Ratiometric fluorescent pH sensor based on a tunable multivariate covalent organic framework.

Ratiometric detection of pH is always significant in environmental regulation, medical diagnosis, synthetic chemistry, and beyond. The construction of practical ratiometric pH sensors with reusability is still challenging. Herein, by exploiting a multivariate strategy, we first synthesized and reported a series of novel three-component covalent organic frameworks (COF-COOH_X, X = 33, 50, and 67) through Schiff base reaction between 2-hydroxybenzene-1,3,5-tricarbaldehyde (HTA), 4,4′-diamino-3,3′-biphenyldicarboxylic acid (DBA), and 5,5′-diamino-2,2′-bipyridine (BPY) at various molar ratios (X = [DBA]/([BPY] + [DBA]) × 100 = 33, 50, and 67). COF-COOH_X (X = 33, 50, and 67) displayed ratiometric pH sensing performance in acidic conditions with selectivity and repeatability. By tuning the molar ratio of DBA and BPY, the fluorescent properties, linear pH responsive ranges, and pK_a values of COF-COOH_X (X = 33, 50, and 67) can be regulated. Meanwhile, the two-component COF-COOH₀ and COF-COOH₁₀₀ did...