In:
Angewandte Chemie, Wiley, Vol. 135, No. 38 ( 2023-09-18)
Abstract:
High quantum yield triplets, populated by initially prepared excited singlets, are desired for various energy conversion schemes in solid working compositions like porous MOFs. However, a large disparity in the distribution of the excitonic center of mass, singlet‐triplet intersystem crossing (ISC) in such assemblies is inhibited, so much so that a carboxy‐coordinated zirconium heavy metal ion cannot effectively facilitate the ISC through spin‐orbit coupling. Circumventing this sluggish ISC, singlet fission (SF) is explored as a viable route to generating triplets in solution‐stable MOFs. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron super‐exchange to generate triplet pairs. Here we show that a predesigned chromophoric linker with extremely poor ISC efficiency ( k ISC ) but form triplets in MOF in contrast to the frameworks that are built from linkers with sizable k ISC but . This work opens a new photophysical and photochemical avenue in MOF chemistry and utility in energy conversion schemes.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v135.38
DOI:
10.1002/ange.202305323
Language:
English
Publisher:
Wiley
Publication Date:
2023
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