Covalent
organic frameworks (COFs) usually have weak emission because
of π–π stacking between layers, linkage bond rotation,
or photoinduced electron transfer (PET) between monomer parts, which
gives a chance to prepare “off–on” fluorescent
sensors based on these weakly emissive COFs. Here, nitrogen-doped
carbon dots (NCDs) encapsulated in COFTAPT‑TT (NCCOFTAPT‑TT) are successfully prepared by a one-pot method,
in which COFTAPT‑TT is synthesized by ammonaldehyde
condensation between 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT)
and thieno[3,2-b]thiophene-2,5-dicarboxaldehyde (TT)
in the presence of NCDs. NCCOFTAPT‑TT emits a strong
NCD peak at 445 nm and a weak peak of COFTAPT‑TT at 337 nm due to PET between electron-deficient TAPT and electron-rich
TT. The NCDs lead spherical stacked COFTAPT‑TT to
self-exfoliate into NCCOFTAPT‑TT nanosheets, which
greatly improves the dispersion and stability of NCCOFTAPT‑TT. In the presence of Cu2+ (0–10.0 μM), the
fluorescence of NCDs is quenched but the fluorescence of COFTAPT‑TT remains unchanged. The linear range is 51.9 nM to 0.75 μM,
and the detection limit is 17.3 nM. Then, Cu2+ inhibits
the PET process to result in an enhancement of COFTAPT‑TT fluorescence and the fluorescence of NCDs remains unchanged, thus
realizing a Cu2+ off–on ratiometric fluorescent
sensor with high sensitivity, good selectivity, and good stability.
This off–on fluorescent sensor has a linear range of 18–26
μM. This work provides a new idea for application of COFs with
weak emission to construct off–on fluorescent sensors.