Tetra-aryl Functionalization of Tetracyanodiacenaphthoanthracene Diimides and Their Tunable Optoelectronic Properties

doi:10.6023/cjoc202601005

Abstract

In this study, we report the synthesis of a dibrominated acenaphthenequinone imide intermediate, which is subsequently used to conduct the one-step fourfold Knoevenagel condensation with 2,2',2'',2'''-(benzene-1,2,4,5-tetrayl)tetraaceto- nitrile to give another important intermediate, namely, tetra-brominated tetracyanodiacenaphthoanthracene diimides (TCD- ADI-4Br). By applying Suzuki coupling reactions, TCDADI-4Br is successfully converted into a novel series of tetra-aryl substituted TCDADI derivatives, including TCDADI-4Ph, TCDADI-4OMe, TCDADI-4CF₃, TCDADI-4CN, and TCDADI-4NMe₂. The effect of different aryl substituents on the materials backbone structures, absorption spectra, fluorescence properties, electrochemical energy levels as well as nonlinear optical properties has been studied comparatively by combining theoretical calculations and experimental characterizations. It is found that: (1) incorporating the electron-donating methoxy and dimethylamino groups into TCDADI-4OMe andTCDADI-4NMe₂ endows them with extended absorption bands compared to TCDADI, resulting from the improved intramolecular charge-transfer interactions; (2) both TCDADI-4CN and TCDADI-4CF₃featuring electron-poor cyano and trifluoromethyl group are proven to show extremely high fluorescence quantum yields of up to 98.1% and 98.7%, respectively. The Z-scan experiments indicate the typical reverse saturable absorption behaviors for both TCDADI-4OMe and TCDADI-4NMe₂, while the saturable absorption characteristics are clearly detectable for the other materials of this series. At an incident laser energy of 5 μJ, TCDADI-4OMe and TCDADI-4NMe₂ achieve the nonlinear absorption coefficients of 232 and 109 cm•GW^－1, respectively. This study indicates that tetra-aryl functionalization of tetracyanodiacenaphthoanthracene diimides is an effective approach to regulate their molecular structures and optoelectronic properties. The tetra-aryl substituted TCDADI derivatives reported here hold promising application potentials in various fields like fluorescent dyes, biosensors and organic nonlinear optics.

Key words: polycyclic aromatic diimides, acenaphthenequinone imide, Knoevenagel condensation, optoelectronic property, nonlinear optical property

Cite this article

Zhipeng Ma, Wentao Liu, Chenghua Sun, Jibin Sun, Huajie Chen. Tetra-aryl Functionalization of Tetracyanodiacenaphthoanthracene Diimides and Their Tunable Optoelectronic Properties[J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 3169-3179.

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Fig. & Tab. 8

Scheme 1. Reported synthetic methods and chemical structures of the acenaphthenequinone imide-derived polycyclic aromatic diimides

Scheme 2. Chemical structures and synthetic strategy toward tetra-aryl substituted tetracyanodiacenaphthoanthracene diimide derivatives

Scheme 3. Synthetic routes to the TCDADI-4Br and its tetraaryl-functionalized derivatives

Sample	${\lambda }_{\text{sol}}^{max}$^a/nm	${\lambda }_{\text{PL}}^{max}$^b/nm	${\lambda }_{\text{onset}}^{\text{sol}}$^c/nm	${E}_{\text{g}}^{\text{opt}}$^d/eV	PLQY^e/%	${E}_{\text{red}}^{\text{onset}}$/V	E_LUMO^f/eV	E_HOMO^g/eV
TCDADI	401	509	513	2.42	41.21	－0.09	－4.33	－6.75
TCDADI-4Br	407	540	541	2.29	4.76	－0.22	－4.20	－6.49
TCDADI-4Ph	423	555	557	2.23	82.6	－0.45	－3.97	－6.20
TCDADI-4OMe	379	580	580	2.14	48.22	－0.51	－3.91	－6.05
TCDADI-4CF₃	414	550	552	2.25	98.12	－0.33	－4.09	－6.34
TCDADI-4CN	416	551	554	2.24	98.73	－0.26	－4.16	－6.41
TCDADI-4NMe₂	403	—	750	1.65	0	－0.59	－3.83	－5.49

Table 1. Optical physics and electrochemical data of TCDADI and its derivatives

Figure 1. (a) Absorption spectra and (b) normalized photoluminescence spectra of TCDADI and its derivatives in chloroform

Figure 2. (a) Cyclic voltammogram profiles of TCDADI and its derivatives measured in chloroform at room temperature; (b) DFT- optimized molecular orbital profiles and the energy level diagrams of the HOMOs and LUMOs obtained from experiment and calculation at the level of B3LYP-D3(BJ)/6-31G(d)

Figure 3. Z-scan curves of compounds at different incident energies of (a) 5, (b )10 and (c) 20 μJ toward the wavelength of 532 nm laser pulses

Sample	E₀^a/μJ	T_m^b	σ_ex/σ₀^c	F_on^d/ (J•cm^－2)	β_eff^e/(cm• GW^－1)
TCDADI-4NMe₂	5	0.78	1.28	0.15	109
TCDADI-4OMe	5	0.77	1.31	0.02	232
TCDADI-4NMe₂	10	0.67	1.47	0.19	90
TCDADI-4OMe	10	0.71	1.35	0.03	119
TCDADI-4NMe₂	20	0.23	1.75	0.09	127
TCDADI-4OMe	20	0.70	1.39	0.03	85

Table 2. Z-scan experimental data with a linear transmittance of 60% at 532 nm

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