Mixed N,O‐donor Directed Blue Emissive Nano‐dispersed Mesoporous Mn(II)‐MOF: Dual Sensing Probe for Recyclable and Ultrasensitive ppb‐Level Recognition of TNP and Cr(VI)‐Oxoanions
Udayan Mondal, Kumari Raksha, Priyantan Mondal, Priyabrata Banerjee
Abstract
Abstract A new mesoporous Mn(II)‐MOF [Mn 2 (phen) 2 (nia) 2 ] ∞ with 4‐c uninodal net topology and reiterating rectangular channels in its cargo‐net like extension was synthesized using π‐conjugated phenanthroline ( phen ) and syn‐syn bridging 5‐nitroisopthalic acid ( nia ) linkers. The MOF ( 1 ) exhibited phase purity, uniform morphology, photo and thermal stability, and robustness; duly triggered by the exceptional framework rigidity via intermolecular H‐bonding and interlayer π–π stacking interactions. The bright‐blue luminescence of the MOF nano‐dispersion was explored for sensitive, specific and ultrafast detection of trinitrophenol (TNP) with extremely low LOD (90.62 nM), high K SV (18.27×10 4 M −1 ) and Kq (4×10 14 M −1 s −1 ). The vapor‐phase TNP sensing was also accomplished. Additionally, 1 served towards discriminatory, aqueous‐phase monitoring of Cr(VI)‐oxoanions, depicting LODs: 36.08 and 35.70 ppb; K SV : 3.46×10 4 and 4.87×10 4 M −1 ; Kq: 3.26×10 13 M −1 s −1 and 4.31×10 13 M −1 s −1 ; and response time: 32 and 40s for CrO 4 2− and Cr 2 O 7 2− respectively. The quenching mechanisms ( i. e ., RET, PET, IFE, weak interactions, collisional quenching and π⋅⋅⋅π stacking) was explained from several experimental investigations and theoretical DFT calculations. The recyclable sensing events and quantification from complex environmental matrices with admirable recovery rates and high K SV (13.02–22.44×10 4 ; ~6.31–10.98×10 4 and ~6.60–11.42×10 4 M −1 for TNP, CrO 4 2− and Cr 2 O 7 2− ) undoubtedly advocated the consistency of the probe.