Fluorescent Detection of Carbon Disulfide by a Highly Emissive and Robust Isoreticular Series of Zr-Based Luminescent Metal Organic Frameworks (LMOFs)

Ever Velasco,Timo Thonhauser,Kui Tan,Jing Li,Simon J Teat,Yuki Osumi,Stephanie Jensen

doi:10.3390/chemistry3010024

Abstract

Carbon disulfide (CS2) is a highly volatile neurotoxic species. It is known to cause atherosclerosis and coronary artery disease and contributes significantly to sulfur-based pollutants. Therefore, effective detection and capture of carbon disulfide represents an important aspect of research efforts for the protection of human and environmental health. In this study, we report the synthesis and characterization of two strongly luminescent and robust isoreticular metal organic frameworks (MOFs) Zr6(µ3-O)4(OH)8(tcbpe)2(H2O)4 (here termed 1) and Zr6(µ3-O)4(OH)8(tcbpe-f)2(H2O)4 (here termed 2) and their use as fluorescent sensors for the detection of carbon disulfide. Both MOFs demonstrate a calorimetric bathochromic shift in the optical bandgap and strong luminescence quenching upon exposure to carbon disulfide. The interactions between carbon disulfide and the frameworks are analyzed by in-situ infrared spectroscopy and computational modelling by density functional theory. These results reveal that both the Zr metal node and organic ligand act as the preferential binding sites and interact strongly with carbon disulfide.

Highlights

Metal organic frameworks (MOFs) are an extremely versatile class of crystalline, permanently porous inorganic-organic materials that have gained significant attention over the past two decades
The ability to control the nature of the metal ions and linkers make metal organic frameworks (MOFs) a promising class of materials for applications in gas storage and separation, catalysis, luminescent sensing, and other areas [1,2,3,4,5,6,7,8,9]
They serve as promising candidates for the detection of a wide range of molecules whereby analyte interactions alter the optical properties of the luminescent MOFs (LMOFs)

Summary

Introduction

Metal organic frameworks (MOFs) are an extremely versatile class of crystalline, permanently porous inorganic-organic materials that have gained significant attention over the past two decades. As a subcategory of MOFs, LMOFs have been extensively studied for the luminescent detection of chemical species, as LED phosphors, and so on [10,11,12,13,14,15,16] As chemical sensors, they serve as promising candidates for the detection of a wide range of molecules whereby analyte interactions alter the optical properties of the LMOF. These changes in their optical properties may manifest as either quenching or enhancement in luminescence intensity, and/or shifts in emission energy.

Methods

Results

Conclusion