Two novel hybrid compounds based on [MW_(12)O_(40)] ~(5-) (M = B, Al) heteropolyanions and copper coordination polymer with bpp ligands

摘要

Under hydrothermal condition, two novel organic-inorganic hybrid compounds, [Cu(bpp)][Cu_(2.5)(bpp)_3(Hbpp)]H_(0.5)[BW _(12)O_(40)]·1.5H_2O (1) and [Cu(en) _2(H_2O)]{[Cu(bpp)]_3[AlW_(12)O _(40)]}·H_2O (2) (bpp = 1,3-bis(4-pyridyl)propane; en = ethylenediamine), have been synthesized based on B/Al atom-centered Keggin-type polyoxometalates combined with Cu ions and bpp ligands. The two compounds are characterized through single-crystal X-ray diffraction analysis, elemental analyse, IR, UV and TG. For compound 1, as the nodes, the [BW_(12)O _(40)]~(5-) polyanions link to the [Cu_(2.5)(bpp) _3(Hbpp)]~(3.5+) oligomers, leading to the formation of 1D helical chains which further attach to the macrocycles [Cu_2(bpp) _2]~(2+) via the Cu-O weak interaction to construct the 2D "wave-like" layers. For compound 2, the {[Cu(bpp)] _4[AlW_(12)O_(40)]_2} unit is obtained by the interaction between two Keggin-type [AlW_(12)O_(40)] ~(5-) polyanions and one tetranuclear macrocycle composed by four [Cu(bpp)]~+ complex cations. Furthermore, the units are sandwiched by two 1D "wave-like" polymeric chains resulting in a new 1D structure. In addition, the electrochemical properties and electrocatalytic activities of these two compounds have been studied in this paper.