed for further investigation. The initial injection of these molecules into a chiral high performance liquid chromatography (HPLC) with a Daicel Chiralpak IA column resulted in two separated peaks with 1∶1 area. We try to further explore their chiral optical properties, including circular dichroism (CD) and circular polarized luminescence (CPL). The signal of CD indicates their chiral properties in the ground state. However, the difference of CPL signals of these compounds shows that the difference of group and skeleton will affect the chiral properties of molecules in the excited state. BN showed high brightness and Φ_L of BN in solution can reach 0.99. In addition, 4N2CN exhibit aggregation-induced emission (AIE) properties in polar solvent and dynamic light scattering (DLS) was employed to monitor the process of aggregate formation. Based on this, we believe that the skeleton expansion and the introduction of electron-donor/acceptor groups make 4N2CN have unique photophysical properties. This work not only expands the family of chiral optical structures but also provides an idea to enhance the CPL signal and glum values.

Key words: binaphthol, circularly polarized luminescence, thermoresponsive emission, aggregation-induced emission, electron-donor/acceptor

Cite this article

Bin Liu, Pangkuan Chen. Synthesis and Properties of Novel Circularly Polarized Luminescence Materials Based on Binaphthol Skeleton[J]. Acta Chimica Sinica, 2022, 80(7): 929-935.

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Fig. & Tab. 9

Figure 1. Structures of BN, NN and 4N2CN (display in S configuration)

Figure 2. Synthetic route of BN, NN and 4N2CN Reagents and conditions: (i) CuCl(OH)·TMEDA, CH2Cl2, O2; (ii) CH2BrCl, K2CO3, DMF, 50 ℃; (iii) tetrafluoroterephthalonitrile, K2CO3, DMF, 50 ℃; (iv) bis(4-tert-butylphenyl)amine, Pd(OAc)2, t-BuONa, Xantphos, toluene, reflux; (v) n-BuLi, Mes2BF, THF, –78 ℃ to r.t.

Figure 3. UV/Vis absorption and emission spectra of BN, NN and 4N2CN UV/Vis absorption and emission spectra of NN (λex=390 nm), BN (λex=400 nm) and 4N2CN (λex=390 nm) (THF, c=1.0×10–5 mol/L). Inset: photograph showing the emission colors under the 365 nm UV lamp

	λ_abs^a/nm	λ_em^a/nm	Φ_L^b	Φ_S^c	τ_ave^d/ns
BN	400	534	0.90	0.16	2.5
NN	397	457	0.69	0.18	2.8
4N2CN	387	581	0.03	0.13	17

Table 1. Photophysical properties of BN, NN and 4N2CN

Figure 4. Cyclic voltammogram (CV) curves (vs. Fc+/Fc) of BN, NN and 4N2CN Oxidation potentials diagrams of NN, BN and 4N2CN were recorded in CH2Cl2. Reduction potentials diagrams of 4N2CN and BN were recorded in THF vs. Fc/Fc+, using n-Bu4NPF6 (c=0.1 mol/L) as the electrolyte, v=100 mV/s

Figure 5. Aggregation induced emission properties of 4N2CN (a) Emission spectra of 4N2CN in Water/DMF with increasing fw (c=1.0×10–5 mol/L, λex=390 nm) and photograph taken under 365 nm UV irradiation (inset); (b) dynamic Light Scattering (DLS) spectra of 4N2CN

Figure 6. Thermoresponsive emission properties of 4N2CN (a) Temperature-dependent emission spectra of 4N2CN recorded in 2-methyltetrahydrofuran between 180 and 345 K (c=1.0×10–5 mol/L, λex=390 nm); (b) CIE color coordinates; (c) data fitting of the emission (λmax) dependence on T for 4N2CN, and (d) reversible emission modulation with cycling T changes for 4N2CN

Figure 7. CPL signals of BN, NN and 4N2CN Smoothed CPL spectra of enantiomers for BN, NN and 4N2CN in toluene (a) and THF (b) (c=1.0×10–5 mol/L)

	g_lum of BN (×10^–4)	g_lum of NN (×10^–4)	g_lum of 4N2CN (×10^–3)
THF (+)	2.7	4.0	1.5
THF (–)	—	–2.9	–1.6
Toluene (+)	2.8	4.6	0.95
Toluene (–)	–1.0	–3.4	–0.84

Table 2. Comparison of glum of BN, NN and 4N2CN in THF and toluene

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