Enhancement of Intrinsic Proton Conductivity and Aniline Sensitivity by Introducing Dye Molecules into the MOF Channel

The encapsulation
of dyes into metal–organic frameworks (MOFs) has generated
a variety of platforms for luminescence, but little attention has
been paid to their application in proton conduction. Here, a cationic
MOF {{[In3OL1.5(H2O)3]­(NO3)}·(DMA)3·(CH3CN)6·(H2O)30}n (FJU-10, H4L = 4,4′,4″,4‴-(1,4-phenylenbis­(pyridine-4,2,6-triyl))-tetrabenzoic
acid, DMA = N,N-dimethylacetamide)
was synthesized, and the dye molecule 8-hydroxy-1,3,6-pyrenetrisulfonic
acid trisodium salt (HPTS) was further added to the MOF growth solution,
but during the reaction, HPTS was nitrated and nitrated HPTS was encapsulated
into the FJU-10 to obtain dye@FJU-10. As
a result, the intrinsic proton conductivity of dye@FJU-10 is nearly 5 times higher than that of FJU-10 at 90
°C. Dye@FJU-10 exhibits more sensitive fluorescence
quenching toward aniline than FJU-10 in DMF solution
(the detection limits of FJU-10 and dye@FJU-10 are as low as 0.58 and 0.62 μM, respectively). Here, it is
demonstrated for the first time that intrinsic proton conductivity
can be effectively improved by encapsulating a nitrated HPTS dye into
an MOF.