Fine Tuning of Multicolored Photoluminescence in Crystalline Magnetic Materials Constructed of Trimetallic Eu x Tb 1-x [Co(CN) 6 ] Cyanido-Bridged Chains.

Coordination compounds built of trivalent lanthanide ions have been demonstrated as promising solid-state materials for diverse photoluminescent applications and as attractive magnetic objects with the prospective application in information storage and spintronics. We present a synthetic methodology in which both luminescent and magnetic functionalities are induced within lanthanide-based coordination polymers by the application of hexacyanocobaltate(III) anions and 3-hydroxypyridine (3-OHpy), both coordinated to 4f-metal ions modulating the lanthanide-centered properties. We report a series of trimetallic cyanido-bridged chains {[EuIII x TbIII 1-x (3-OHpy)2 (H2 O)4 ][CoIII (CN)6 ]}·H2 O (x = 1, 0.8, 0.5, 0.4, 0.3, 0.2, 0.1, 0; compounds 1, 2, ..., 7, 8). They reveal tunable visible photoluminescence ranging from green, through yellow and orange, to red color depending on the composition of material and the wavelength of UV excitation light. Such multicolored emission is realized by the adjusted ratio between red emissive Eu3+ and green emissive Tb3+ and by the selection of wavelengths of UV light controlling the intensities of Eu- and Tb-based components of visible luminescence. The photoluminescence is enhanced by the energy-transfer (ET) process from [CoIII (CN)6 ]3- and 3-OHpy to lanthanides, and the efficiencies of ET to Eu and Tb play an important role in the switchable emission. The whole family, 1-8, exhibits temperature-dependent paramagnetism due to the intrinsic property of lanthanide(3+) ions. Tb-containing 2-8 reveal the field-induced slow relaxation of magnetization due to the magnetic anisotropy of Tb3+ . Moreover, the compounds built of large amounts of Tb reveal the double relaxation, the faster of a typical TbIII single-ion origin, and the slower originating from the magnetic dipole-magnetic dipole interactions between neighboring TbIII centers. Compound 2, which can be considered as a magnetically diluted sample, exhibits almost single relaxation process with the thermal energy barrier ΔE/kB of 35.8(6) K and τ0 = 1.1(2) × 10-8 s at Hdc = 1500 Oe, indicating a single-molecule magnet behavior.