A zinc metal-organic framework, i.e., Zn-MOF (Zn-DBC), with ca. 27% solvent-accessible void volume was synthesized from a rationally designed tetraacid based on sterically insulated dibenzo[g,p]chrysene core; the latter inherently features concave shapes. Due to rigidification of the fluorophore in the MOF, Zn-DBC exhibits a respectable fluorescence quantum yield of ca. 30% in the solid state. The fluorescent and water-stable Zn-DBC MOF was found to display intriguing temperature-dependent emission behavior with an activation barrier of 1.06 kcal/mol for radiationless deactivation from the singlet-excited state. It is shown that the Zn-MOF can be employed as an efficient sensory material for detection of hazardous "quat" dicationic herbicides in water by diffusion-limited "turn-off' fluorescence. Due to confinement of the cationic guest analytes within the pores of the MOF, the fluorescence quenching via excited-state charge transfer mechanism is shown to depend on the molecular size of the analyte in addition to the redox potentials. Remarkably, Zn-DBC permits sensing of DQ a well-known toxic "quat" herbicide, with a detection limit as low as 2.8 ppm in water. The unique structural attributes of the Zn-MOF for highly efficient fluorescence sensing of toxic herbicides in water are thus exemplified for the first time.