Simple Hydrazone Building Blocks for Complicated Functional Materials

Abstract

CONSPECTUS: The ability to selectively and effectively control various molecular processes via specific stimuli is a hallmark of the complexity of biological systems. The development of synthetic structures that can mimic such processes, even on the fundamental level, is one of the main goals of supramolecular chemistry. Having this in mind, there has been a foray of research in the past two decades aimed at developing molecular architectures, whose properties can be modulated using external inputs. In most cases, reversible conformational, configurational, or translational motions, as well as bond formation or cleavage reactions have been used in such modulations, which are usually initiated using inputs including, irradiation, metalation, or changes in pH. This research activity has led to the development of a diverse array of impressive adaptive systems that have been used in showcasing the potential of molecular switches and machines. That being said, there are still numerous obstacles to be tackled in the field, ranging from difficulties in getting molecular switches to communicate and work together to complications in integrating and interfacing them with surfaces and bulk materials. Addressing these challenges will necessitate the development of creative new approaches in the field, the improvement of the currently available materials, and the discovery of new molecular switches. This Account will describe how our quest to design new molecular switches has led us to the development of structurally simple systems that can be used for complicated functions. Our focus on the modular and tunable hydrazone functional group was instigated by the desire to simplify the structure and design of molecular switches in order to circumvent multistep synthesis. We hypothesized that by avoiding this synthetic bottleneck, which is one of the factors that hinder fast progress in the field, we can expedite the development and deployment of our adaptive materials. It should be noted though that designing structurally simple switches cannot be an end goal by itself! Therefore, we showed that our molecules can be used in applications that are beyond a simple molecular switching event (i.e., the control of the photophysical properties of liquid crystals and multistep switching cascades). While focusing on these switches, we discovered that the hydrazones can be easily transformed, using straightforward one-step reactions, into visible light activated azo switches, and two different families of fluorophores that can be used in sensing applications. These findings demonstrate that our approach of developing simple systems for sophisticated functions is not limited to the field of molecular switches and machines but can also encompass other adaptive materials.