Understanding and Controlling the Structure at Organic-Inorganic Interfaces for the Generation of Stimuli Responsive Multilayered Materials
Abstract
The rate, efficiency, and direction of energy and electron transfer at organic-inorganic interfaces is critical for their application in bioelectronics, solar energy conversion, electrocatalysis, sensing, and more. There is typically a barrier to electronic communication across these hybrid interfaces but self-assembly of molecular multilayers has emerged as a simple and modular means of gaining unprecedented control over interfacial energy and electron transfer events. While tuning the energetics of the molecular assemblies has proven successful thus far, the lack of structural knowledge and architectural control of these interfaces has limited our ability to unlock the full potential of self-assembled interfaces. To remedy this shortcoming, this proposal outlines a three-year program with the objective of using carefully designed molecular derivatives, metal linking ions, and self-assembly methods, along with a combination of Fšrster resonance energy transfer and polarized attenuated total reflectance, to determine the parameters that dictate the structure (i.e. the relative distances and orientation) of the molecules in the self-assembled films. We will then use steady-state and time-resolved measurement techniques determine how the structure of the multilayer film dictates the properties of the interface. Additionally, we will incorporate stimuli responsive molecular motifs into the assemblies that will act as reversible molecular switch to externally control, using either optical or electrical stimuli, electron and energy transfer at the interface. Collectively, this work will elucidate the role of the metal ion and molecular structure in dictating the structure of the self-assembled bilayer as well as how that structure influences the electrochemical and photophysical properties of the interface. This contribution is significant because this structure-property knowledge can be used to design new interfaces with exquisite control over energy and electron transfer at hybrid interfaces. In addition to improving the performance of electrocatalysts, photodetectors, and other applications mentioned above, the generation of interfaces that exhibit structural changes under external stimulation opens the door to new applications for self-assembled hybrid interfaces including non-linear optics, electrochromic windows, logic gates, read-write arrays, and more. Thus, these insights have broad implications for increasing both fundamental knowledge and utility of hybrid interfaces. Equally important is that we will have introduced two new strategies, Fšrster resonance energy transfer and polarized attenuated total reflectance, to characterize the structure of assemblies at multimolecular interfaces.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Jun 10, 2019
- Source ID
- W911NF1910357
Entities
People
- Kenneth Hanson
Organizations
- Army Contracting Command
- Florida State University
- United States Army