Annulated bis(imidazolium) salts: synthesis, characterization, and applications

Abstract

The design, synthesis, characterization, and applications of annulated bis(imidazolium) salts are described. New synthetic methodologies have been developed that allow access to a broad structural range of bis(imidazolium) salts. Initial studies focused on thee use of bis(imidazolium) salts as comonomers in the formation of mainchain organometallic polymers. Two distinct polymer scaffolds were synthesized, one featuring metal(II)dihalides in the main-chain, and the other featuring a chelated metal center. Ultimately, polymerizations were conducted under ambient atmosphere, proceeded in excellent overall yield, and provided main-chain organometallic polymers comprising Ni(II), Pd(II), and Pt(II) with molecular weights up to 106 Da. Departing polymer studies, focus was shifted toward the study of the physical and photophysical properties of the bis(imidazolium) salts. In few synthetic manipulations, a series of highly photoluminescent bis(imidazolium) salts were prepared whose substituents enable emission in solution, in the solid-state, and, uniquely, as free-flowing liquids. Importantly, these materials display excellent physical properties, such as low glass-transition temperatures (< 0 °C) and high thermal stabilities (> 300 °C). In addition, the bis(imidazolium) platform enabled access to two new fluorescent ionic liquid crystals, demonstrating an ability to also control mesomorphic properties of these materials. Further investigations were conducted regarding the photophysical properties of bis(imidazolium) salts. Focus was placed upon absorption and emission wavelength tunability, solvatochromism, red-edge excitation, and chemical stability. Through functional group modulation, the [lambda]em were varied from 329 -- 561 nm with [Phi]fs up to 0.91. Both the absorption and emission characteristics were found to display strong solventdependencies which were found to be strongly influenced by the nature of the bis(imidazolium) core. The red-edge effect was investigated for a series of bis(imidazolium) salts and was found to be similar between Br and BF4 salts, but distinctly different when MeSO4 anions were incorporated. The stability of an amphiphilic BBI was quantified in aqueous solutions of varying pH and > 85% of the emission intensity was retained after 2 h at pH levels of 3 -- 9.