A strategically synthesized arseno-discriminatory tetra-phenoxido hetero-trinuclear complex envisioned for the recognition of iAs and oAs from sp. and aquatic crustaceans.

A heterotrimetallic [Mn(Cu)(CHNO)] complex VBCMERI has been unveiled herein to monitor its synergistic propensity towards aqueous phase As3+ (iAs and oAs) detection. VBCMERI was structurally probed by numerous analytical tools like ESI-MS, FT-IR, and SCXRD. The aqueous phase selective chromogenic alteration of the sensory probe from greenish-yellow to colorless was observed owing to interaction with As (cationic form, iAs). This phenomenon can be ascribed to the displacement of the Mn center with As, which has further been experimentally validated through cyclic voltammetric titration studies, FT-IR, and ESI-MS, and theoretically corroborated with density functional theory calculations. Interestingly, aqueous phase selective fluorogenic enhancement of the sensory probe was observed upon interaction with AsO (anionic form, iAs) owing to the displacement of the arsenite anion with the pivalic acid group. The distinct chromogenic alteration from greenish-yellow to colorless and the fluorogenic enhancement of VBCMERI upon interaction with the respective As (iAs) and AsO (iAs) were successfully implemented for monitoring arsenic contamination in groundwater samples and diverse types of sp. grains from the assorted arsenic-affected zones. The competitive accumulation of arsenobetaine (oAs) in the exoskeleton and muscles of aquatic crustaceans (herein, sp.) can be distinctly differentiated based on the fluorogenic response. Based on the sensing response and competitive accumulation tendency of different forms of arsenic in different environments, arseno-adducts with VBCMERI have been theoretically modeled for corroboration with experimental findings. The VBCMERI-AsO2- adduct was also highly efficient in regenerating the VBCMERI sensor selectively in the presence of contaminants like Pb2+. This reversible behavior was further exploited to mimic a molecular-level 3-input-2-output logic gate ensemble.