title: Red/near-infrared luminescence tuning of group-14 element complexes of dipyrrins based on a central atom.
abstract: A dipyrrin complex has been one of the most utilized fluorescent dyes, and a variety of dipyrrin complexes show intriguing functions based on the various coordination structures of the central element. We now report the synthesis, structure, and photophysical properties of germanium and stannane complexes of the N2O2-type tetradentate dipyrrin, L·Ge and L·Sn, which are heavier analogues of the previously reported dipyrrin silicon complex, L·Si. The central group-14 atoms of the monomeric complexes have geometries close to trigonal bipyramidal (TBP), in which the contribution of the square-pyramidal (SP) character becomes higher as the central atom is heavier. Interestingly, L·Sn formed a dimeric structure in the crystal. All complexes L·Si, L·Ge, and L·Sn showed a fluorescence in the red/NIR region. Fluorescence quantum yields of L·Ge and L·Sn are higher than that of L·Si. These results indicated that the central atom on the dipyrrin complexes contributes not only to the geometry difference but also to tuning the fluorescence properties.
authors.affiliation: Graduate School of Pure and Applied Sciences & Tsukuba Research Center for Interdisciplinary Materials Science, University of Tsukuba , 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan.
authors.forename: Masaki
authors.initials: M
authors.lastname: Yamamura
authors.forename: Marcel
authors.initials: M
authors.lastname: Albrecht
authors.forename: Markus
authors.initials: M
authors.lastname: Albrecht
authors.forename: Yoshinobu
authors.initials: Y
authors.lastname: Nishimura
authors.forename: Tatsuo
authors.initials: T
authors.lastname: Arai
authors.forename: Tatsuya
authors.initials: T
authors.lastname: Nabeshima
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005857:Germanium / Q000737:chemistry*; D049449:Luminescence; D008958:Models, Molecular; D011721:Pyrenes / Q000737:chemistry*; D012825:Silicon / Q000737:chemistry*; D014001:Tin / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D011721:Pyrenes; D005857:Germanium; D014001:Tin; D012825:Silicon