Supramolecular electron transfer-based switching involving pyrrolic macrocycles. A new approach to sensor development?

Abstract

This Feature focuses on pyrrolic macrocycles that can serve as switches via energy-or electron transfer (ET) mechanisms. Macrocycles operating by both ground state (thermodynamic) and photoinduced ET pathways are reviewed and their ability to serve as the readout motif for molecular sensors is discussed.The aim of this article is to highlight the potential utility of ET in the design of systems that perform molecular switching or logic functions and their applicability in chemical sensor development. The conceptual benefits of this paradigm are illustrated with examples drawn mostly from the authors' laboratories.

Protein bioelectronics: a review of what we do and do not know

“…In the Marcus description, nuclear motions of the reactant and the surrounding environment are approximated by a simple harmonic oscillator potential along a reaction coordinate ( Figure 3). 105,106 The left parabola in Figure 3A represents the Gibbs free energy surfaces for the nuclear motion of the reactants prior to ET, and the right parabola represents this free energy for the nuclear motion of the products after ET. The two driving parameters for the ET reaction to overcome the activation free-energy barrier (-ΔG ‡ ) are the driving force, characterized by the Gibbs free energy of activation (-ΔGᵒ), determined from the difference in oxidation potentials of the donor and acceptor, and the reorganization energy (λ) needed for the nuclear rearrangements that accompany ET.…”

“…Note that λ does not change for the different scenarios in B), because the nuclear coordinate (X-axis) of the post-ET state does not change. Adapted with permission from reference 106 where HAD is the quantum mechanical electronic coupling between the initial and final (donor and acceptor) states, kB is the Boltzmann constant, and T is the temperature. A maximum, or optimal ET rate occurs for activation-less ET (-ΔGᵒ = λ) that decreases with decreasing driving force.…”

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“…14 Jiang and coworkers developed a common theory that helps to understand the structure-property relationship for this class of molecules. [14][15][16][17] Consequently, double-decker Pc derivatives, which are being actively investigated as promising materials for sensing devices, optoelectronics and spintronics, [14][15][16][18][19][20][21][22][23][24][25][26][27][28][29] can serve as ideal model systems to study the character of interligand interactions. Recently, we reported the first examples of tetradiazepinoporphyrazine-based sandwich-type lanthanide complexes and assumed the presence of additional intramolecular interactions between the macrocycles.…”

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