Eli M. Espinoza

Building blocks for bioinspired electrets: molecular-level approach to materials for energy and electronics

Abstract In biology, an immense diversity of protein structural and functional motifs originates from only 20 common proteinogenic native amino acids arranged in various sequences. Is it possible to attain the same diversity in electronic materials based on organic macromolecules composed of non-native residues with different characteristics? This publication describes the design, preparation and characterization of non-native aromatic β-amino acid residues, i.e. derivatives of anthranilic acid, for polyamides that can efficiently mediate hole transfer. Chemical derivatization with three types of substituents at two positions of the aromatic ring allows for adjusting the energy levels of the frontier orbitals of the anthranilamide residues over a range of about one electronvolt. Most importantly, the anthranilamide residues possess permanent electric dipoles, adding to the electronic properties of the bioinspired conjugates they compose, making them molecular electrets.

What Makes Oxidized N-Acylanthranilamides Stable?

Oligoamides composed of anthranilic acid derivatives present a promising choice for mediating long-range charge transfer and controlling its directionality. Hole hopping, modulated by the anthranilamide (Aa) permanent dipoles, provides a plausible means for such rectified long-range charge transduction. All aliphatic and most aromatic amides, however, decompose upon oxidation, rendering them unacceptable for hole-hopping pathways. We, therefore, employ electrochemical and computational analysis to examine how to suppress oxidative degradation and stabilize the radical cations of N-acylated Aa derivatives. Our findings reveal two requirements for attaining long-lived radical cations of these aromatic amides: (1) keeping the reduction potentials for oxidizing the Aa residues under about 1.4 V vs SCE and (2) adding an electron-donating group para to the N-terminal amide of the aromatic ring, which prevents the electron spin density of the radical cation from extending over the C-terminal amide. These findings provide essential information for the design of hole-transfer amides.

Bioinspired molecular electrets: bottom-up approach to energy materials and applications

Abstract. The diversity of life on Earth is made possible through an immense variety of proteins that stems from less than a couple of dozen native amino acids. Is it possible to achieve similar engineering freedom and precision to design electronic materials? What if a handful of non-native residues with a wide range of characteristics could be rationally placed in sequences to form organic macromolecules with specifically targeted properties and functionalities? Referred to as molecular electrets, dipolar oligomers and polymers composed of non-native aromatic beta-amino acids, anthranilamides (Aa) provide venues for pursuing such possibilities. The electret molecular dipoles play a crucial role in rectifying charge transfer, e.g., enhancing charge separation and suppressing undesired charge recombination, which is essential for photovoltaics, photocatalysis, and other solar-energy applications. A set of a few Aa residues can serve as building blocks for molecular electrets with widely diverse electronic properties, presenting venues for bottom-up designs. We demonstrate how three substituents and structural permutations within an Aa residue widely alter its reduction potential. Paradigms of diversity in electronic properties, originating from a few changes within a basic molecular structure, illustrate the promising potentials of biological inspiration for energy science and engineering.

Bioinspired approach toward molecular electrets: synthetic proteome for materials

Abstract Molecular-level control of charge transfer (CT) is essential for both, organic electronics and solar-energy conversion, as well as for a wide range of biological processes. This article provides an overview of the utility of local electric fields originating from molecular dipoles for directing CT processes. Systems with ordered dipoles, i.e. molecular electrets, are the centerpiece of the discussion. The conceptual evolution from biomimicry to biomimesis, and then to biological inspiration, paves the roads leading from testing the understanding of how natural living systems function to implementing these lessons into optimal paradigms for specific applications. This progression of the evolving structure-function relationships allows for the development of bioinspired electrets composed of non-native aromatic amino acids. A set of such non-native residues that are electron-rich can be viewed as a synthetic proteome for hole-transfer electrets. Detailed considerations of the electronic structure of an individual residue prove of key importance for designating the points for optimal injection of holes (i.e. extraction of electrons) in electret oligomers. This multifaceted bioinspired approach for the design of CT molecular systems provides unexplored paradigms for electronic and energy science and engineering.