Dataset Information

Devising Mixed-Ligand Based Robust Cd(II)-Framework From Bi-Functional Ligand for Fast Responsive Luminescent Detection of Fe³⁺ and Cr(VI) Oxo-Anions in Water With High Selectivity and Recyclability.

ABSTRACT: Environmental issue related applications have globally surfaced as hottest areas of research, wherein luminescent metal-organic frameworks (LMOFs) with functionalized pores put unique signature in real-time monitoring of multiple classes of toxic compounds, and overcome many of the challenges of conventional materials. We report a two-fold interpenetrated, mixed-ligand Cd(II)-organic framework (CSMCRI-11) [Cd_1.5(L)₂(bpy)(NO₃)]·DMF·2H₂O (CSMCRI = Central Salt and Marine Chemical Research Institute, HL = 4- (1H-imidazol-1-yl)benzoic acid, bpy = 4,4'-bipyridine) that exemplifies bipillar-layer structure with two different Cd(II) nodes, and displays notable robustness in diverse organic solvents and water. Intense luminescence signature of the activated MOF (11a) is harnessed in extremely selective and fast responsive sensing of Fe³⁺ ions in aqueous phase with notable quenching constant (1.91 × 10⁴ M^-1) and impressive 166 ppb limit of detection (LOD). The framework further serves as a highly discriminative and quick responsive scaffold for turn-off detection of two noxious oxo-anions (Cr₂O₇ ^2- and CrO₄ ^2-) in water, where individual quenching constants (CrO₄ ^2-: 1.46 × 10⁴ M^-1; Cr₂O₇ ^2-: 2.18 × 10⁴ M^-1) and LOD values (CrO₄ ^2-: 179 ppb; Cr₂O₇ ^2-: 114 ppb) rank among best sensory MOFs for aqueous phase detection of Cr(VI) species. It is imperative to stress the outstanding reusability of the MOF towards detection of all these aqueous pollutants, besides their vivid monitoring by colorimetric changes under UV-light. Mechanism of selective quenching is comprehensively investigated in light of absorption of the excitation/emission energy of the host framework by individual studied analyte.

SUBMITTER: Singh M

PROVIDER: S-EPMC8131680 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Similar Datasets

Project description:The oxo- and catecholate-bridged UIV/UIV Pacman complex [{(py)UIVOUIV(μ-O2C6H4)(py)}(LA)] A (LA = a macrocyclic "Pacman" ligand; anthracenylene hinge between N4-donor pockets, ethyl substituents on meso-carbon atom of each N4-donor pocket) featuring a bent UIV-O-UIV oxo bridge readily reacts with small molecule substrates to undergo either oxo-atom functionalisation or substitution. Complex A reacts with H2O or MeOH to afford [{(py)UIV(μ-OH)2UIV(μ-O2C6H4)(py)}(LA)] (1) and [{(py)UIV(μ-OH)(μ-OMe)UIV(μ-O2C6H4)(py)}(LA)] (2), respectively, in which the bridging oxo ligand in A is substituted for two bridging hydroxo ligands or one bridging hydroxo and one bridging methoxy ligand, respectively. Alternatively, A reacts with either 0.5 equiv. of S8 or 4 equiv. of Se to provide [{(py)UIV(μ-η2:η2-E2)UIV(μ-O2C6H4)(py)}(LA)] (E = S (3), Se (4)) respectively, in which the [E2]2- ion bridges the two UIV centres. To the best of our knowledge, complex A is the first example of either a d- or f-block bimetallic μ-oxo complex that activates elemental chalcogens. Complex A also reacts with XeF2 or 2 equiv. of Me3SiCl to provide [{(py)UIV(μ-X)2UIV(μ-O2C6H4)(py)}(LA)] (X = F (5), Cl (6)), in which the oxo ligand has been substituted for two bridging halido ligands. Reacting A with either XeF2 or Me3SiCl in the presence of O(Bcat)2 at room temperature forms [{(py)UIV(μ-X)(μ-OBcat)UIV(μ-O2C6H4)(py)}(LA)] (X = F (5A), Cl (6A)), which upon heating to 80 °C is converted to 5 and 6, respectively. In order to probe the importance of the bent UIV-O-UIV motif in A on the observed reactivity, the bis(boroxido)-UIV/UIV complex, [{(py)(pinBO)UIVOUIV(OBpin)(py)}(LA)] (B), featuring a linear UIV-O-UIV bond angle was treated with H2O and Me3SiCl. Complex B reacts with two equiv. of either H2O or Me3SiCl to provide [{(py)HOUIVOUIVOH(py)}(LA)] (7) and [{(py)ClUIVOUIVCl(py)}(LA)] (8), respectively, in which reactions occur preferentially at the boroxido ligands, with the μ-oxo ligand unchanged. The formal UIV oxidation state is retained in all of the products 1-8, and selective reactions at the bridging oxo ligand in A is facilitated by: (1) its highly nucleophilic character which is a result of a non-linear UIV-O-UIV bond angle causing an increase in U-O bond covalency and localisation of the lone pairs of electrons on the μ-oxo group, and (2) the presence of the bridging catecholate ligand, which destabilises a linear oxo-bridging geometry and stabilises the resulting products.

Dataset Information

Devising Mixed-Ligand Based Robust Cd(II)-Framework From Bi-Functional Ligand for Fast Responsive Luminescent Detection of Fe³⁺ and Cr(VI) Oxo-Anions in Water With High Selectivity and Recyclability.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Dataset Information

Devising Mixed-Ligand Based Robust Cd(II)-Framework From Bi-Functional Ligand for Fast Responsive Luminescent Detection of Fe3+ and Cr(VI) Oxo-Anions in Water With High Selectivity and Recyclability.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Devising Mixed-Ligand Based Robust Cd(II)-Framework From Bi-Functional Ligand for Fast Responsive Luminescent Detection of Fe³⁺ and Cr(VI) Oxo-Anions in Water With High Selectivity and Recyclability.