Substrate and product binding inside a stimuli-responsive coordination cage acting as a singlet oxygen photosensitizer

Abstract

Multiple functionalities of an acridone-based metallosupramolecular assembly: photosensitization of singlet oxygen, allosteric activation as host and encapsulation of the substrate and product of a hetero-Diels-Alder reaction.

Perylene Diimide-Based Multicomponent Metallacages as Photosensitizers for Visible Light-Driven Photocatalytic Oxidation Reaction

“…[20][21][22][23][24][25][26][27][28] Especially, the preparation of photosensitizers using this method not only avoids their self-aggregation through the formation of geometric structures, but also facilitates the intersystem crossing owing to the introduction of heavy metal atoms, giving high 1 O 2 generation ability and photostability. [29][30][31][32][33][34] Moreover, different buliding blocks capable of generating 1 O 2 can be integrated into a single metallacage. Such metallacage possesses three-dimentional cavity, which is capable of encapsulating guest molecules (Scheme 1c).…”

M6L12 Nanospheres with Multiple C70 Binding Sites for 1O2 Formation in Organic and Aqueous Media

“…Whereas [Pd 6 L O 12 ] showed a marginal productivity (TON = 20), which is attributed to the background reaction, [Pd 6 L N 12 ] showed to be a good photocatalyst for the peroxidation of anthracene (TON = 630). We attribute the catalytic productivity of [Pd 6 L N 12 ] to the weak absorption of the nanosphere above 400 nm (Figure D), which is an excitation wavelength of the carbazole unit of the building block, which is part of the nanosphere (for comparison with other systems, see for example, refs − ). [Pd 6 L O 12 ] has no absorption above 400 nm, making the sphere itself less effective in 1 O 2 generation using white LED light.…”

Coordination Cage‐Based Emulsifiers: Templated Formation of Metal Oxide Microcapsules Monitored by In Situ LC‐TEM

“…[10] During the past four decades, the development of rational selfassembly approaches resulted in a large variety of artificial hosts of nanometre dimensions with applications in selective recognition, adaptive guest binding, stabilization of reactive intermediates, and catalysis. [11][12][13][14][15][16][17][18] However, the potential of such discrete self-assemblies as tools in the development of structured inorganic materials has rarely been tested. [19,20] Surfactants or amphiphiles consist of two different moieties, one with hydrophilic/polar and the second with hydrophobic/ non-polar character, connected via covalent and dynamic covalent bonding, as well as noncovalent interactions.…”

“…Functional multicomponent systems are ubiquitous in nature; for example multimeric enzyme complexes, which utilize their microenvironment and reactive interior to promote reactions with remarkable rate acceleration, substrate specificity, and product selectivity [10] . During the past four decades, the development of rational self‐assembly approaches resulted in a large variety of artificial hosts of nanometre dimensions with applications in selective recognition, adaptive guest binding, stabilization of reactive intermediates, and catalysis [11–18] . However, the potential of such discrete self‐assemblies as tools in the development of structured inorganic materials has rarely been tested [19,20] …”

“… [10] During the past four decades, the development of rational self‐assembly approaches resulted in a large variety of artificial hosts of nanometre dimensions with applications in selective recognition, adaptive guest binding, stabilization of reactive intermediates, and catalysis. [ 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ] However, the potential of such discrete self‐assemblies as tools in the development of structured inorganic materials has rarely been tested. [ 19 , 20 ]…”