Excitation Energy Delocalization and Transfer to Guests within M^II₄L₆ Cage Frameworks.

ABSTRACT: We have prepared a series of M^II₄L₆ tetrahedral cages containing one or the other of two distinct BODIPY moieties, as well as mixed cages that contain both BODIPY chromophores. The photophysical properties of these cages and their fullerene-encapsulated adducts were studied in depth. Upon cage formation, the charge-transfer character exhibited by the bis(aminophenyl)-BODIPY subcomponents disappeared. Strong excitonic interactions were instead observed between at least two BODIPY chromophores along the edges of the cages, arising from the electronic delocalization through the metal centers. This excited-state delocalization contrasts with previously reported cages. All cages exhibited the same progression from an initial bright singlet state (species I) to a delocalized dark state (species II), driven by interactions between the transition dipoles of the ligands, and subsequently into geometrically relaxed species III. In the case of cages loaded with C₆₀ or C₇₀ fullerenes, ultrafast host-to-guest electron transfer was observed to compete with the excitonic interactions, short-circuiting the I ? II ? III sequence.

SUBMITTER: Musser AJ 

PROVIDER: S-EPMC5579544 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature