title: Tuning Electronic Structure, Redox, and Photophysical Properties in Asymmetric NIR-Absorbing Organometallic BODIPYs.
abstract: Stepwise modification of the methyl groups at the α positions of BODIPY 1 was used for preparation of a series of mono- (2, 4, and 6) and diferrocene (3) substituted donor-acceptor dyads in which the organometallic substituents are fully conjugated with the BODIPY π system. All donor-acceptor complexes have strong absorption in the NIR region and quenched steady-state fluorescence, which can be partially restored upon oxidation of organometallic group(s). X-ray crystallography of complexes 2-4 and 6 confirms the nearly coplanar arrangement of the ferrocene groups and the BODIPY π system. Redox properties of the target systems were studied using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). It was found that the first oxidation process in all dyads is ferrocene centered, while the separation between the first and the second ferrocene-centered oxidation potentials in diferrocenyl-containing dyad 3 is ∼150 mV. The density functional theory-polarized continuum model (DFT-PCM) and time-dependent (TD) DFT-PCM methods were used to investigate the electronic structure as well as explain the UV-vis and redox properties of organometallic compounds 2-4 and 6. TDDFT calculations allow for assignment of the charge-transfer and π → π* transitions in the target compounds. The excited state dynamics of the parent BODIPY 1 and dyads 2-4 and 6 were investigated using time-resolved transient spectroscopy. In all organometallic dyads 2-4 and 6 the initially excited state is rapidly quenched by electron transfer from the ferrocene ligand. The lifetime of the charge-separated state was found to be between 136 and 260 ps and demonstrates a systematic dependence on the electronic structure and geometry of BODIPYs 2-4 and 6.
authors.affiliation: ‡Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 5 Murmanska Strasse, 02660 Kyiv, Ukraine.
authors.forename: Yuriy V
authors.initials: YV
authors.lastname: Zatsikha
authors.forename: Eranda
authors.initials: E
authors.lastname: Maligaspe
authors.forename: Anatolii A
authors.initials: AA
authors.lastname: Purchel
authors.affiliation: ‡Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 5 Murmanska Strasse, 02660 Kyiv, Ukraine.
authors.forename: Natalia O
authors.initials: NO
authors.lastname: Didukh
authors.affiliation: ¶Department of Chemistry, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455, United States.
authors.forename: Yefeng
authors.initials: Y
authors.lastname: Wang
authors.affiliation: ‡Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 5 Murmanska Strasse, 02660 Kyiv, Ukraine.
authors.forename: Yuriy P
authors.initials: YP
authors.lastname: Kovtun
authors.affiliation: ¶Department of Chemistry, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455, United States.
authors.forename: David A
authors.initials: DA
authors.lastname: Blank
authors.forename: Victor N
authors.initials: VN
authors.lastname: Nemykin