Structure study and luminescence thermochromism in hexanuclear 6-methyl-2-pyridinethiolato copper(I) crystals.
The structure of hexanuclear 6-methyl-2-pyridinethiolato copper(I) [Cu6(6-mpyt)(6)] crystals has been studied by the X-ray diffraction analysis. These crystals show highly efficient luminescence whose color changes drastically from red to green-blue with lowering temperature from room temperature (RT) to liquid nitrogen temperature (LNT). This is a new example of luminescence thermochromism for hexanuclear copper(I) cluster compounds. Two relaxed luminescence bands appear predominantly: one (CC-band), red luminescence appearing in the lower-energy region around 1.8 eV at higher temperature, is assigned to the transition between intramolecular orbitals (MO) of a Cu cluster center (CC), and the other (CT-band), green-blue luminescence appearing at the higher energy side of 2.6 eV than the CC-band at lower temperature, is assigned to a charge transfer (CT) transition from the CC-MO to a ligand MO. Additionally, the CT band can be deconvoluted to two subbands CT(L) and CT(H). The intensities of the CC- and the CT-bands change complementarily with temperature via a thermal activation process, giving the thermochromism. All of these band shapes can be fitted by a Gaussian function, and their widths are fairly large obeying the hyperbolic cotangent law. These features reflect our system to be a strong electron-lattice coupling one. The relaxation process of the photoexcited states is discussed in terms of a configuration coordinate model.
Xie
Haiyan
H
Department of Physics, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558-8585 Japan.
Kinoshita
Isamu
I
Karasawa
Tsutomu
T
Kimura
Kentarou
K
Nishioka
Takanori
T
Akai
Ichiro
I
Kanemoto
Katsuichi
K