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A heterogeneous photocatalyst amenable to catalyze different chemical reactions is a highly enabling and sustainable material for organic synthesis. Herein we report the synthesis and characterization of an azobenzene-based organic π–conjugated porous polymer (AzoCPP) as heterogeneous dual photocatalyst manifesting net-oxidative bromination of arenes and dehydroxylation of boronic acids to corresponding phenols. Hierarchical porosity and high surface area of the nano-sized AzoCPP allowed superior catalyst-substrate contact during catalyses, whereas the inherent structural defect present in the CPP backbone resulted in low-energy sinks functioning as de facto catalytic sites. A combination of these two structure-property aspects of AzoCPP, in addition to the dielectric constant manipulation of the system, led to excellent catalytic performance. The protocols remained valid for a wide substrate scope and the catalyst was recycled multiple times without substantial loss in catalytic activity. With the aid of subsequent control experiments and analytical characterizations, mechanisms for each catalysis are proposed and duly corroborated. [ABSTRACT FROM AUTHOR]

• Novel, rapid, room temperature synthesis of semiconducting conjugated microporous polymer (CMP). • Visible-light-induced, metal-free, external oxidant-free prompt degradation of fluoroquinolones (FQs) from water. • Retention of efficient degradation capability in variable pH, pollutant concentration, and light intensity. • A plausible mechanism of degradation from control experiments. The existence of Fluoroquinolones (FQs), non-biodegradable pharmacophores, in the natural environment possesses a serious threat. We herein report a novel, rapid, room-temperature synthesis of semiconducting conjugated microporous polymer (CMP) for the decontamination of four second-generation FQs, Norfloxacin, Enrofloxacin, Ciprofloxacin, and Ofloxacin. The CMP demonstrated impressive gas uptake and FQ adsorption ability. Decreased HOMO-LUMO bandgap resulted in enhanced exciton pair generation on visible-light-illumination. Additionally, a high degree of photocurrent response and suitable redox potentials of the material conjointly endorsed its almost quantitative FQ-degradation efficiency. Ofloxacin showed the best removal efficiency with 0.061 and 0.207 min−1 adsorption and degradation rate constants, respectively, one of the highest values reported. The CMP exhibited equipotent activity for other FQs as well. On increasing the concentration of the FQs or decreasing the incident photo-intensity, quantitative removal efficiencies are observed. Changing the pH of the medium from acidic to alkaline did not impart any change in catalytic activity as well. The reactive species involved viz. O 2 −, 1O 2 , etc. and their roles in the degradation process were determined through control and trapping experiments. A plausible in-depth mechanistic pathway was assessed from the FQ degradation intermediates, and the reactive catalytic species substantiating step-by-step break down of the antibiotic backbone. [ABSTRACT FROM AUTHOR]