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Tuning Chromophore-Based LMOF Dimensionality to Enhance Detection Sensitivity for Fe³⁺ Ions.

ABSTRACT: Herein, we report the synthesis of two new manganese-based luminescent metal-organic frameworks (LMOFs) [Mn_0.5(tipe)(1,4-ndc)] _n (1) and [Mn(tipe)(1,4-ndc) (H₂O)·(DMF)₂·(H₂O)₃] _n (2) [tipe = 1,1,2,2-tetrakis(4-(1H-imidazol-1-yl)phenyl)ethene (tipe) and 1,4-ndc = 1,4-naphthalenedicarboxylic acid] constructed from an aggregation-induced emission (AIE) chromophore ligand. Compound 1 can undergo a facile single-crystal-to-single-crystal transformation to form compound 2, which results in an increase in dimensionality from a two-dimensional (2D) network to a three-dimensional (3D) network. Both compounds demonstrate excellent performance for the solution-phase detection of Fe³⁺ ions through a significant and rapid quench in luminescence emission. Fluorescence titration experiments reveal that compound 2 is more selective toward Fe³⁺ compared to compound 1 because of its 3D stacking mode. The K _sv value for compound 2 (32 378 M^-1) is twice as large as that for compound 1 (15 854 M^-1) for the detection of Fe³⁺ ions. We attribute this significant increase in performance to the increase in dimensionality. In addition, compound 2 demonstrates high selectivity and sensitivity for the detection of Cr³⁺ cations and Cr₂O₇ ^2- anions.

SUBMITTER: Wang FM

PROVIDER: S-EPMC8246450 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Inspired by the remarkable electronic and optical properties of single walled carbon nanotubes (SWNTs), various molecular sensing devices with sensitivity down to the single molecule level have been developed. However, most sensing approaches such as field effect transistors or near infrared (NIR) fluorescence require the rigorous debundling and separation of metallic tubes and semiconducting tubes in order to reach the desired high sensitivity. Interestingly, all carbon nanomaterials including carbon nanotubes, graphite, graphene, and even amorphous carbon exhibit extremely strong π-plasmon absorption in the ultraviolet region. This strong absorption has been studied as an undesired optical background for applications based on visible and NIR absorptions. For the first time, we found that the strong π-plasmon absorption of SWNTs in the ultraviolet region is extremely sensitive to ion binding. It is even much more sensitive than the absorption in the visible and NIR regions. Herein, we present our first exploration into using the extremely strong plasmon absorption of SWNTs to develop a new sensing platform for the detection of metallic ions. The detection selectivity is realized by modifying the surface of SWNTs with molecular ligands that have a high specificity for metal ions. As a demonstration, the new method is applied to selectively detect iron ions (Fe3+) by modifying the surface of the SWNTs with deferoxamine (DFO), a natural bacterial siderophore, which has a high specificity and affinity for Fe3+. The selective detection of Fe3+ in both aqueous solution and complex rain water is achieved with a pM level of sensitivity and detection limit. In situ resonant Raman spectroscopy demonstrated that the sensitive detection possibly involves electron transfer between the formed Fe-DFO complexes and the SWNTs. We envisage that it can be used to detect other metal ions when a specific binding chelator is attached to the carbon nanotube surface.

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Tuning Chromophore-Based LMOF Dimensionality to Enhance Detection Sensitivity for Fe³⁺ Ions.

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Tuning Chromophore-Based LMOF Dimensionality to Enhance Detection Sensitivity for Fe3+ Ions.

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OmicsDI is part of the ELIXIR infrastructure

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Tuning Chromophore-Based LMOF Dimensionality to Enhance Detection Sensitivity for Fe³⁺ Ions.