Control of Lanthanide Coordination Environment: Synthesis, Structure, and Oxygen-Sensitive Luminescence Properties of an Eight-Coordinate Tb(III) Complex.
Coordination environment of the Tb(3+) ion in oxygen-sensitive luminescent complexes can be successfully controlled through the size of alkyl substituents on ligands {((RMe)ArOH)4cyclen} (R = tBu or Me; cyclen = 1,4,7,10-tetraazacyclododecane); a newly prepared eight-coordinate complex 1(tBu) shows higher oxygen sensitivity (KSV = 17 600) and lower luminescence quantum yield (Φ = 0.67 under N2) than those of the previously reported seven-coordinate analogues 1(Me) and [{((MeMe)ArO)3tacn}Tb(III)(THF)] (KSV = 12 600 and 8300, Φ = 0.91 and 0.91 under N2, respectively; tacn = 1,4,7-triazacyclononane; THF = tetrahydrofuran). The oxygen-sensitive mechanism is discussed on the basis of the photophysical properties of the corresponding Gd(III) complexes.
Department of Chemistry and Biochemistry, Graduate School of Engineering, ‡Center for Small Molecule Energy, and §International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University , 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
Hidetaka
H
Nakai
Department of Chemistry and Biochemistry, Graduate School of Engineering, ‡Center for Small Molecule Energy, and §International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University , 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
Juncheol
J
Seo
Department of Chemistry and Biochemistry, Graduate School of Engineering, ‡Center for Small Molecule Energy, and §International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University , 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
Kazuhiro
K
Kitagawa
Department of Chemistry and Biochemistry, Graduate School of Engineering, ‡Center for Small Molecule Energy, and §International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University , 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
Takahiro
T
Goto
Department of Chemistry and Biochemistry, Graduate School of Engineering, ‡Center for Small Molecule Energy, and §International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University , 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
Kyoshiro
K
Nonaka
Department of Chemistry and Biochemistry, Graduate School of Engineering, ‡Center for Small Molecule Energy, and §International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University , 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
Takahiro
T
Matsumoto
Department of Chemistry and Biochemistry, Graduate School of Engineering, ‡Center for Small Molecule Energy, and §International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University , 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
Seiji
S
Ogo