Donor-Acceptor Superstructures with Emergent Optoelectronic Properties: Synergistic Approaches to Functional Self-Assembling Aggregates
Abstract
Natural materials with elaborate hierarchical nano- and microstructures possess sophisticated optoelectronic properties that arise as a result of interactions between the orbitals of individual components that mix upon assembly. Emulating the robustness, sophisticated architectures, and stimuli-responsive optoelectronic characteristics of natural materials remains a major challenge in chemical and materials research, whose resolution could have far-reaching consequences in biology, materials science, and nanotechnology. To create synthetic materials with optoelectronic properties comparable to their biological counterparts, two fundamental challenges must be overcome, namely, understanding how multicomponent supramolecular systems assemble into mesoscale structures, and determining how novel optical and electronic properties can emerge by bringing together donor and acceptor components that individually lack the desired properties. Herein we propose the design, preparation, and study of a novel self-assembling system composed of diketopyrrolopyrrole (DPP) electron donors and perylene diimide (PDI) electron acceptors, where multiple, complementary noncovalent interactions direct the assembly of hierarchical superstructures that will undergo efficient charge generation and Jong-distance charge separation. Specifically, we propose to: (I) Explore the assembly of DPP-PDI superstructures in solution nod in the solid-state to develop new predictive models that quantitatively describe heteroaggregation with different components, donor-acceptor ratios, and environmental conditions, (2) Understand how structure and FMO energies interact to produce emergent properties that respond external stimuli, and (3) Produce stable solid-state materials that can be incorporated into electronic devices. Libraries of DPP donors and PDI acceptors will be prepared, and their assembly in films will be studied by various surface-sensitiveanalytical methods. The emergent optoelectronic properties will be characterized by transient absorption microscopies and scanning probe spectroscopies to establish relationships between superstructure architecture, frontier molecular orbital levels, and emergent optoelectronic properties. Co-crystalline superstructures and films will be prepared to understand how the advantageous properties of donor-acceptor superstructures, including architecture and emergent optoelectronic properties, can be transitioned to the solid-state, and charge separation and charge migration through these films will be investigated by transient absorption microscopy and scanning probe microscopies. This hierarchial approach towards understanding sclf-asscmbling systems is the only way to develop new multi-lengthscale materials with the structural complexity, emergent properties, and stimuli-responsiveness comparable to biological systems, and through this research program, we hope to create sophisticated new materials to address current and future ARO optoelectronic needs related to sensing, organic electronics, and optical devices.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Oct 16, 2018
- Source ID
- W911NF1710215
Entities
People
- Adam B Braunschweig
Organizations
- Army Contracting Command
- Research Foundation of The City University of New York
- United States Army