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)tetraacetonitrile to give another important intermediate, namely, tetra-brominated tetracyanodiacenaphthoanthracene diimides (TCDADI-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 intramolelcular charge-transfer interactions; 2) both TCDADI-4CN and TCDADI-4CF3 featuring 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. Upon treatment with the 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.
Ma Zhipeng
,
Liu Wentao
,
Sun Chenghua
,
Sun Jibin
,
Chen Huajie
. Tetra-aryl Functionalization of Tetracyanodiacenaphthoanthracene Diimides and their Tunable Optoelectronic Properties[J]. Chinese Journal of Organic Chemistry, 0
: 260516
.
DOI: 10.6023/cjoc202601005
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