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

• Published in: Crystal growth & design Vol. 19; no. 2; pp. 925 - 931
• Main Authors: Zhu, Mao-Chun, Huang, Ying-Ying, Ma, Jian-Ping, Hu, Sheng-Min, Wang, Yue, Guo, Jun, Zhao, Yan-Xi, Wang, Long-Sheng
• Format: Journal Article
• Language: English
• Published: American Chemical Society 06.02.2019
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/acs.cgd.8b01467

To construct polyoxometalates (POMs) coordination polymers (PCPs), we prepared two pyridine ligand-functionalized Anderson POMs: (TBA)3[MnMo6O18­((OCH2)3CNCH-4-Py)2]·DMF ((TBA)3POM-1, TBA = tetrabutyl ammonium, Py = pyridine, DMF = dimethylformamide) and (TBA)3[MnMo6O18­((OCH2)3CNCH-3-Py)2] ((TBA)3POM-2) via the postfunctionalization of (TBA)3[MnMo6O18­((OCH2)3CNH2)2] (Anderson-NH2) by 4-pyridinealdehyde and 3-pyridinealdehyde, respectively. They are characterized using X-ray single-crystal diffraction, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, electrospray ionization mass spectrometry, Fourier transform infrared spectroscopy, UV–visible spectroscopy, and 1H NMR. The self-assembly of (TBA)3POM-1 and [Cu­(PPh3)2­(CH3CN)2]­ClO4 (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 self-assembly of (TBA)3POM-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 ·(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)·(CH3CN)} n ·(5CH3CN) n (3). Compounds 1–3 can keep their skeleton structures below 230 °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.