title: Dissymmetric Bis(dipyrrinato)zinc(II) Complexes: Rich Variety and Bright Red to Near-Infrared Luminescence with a Large Pseudo-Stokes Shift.
abstract: Bis(dipyrrinato)metal(II) and tris(dipyrrinato)metal(III) complexes have been regarded as much less useful luminophores than their boron difluoride counterparts (4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes, BODIPYs), especially in polar solvent. We proposed previously that dissymmetry in such metal complexes (i.e., two different dipyrrinato ligands in one molecule) improves their fluorescence quantum efficiencies. In this work, we demonstrate the universality and utility of our methodology by synthesizing eight new dissymmetric bis(dipyrrinato)zinc(II) complexes and comparing them with corresponding symmetric complexes. Single-crystal X-ray diffraction analysis, (1)H and (13)C NMR spectroscopy, and high-resolution mass spectrometry confirm the retention of dissymmetry in both solution and solid states. The dissymmetric complexes all show greater photoluminescence (PL) quantum yields (ϕPL) than the corresponding symmetric complexes, allowing red to near-infrared emissions with large pseudo-Stokes shifts. The best performance achieves a maximum PL wavelength of 671 nm, a pseudo-Stokes shift of 5400 cm(-1), and ϕPL of 0.62-0.72 in toluene (dielectric constant εs = 2.4), dichloromethane (εs = 9.1), acetone (εs = 21.4), and ethanol (εs = 24.3). The large pseudo-Stokes shift is distinctive considering BODIPYs with small Stokes shifts (∼500 cm(-1)), and the ϕPL values are higher than or comparable to those of BODIPYs fluorescing at similar wavelengths. Electrochemistry and density functional theory calculations illustrate that frontier orbital ordering in the dissymmetric complexes meets the condition for efficient PL proposed in our theory.
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.|JST-PRESTO , 4-1-8, Honcho, Kawaguchi, Saitama 332-0012, Japan.
authors.forename: Ryota
authors.initials: R
authors.lastname: Sakamoto
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Toshiki
authors.initials: T
authors.lastname: Iwashima
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Julius F
authors.initials: JF
authors.lastname: Kögel
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Shinpei
authors.initials: S
authors.lastname: Kusaka
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Mizuho
authors.initials: M
authors.lastname: Tsuchiya
authors.affiliation: Division of Chemical Engineering, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University , 1-3, Machikaneyama, Toyonaka, Osaka 560-8531, Japan.
authors.forename: Yasutaka
authors.initials: Y
authors.lastname: Kitagawa
authors.affiliation: Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Nishihara