Although
electroactive chiral covalent–organic
frameworks
(CCOFs) are considered an ideal platform for chiral electroanalysis,
they are rarely reported due to the difficult selection of suitable
precursors. Here, a facile strategy of liquid–liquid interfacial
polymerization was carried out to synthesize the target electroactive
CCOFs Ph-Py+-(S,S)-DPEA·PF6
– and Ph-Py+-(R,R)-DPEA·PF6
–.
That is, a trivalent Zincke salt (4,4′,4″-(benzene-1,3,5-triyl)tris(1-(2,4-dinitrophenyl)pyridin-1-ium))
trichloride (Ph-Py+-NO2) and enantiopure 1,2-diphenylethylenediamine
(DPEA) were dissolved in water and chloroform, respectively. The Zincke
reaction occurs at the interface, resulting in uniform porosity. As
expected, the cyclic voltammetry and differential pulse voltammetry
measurements showed that the tripyridinium units of the CCOFs afforded
obvious electrochemical responses. When Ph-Py+-(S,S)-DPEA·PF6
– was modified onto the surface of a glassy carbon electrode as a
chiral sensor, the molecules, which included tryptophan, aspartic
acid, serine, tyrosine, glutamic acid, mandelic acid, and malic acid,
were enantioselectively recognized in the response of the peak current.
Very importantly, the discriminative electrochemical signals were
derived from Ph-Py+-(S,S)-DPEA·PF6
–. The best peak current
ratios between l- and d-enantiomers were in the
range of 1.31–2.68. Besides, a good linear relationship between
peak currents and enantiomeric excess (ee) values was established,
which was successfully harnessed to determine the ee values for unknown
samples. In a word, the current work provides new insight and potential
of electroactive CCOFs for enantioselective sensing in a broad range.