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Access Type
WSU Access
Date of Award
January 2023
Degree Type
Dissertation
Degree Name
Ph.D.
Department
Chemistry
First Advisor
Federico A. Rabuffetti
Abstract
Our studies have shown that the trifluoroacetato ligand (tfa, CF3COO−) has the ability to bridge mono, di, and trivalent cations spanning a broad range of sizes featuring a variety of structural motifs. These structurally diverse materials are known as metal trifluoroacetates and may be classified as hybrid organic–inorganic materials. Despite the chemical and structural diversity of metal trifluoroacetates, there is a lack of research with respect to functionalities of these materials. This dissertation focuses on two major potential functionalities for these fluorinated hybrids: (1) single-source precursors to optical and energy relevant mixed-metal fluorides; and (2) solid-state light emitters that have the ability to act as optical sensors. Therefore, it is important to place emphasis on investigating the potential applicability of this family of materials for practical uses. The work presented in this dissertation aimed at investigating solid-state and solution phase reactivity and luminescence response of mixed-metal trifluoroacetates. From the perspective of the reactivity, a series of alkali–alkaline-earth trifluoroacetates is examined as self-fluorinating single-source precursors to mixed-metal fluorides with formulas RbAEF3 (AE = Mg, Ca, Sr). Finally, the luminescence response of two series of lanthanide-based trifluoroacetates is explored: (1) Cs4Ln4(tfa)16(tfaH) (Ln= Eu, Gd, Tb, and Dy) and (2) Eu1-xTbx(tfa)3(H2O)3 (x= 0, 0.1, 0.2, 0.5, 0.8, 0.9, 1). To our knowledge, Cs4Ln4(tfa)16(tfaH) is the only luminescent extended inorganic hybrid material employing trifluoroacetato as the sole bridging ligand. Eu1-xTbx(tfa)3(H2O)3 was probed as a luminescent ratiometric thermometer. While investigating the luminescent thermometric response a pressure-dependent phase transition was observed. Thus, Eu1-xTbx(tfa)3(H2O)3 may be regarded as potential as an optical temperature and pressure sensor. This dissertation highlights the significance of expanding the current library of metal trifluoroacetates featuring different compositions and structural motifs to unveil potential functionalities.
Recommended Citation
Szlag Silva, Regina Szlag Silva Grace, "Mixed-Metal Trifluoroacetates As Single-Source Precursors And Optical Sensors" (2023). Wayne State University Dissertations. 3877.
https://digitalcommons.wayne.edu/oa_dissertations/3877