Supramolecular Energy Materials

Abstract

Self‐assembly is a bioinspired strategy to craft materials for renewable and clean energy technologies. In plants, the alignment and assembly of the light‐harvesting protein machinery in the green leaf optimize the ability to efficiently convert light from the sun to form chemical bonds. In artificial systems, strategies based on self‐assembly using noncovalent interactions offer the possibility to mimic this functional correlation among molecules to optimize photocatalysis, photovoltaics, and energy storage. One of the long‐term objectives of the field described here as supramolecular energy materials is to learn how to design soft materials containing light‐harvesting assemblies and catalysts to generate fuels and useful chemicals. Supramolecular energy materials also hold great potential in the design of systems for photovoltaics in which intermolecular interactions in self‐assembled structures, for example, in electron donor and acceptor phases, maximize charge transport and avoid exciton recombination. Possible pathways to integrate organic and inorganic structures by templating strategies and electrodeposition to create materials relevant to energy challenges including photoconductors and supercapacitors are also described. The final topic discussed is the synthesis of hybrid perovskites in which organic molecules are used to modify both structure and functions, which may include chemical stability, photovoltaics, and light emission.

Influence of the Z/E Isomerism on the Pathway Complexity of a Squaramide‐Based Macrocycle

“…Self‐assembly of molecules has become a powerful tool for the development of supramolecular nanoscale materials with a myriad of applications in photonics, electronics, and chemical biology among others. [ 1–10 ] In this context, the control over the self‐assembly processes is essential for the development of well‐defined nanostructures with the desired properties and functions. [ 11–18 ] For many years, the design of supramolecular materials has been tackled only considering the equilibrium states of the system.…”

Design of materials with supramolecular polymers

“…The full crystallization of macromolecules in synthetic materials is a major challenge, yet many potential functions benefit from crystalline lattices including ferroelectrics, photovoltaics, exciton movement in photocatalysis, and quantum computing in the future, among many others. In this context it has been interesting to find that supramolecular polymers can indeed form highly crystalline structures, while remaining discrete structures that could physically behave as covalent polymers [89] . In 2014 the Stupp laboratory reported on internally crystalline supramolecular polymers that led to enhanced light-harvesting capabilities [ 31 , [55] , [56] , [57] , 68 , [90] , [91] , [92] ].…”

“…The π–π interactions among chromophores in these systems drive self-assembly of these molecules in water to form crystalline supramolecular polymers in the presence of electrolytes that screen repulsive electrostatic interactions ( Fig. 4 b-c) [ 31 , 55 , 56 , 68 , [89] , [90] , [91] , 98 , 99 ]. These supramolecular polymers photosensitize reactions by serving as light-harvesting assemblies, and their crystallization improves the size and lifetime of the resulting charge transfer excitons participating in the photocatalysis [31] .…”

“…This work clearly demonstrated the importance of crystalline packing of monomers within the supramolecular polymer for photocatalysis [56] . More recently, additional modifications to the chromophore amphiphile monomers have been investigated to elucidate the relationship between molecular structure, supramolecular polymerization, and functional application of these catalytic systems [ 31 , 55 , 56 , [90] , [91] , [92] ], which have recently been reviewed elsewhere [89] . The opportunity for soft organic materials, which can intimately incorporate the components required for catalysis is an exciting prospect, made possible by these crystalline supramolecular polymers and their ability to efficiently photosensitize catalysts for solar fuel production.…”

Supramolecular Ladder Assemblies as a Model for Probing Electronic Interactions between Multiple Stacked π‐Conjugated Systems

“…For these reasons, investigations of the factors governing the formation of structurally defined aggregates of π‐conjugated materials have been pursued vigorously [11,12] . In particular, controlling the formation of specific supramolecular structures has proven important in adjusting the bulk electronic properties [13–20] . Elegant work from several research groups demonstrated the use of tailored supramolecular interactions to achieve this goal, in particular through the use of organogelating systems in which the π‐conjugated components are well‐oriented [1,21–26] .…”