Synthesis and charge-transfer dynamics in a ferrocene-containing organoboryl aza-BODIPY donor-acceptor triad with boron as the hub

Eranda Maligaspe; Tom J Pundsack; Lauren M Albert; Yuriy V Zatsikha; Pavlo V Solntsev; David A Blank; Victor N Nemykin

doi:10.1021/acs.inorgchem.5b00494

Synthesis and charge-transfer dynamics in a ferrocene-containing organoboryl aza-BODIPY donor-acceptor triad with boron as the hub

Inorg Chem. 2015 Apr 20;54(8):4167-74. doi: 10.1021/acs.inorgchem.5b00494. Epub 2015 Mar 30.

Authors

Eranda Maligaspe¹, Tom J Pundsack², Lauren M Albert², Yuriy V Zatsikha¹, Pavlo V Solntsev^{1

2}, David A Blank², Victor N Nemykin¹

Affiliations

¹ †Department of Chemistry and Biochemistry, University of Minnesota-Duluth, 1039 University Drive, Duluth, Minnesota 55812, United States.
² §Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.

PMID: 25822143
DOI: 10.1021/acs.inorgchem.5b00494

Abstract

A N,N'-bis(ferroceneacetylene)boryl complex of 3,3'-diphenylazadiisoindolylmethene was synthesized by the reaction of an N,N'-difluoroboryl complex of 3,3'-diphenylazadiisoindolylmethene and ferroceneacetylene magnesium bromide. The novel diiron complex was characterized by a variety of spectroscopic techniques, electrochemistry, and ultrafast time-resolved methods. Spectroscopy and redox behavior was correlated with the density functional theory (DFT) and time-dependent DFT calculations. An unexpected degree of coupling between the two Fc ligands was observed. Despite a lack of conjugation between the donor and acceptor, the complex undergoes very rapid (τ = 1.7 ± 0.1 ps) photoinduced intramolecular charge separation followed by subpicosecond charge recombination to form a triplet state with a lifetime of 4.8 ± 0.1 μs.