Coordination Polymers Based on Organic-Inorganic Hybrid Rigid Rod Comprising a Backbone of Anderson-Evans POMs

摘要

To construct polyoxometalates (POMs) coordination polymers (PCPs), we prepared two pyridine ligand-functionalized Anderson POMs: (1) (TBA)(3)[MnMo6O18((OCH2)(3)CN=CH-4-Py)(2)]center dot DMF ((TBA)(3)POM-1, TBA = tetrabutyl ammonium, Py = pyridine, DMF = dimethylformamide) and (TBA)(3)[MnMo6O18((OCH2)(3)CN=CH-3-Py)(2)] ((TBA)(3)POM-2) via the postfunctionalization of (TBA)(3)[MnMo6O18((OCH2)(3)CNH2)(2)] (Anderson-NH2) by 4-pyridinealdehyde and 3-pyridinealdehyde, respectively. They are characterized using POM-2 X-ray single-crystal diffraction, matrix-assisted laser desorption/ionization time-offlight mass spectrometry, electrospray ionization mass spectrometry, Fourier transform infrared spectroscopy, UV-visible spectroscopy, and H-1 NMR The self-assembly of (TBA)(3)POM-1 and [Cu(PPh3)(2)(CH3CN)(2)]CIO4(CuP2) in the mole ratios of 1:2 and 1:3 both gave the same one-dimensional double chain with the molecular formula of (NBu4)(n){[Cu(PPh3)(2)](2)(POM-1)}(n) (7.5DMF)(n) (1). On the contrary, the selfassembly of (TBA)(3)POM-2 and CuP2 in the mole ratio of 1:2 yields a two-dimensional (2D) coordination polymer of (TBA)(n){[Cu(PPh3)(2)](2)(POM-2)}(n)center dot(2DMF)(n) (2), while that self-assembly process in the mole ratio of 1:3 results in different 2D coordination polymer of {[Cu(PPh3)(2)](3)(POM-2)center dot(CH3CN)}(n)center dot(5CH(3)CN)(n )(3). Compounds 1-3 can keep their skeleton structures below 230 degrees C. They exhibit intense green emission (496 nm for 1; 537 nm for 2; 530 nm for 3) by ultraviolet irradiation (327 nm for 1; 303 nm for 2; 331 nm for 3), which can be tentatively ascribed as intraligand charge transfer with metal perturbation.