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Probing Electronic Communication and Excited-State Dynamics in the Unprecedented Ferrocene-Containing Zinc MB-DIPY.


ABSTRACT: The electronic communication between two ferrocene groups in the electron-deficient expanded aza-BODIPY analogue of zinc manitoba-dipyrromethene (MB-DIPY) was probed by spectroscopic, electrochemical, spectroelectrochemical, and theoretical methods. The excited-state dynamics involved sub-ps formation of the charge-separated state in the organometallic zinc MB-DIPYs, followed by recovery of the ground state via charge recombination in 12 ps. The excited-state behavior was contrasted with that observed in the parent complex that lacked the ferrocene electron donors and has a much longer excited-state lifetime (670 ps for the singlet state). Much longer decay times observed for the parent complex without ferrocene confirm that the main quenching mechanism in the ferrocene-containing 4 is reflective of the ultrafast ferrocene-to-MB-DIPY core charge transfer (CT).

SUBMITTER: Zatsikha YV 

PROVIDER: S-EPMC7658947 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Probing Electronic Communication and Excited-State Dynamics in the Unprecedented Ferrocene-Containing Zinc MB-DIPY.

Zatsikha Yuriy V YV   Shamova Liliya I LI   Schaffner Jacob W JW   Healy Andrew T AT   Blesener Tanner S TS   Cohen Gabriel G   Wozniak Brandon B   Blank David A DA   Nemykin Victor N VN  

ACS omega 20201027 44


The electronic communication between two ferrocene groups in the electron-deficient expanded aza-BODIPY analogue of zinc manitoba-dipyrromethene (MB-DIPY) was probed by spectroscopic, electrochemical, spectroelectrochemical, and theoretical methods. The excited-state dynamics involved sub-ps formation of the charge-separated state in the organometallic zinc MB-DIPYs, followed by recovery of the ground state via charge recombination in 12 ps. The excited-state behavior was contrasted with that ob  ...[more]

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