A series of 3D PW12O403--based Ag-I-bis(triazole) complexes containing different multinuclear loops: syntheses, structures and properties

作者：Wang Xiuli^*; Zhao Dan; Tian Aixiang; Ying Jun

来源：CrystEngComm, 2013, 15(22): 4516-4526.

DOI：10.1039/c3ce40375k

Four [PW12O40](3-) (PW12)-based inorganic-organic hybrid compounds constructed from Ag-I ions and flexible bis(triazole) ligands with different spacer lengths, [Ag-8(btp)(4)(H2O)(2)((HPW10W2O40)-W-VI-O-V)(2)]center dot H2O (1), [Ag-4(btb)(2)((HPW10W2O40)-W-VI-O-V)] (2), [(btb)(H3PW12O40)]center dot 6H(2)O (3) and [Ag-5(btx)(4)((PW10W2O40)-W-VI-O-V)] (4), (btp = 1,3-bis(1,2,4-triazol-1-yl)propane, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, btx = 1,6-bis(1,2,4-triazol-1-yl)hexane), have been successfully isolated in the pH range 0.5-2.0 under hydrothermal conditions and characterized by single crystal X-ray diffraction analysis. In compound 1, the btp with a shorter spacer -(CH2)(3)- was used, and the 2D Ag-I-btp wave layers containing tetra-nuclear loops have been obtained, which were further extended into a 3D hamburger-style framework by two types of PW12 inorganic linkages. In compound 2, the btp ligand was replaced by btb with a longer spacer -(CH2)(4)-, thus a 2D Ag-I-btb grid layer containing two types of multinuclear loops was obtained. The PW12 anions reside in the void of a large hexa-nuclear loop and as octa-dentate inorganic linkages connect these 2D grid layers to construct a 3D framework. Compound 3 was synthesized under the same conditions as 2 except for a different crystallization time, which only exhibits a supramolecular structure constructed from protonated PW12 and btb molecules. The btx molecule with the longest -(CH2)(6)- spacer was utilized in compound 4, an interesting 3-fold interpenetrating 2D Ag-I-btx network containing large dodeca-nuclear loops formed, which was further linked by the six-connected PW12 anions to construct a 3D skeleton. The influences of -(CH2)(n)- pacers as well as the pH value and crystallization time on forming and tuning different 3D Ag-I/POM-based compounds containing different multinuclear loops have been discussed. Moreover, the electrochemical properties and photochemical catalysis of these four compounds have also been investigated.

• 出版日期2013
• 单位渤海大学