posted on 2017-01-17, 20:40authored byXun Feng, Yuquan Feng, Nan Guo, Yiling Sun, Tian Zhang, Lufang Ma, Liya Wang
A series of five
unique d–f heteronuclear luminescent metal–organic frameworks
(MOFs) in an entangled polyrotaxane array and the light-harvesting
block homonuclear zinc compound have been isolated successfully and
characterized. The series of isostructural polymers feature 3,4-connected
(4.82)(4.83.92)(6.8.9)2(6.92)(83) topology and high stability, exhibiting
diverse void spaces. By taking advantage of the isostructural MOFs 2 and 3, the intensities of red and green emissions
can be modulated by adjusting the ratios of EuIII and TbIII ions correspondingly, and white-light emission can be generated
by a combination of different doped TbIII and EuIII concentrations. The Tb–Zn-based framework {[Tb3Zn6(bipy2)2(Hmimda)7 (H2O)3]·5H2O}n (3; H3mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid and bipy = 4,4′-bipyridine)
can detect trace MgII ion with relatively high sensitivity
and selectivity. Dehydrated MOF 3a shows a remarkable
emission quenching effect through the introduction of I2 solids. Further investigation indicates that it exhibits turn on/off
switchable properties for small solvent molecules or heavy-metal ions.
Steady/transient-state near-IR luminescence properties for MOFs 1, 4, and 5 were investigated under
visible-light excitation.