Syntheses, structures, near-infrared and visible luminescence, and magnetic properties of lanthanide-organic frameworks with an imidazole-containing flexible ligand.
Reactions of tripodal ligand 1,3,5-tris(imidazole-1-ylmethyl)-2,4,6-trimethylbenzene (L) with lanthanide metal salts and triethyl orthoformate led to the formation of six bowl-like dinuclear compounds [Ln2(L)(HL)(NO3)6(HCOO)].3CH3OH (Ln = Gd 1, Tb 2, Dy 3, Er 4, Yb 5, and Eu 6). The single-crystal X-ray diffraction analysis revealed that six complexes are isomorphous and isostructural and that the dinuclear molecules are further connected by hydrogen bonds and pi-pi interactions, resulting in 3D channel-like structures. The luminescence properties have been studied, and the results showed that the Tb(III) (2) and Eu(III) (6) complexes exhibited sensitized luminescence in the visible region and their luminescence lifetimes in powder and DMSO-d6 solution are in the range of milliseconds. The Yb(III) complex (5) emits typical near-infrared luminescence in DMSO-d6 solution. Variable-temperature magnetic susceptibility measurements of 1-6 showed that complex 1 (Gd) is nearly a paramagnet and complexes 2 (Tb), 3 (Dy), and 4 (Er) show the ferromagnetic coupling between magnetic centers, whereas the depopulation of the Stark levels in complexes 5 (Yb) and 6 (Eu) leads to a continuous decrease in (chi M)T when the sample is cooled from 300 to 1.8 K.
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China.
Zheng-Hua
ZH
Zhang
You
Y
Song
Taka-aki
TA
Okamura
Yasuchika
Y
Hasegawa
Wei-Yin
WY
Sun
Norikazu
N
Ueyama
D003460:Crystallization; D018360:Crystallography, X-Ray; D007093:Imidazoles / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008024:Ligands; D049449:Luminescence; D008280:Magnetics; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010777:Photochemistry; D019265:Spectroscopy, Near-Infrared / Q000379:methods*; D013696:Temperature
D007093:Imidazoles; D028581:Lanthanoid Series Elements; D008024:Ligands; D009942:Organometallic Compounds; C029899:imidazole