Because sunlight is the most abundant energy source on earth, it has huge potential for practical applications ranging from sustainable energy supply to light driven chemistry. From a chemical perspective, excited states generated by light make thermodynamically uphill reactions possible, which forms the basis for energy storage into fuels. In addition, with light, open-shell species can be generated which open up new reaction pathways in organic synthesis. Crucial are photosensitizers, which absorb light and transfer energy to substrates by various mechanisms, processes that highly depend on the distance between the molecules involved. Supramolecular coordination cages are well studied and synthetically accessible reaction vessels with single cavities for guest binding, ensuring close proximity of different components. Due to high modularity of their size, shape, and the nature of metal centers and ligands, cages are ideal platforms to exploit preorganization in photocatalysis. Herein we focus on the application of supramolecular cages for photocatalysis in artificial photosynthesis and in organic photo(redox) catalysis. Finally, a brief overview of immobilization strategies for supramolecular cages provides tools for implementing cages into devices. This review provides inspiration for future design of photocatalytic supramolecular host-guest systems and their application in producing solar fuels and complex organic molecules.
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http://dx.doi.org/10.1021/acs.chemrev.2c00759 | DOI Listing |
A 1D coordination compound made of a photochromic dithienylethene linker and [Dy(Tp2-py)F]+ units (with Tp2-py = tris(3-(2-pyridyl)pyrazolyl)hydroborate) and having tetrakis[3,5-bis(trifluoromethyl)phenyl]borate counterions is reported. Full photoconversion from the closed isomer to the open isomer of the dithienyethene within single crystals allow for monitoring of the transformation by photocrystallography. Magnetic slow relaxation as well as magnetic hysteresis are observed and can be both modulated upon light irradiation.
View Article and Find Full Text PDFBeilstein J Org Chem
January 2025
College of Chemistry, Sichuan University, Chengdu 610064, China.
Orthogonal self-assembly represents a useful methodology to construct supramolecular polymers with AA- and AB-type monomers, as commonly used for covalently linked polymers. So far, the design of such monomers has relied heavily on three-dimensional macrocycles, and the use of two-dimensional shape-persistent macrocycles for this purpose remains rather rare. Here, we demonstrate a dimerization motif based on a hydrogen-bonded macrocycle that can be effectively applied to form orthogonal supramolecular polymers.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
NIT Rourkela: National Institute of Technology Rourkela, Department of Chemistry, NIT Rourkela, 769008, Rourkela, INDIA.
Certain proteins and synthetic covalent polymers experience aqueous phase transitions, driving functional self-assembly. Herein, we unveil the ability of supramolecular polymers (SPs) formed by G4.Cu+ to undergo heating-induced unexpected aqueous phase transitions.
View Article and Find Full Text PDFJ Control Release
January 2025
State Key Laboratory of Bioactive Molecules and Druggability Assessment, Guangdong Basic Research Center of Excellence for Natural Bioactive Molecules and Discovery of Innovative Drugs, College of Pharmacy, Jinan University, Guangzhou 511443, China. Electronic address:
Psoriasis is a prevalent relapsing dermatological condition that often necessitates lifelong treatment. The distinctive thickening of the stratum corneum presents a challenge to drug penetration. The employment of microneedles has been demonstrated to enhance the transdermal drug delivery efficacy by creating multiple microchannels in the skin.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Universidad Complutense de Madrid Facultad de Ciencias Quimicas, Inorganic Chemistry Department, 28034, Madrid, SPAIN.
Achieving high battery performance from low-cost, easily synthesisable electrode materials is crucial for advancing energy storage technologies. Metal organic frameworks (MOFs) combining inexpensive transition metals and organic ligands are promising candidates for high-capacity cathodes. Iron-chloranilate-water frameworks are herein reported to be produced in aqueous media under mild conditions.
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