The rational introduction of fluorine atoms into a substance can have a profound and potentially beneficial influence on a wide range of physical properties of that substance. What is the influence of fluorination? The only answer is “it depends”. The influence depends on the exact identity of the substrate, the number of fluorine atoms introduced, the identities of the atoms the fluorines are bonded to, and their overall mutual location and spatial relationships. The influences of fluorination are not manifested only on the molecular level but inevitably also extend to intermolecular interactions and bulk properties. Almost four decades ago a study at IBM Research related to block co-polymers was initiated to examine the infrared spectra of simple n-alkanes containing perfluorinated segments. During that study, it was discovered that this fluorination introduced serendipitous mesogenic behavior into these materials which we came to refer to as semi-fluorinated hydrocarbons. In this presentation, these initial studies will be recounted and other examples of rational fluorination from my subsequent research activities will be presented. These examples are dominated by various types of liquid crystals (calamitic and discotic) wherein rational fluorination plays a profound role in the manipulation and optimization of a range of physical properties and phenomena.

Recognition of the role of fluorination in materials science

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ACS Fall 2022

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