title: Luminescent dipyrrinato complexes of trivalent group 13 metal ions.
abstract: Although free dipyrrins (dipyrromethenes) do not strongly luminesce, certain dipyrrinato complexes of BF2 and zinc(II) are known to be intensely luminescent species. Two new dipyrrinato fluorophores, based on complexes with gallium(III) and indium(III), are described. Using a previously described meso-mesityl-substituted dipyrrin, namely 5-mesityldipyrrin (mesdpm), the complexes [Ga(mesdpm)3] and [In(mesdpm)3] were prepared and structurally characterized. The complexes display the expected octahedral geometry about the metal ions. In some solvents, such as hexanes, the complexes emit green light upon excitation with UV light at room temperature, with quantum yields of 2.4% ([Ga(mesdpm)3]) and 7.4% ([In(mesdpm)3]) and lifetimes in the low nanosecond range. Observations are consistent with assignment to ligand-localized transitions, and this interpretation is further confirmed by density functional calculations described herein. The new complexes are important additions to the widely used family of dipyrrin-based fluorescent species and show that dipyrrinato complexes containing metals other than BF2 and zinc(II) may be useful fluorophores.
authors.affiliation: Department of Chemistry and Biochemistry, University of California-San Diego, La Jolla, CA 92093-0358, USA.
authors.forename: Van S
authors.initials: VS
authors.lastname: Thoi
authors.forename: Jay R
authors.initials: JR
authors.lastname: Stork
authors.forename: Douglas
authors.initials: D
authors.lastname: Magde
authors.forename: Seth M
authors.initials: SM
authors.lastname: Cohen
mesh_terms: D005708:Gallium / Q000737:chemistry*; D007204:Indium / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D049449:Luminescence; D008958:Models, Molecular; D015394:Molecular Structure; D011758:Pyrroles / Q000737:chemistry*
chemical_list: D007477:Ions; D011758:Pyrroles; C512015:dipyrromethane; D007204:Indium; D005708:Gallium