Discrete and Polymeric Coordination Assemblies Derived from 3-Pyridyl Attached Flexible Phosphoric Triamide Ligand and Copper Salts

作者：Gupta Arvind K; Yadav Ashok; Boomishankar Ramamoorthy^*

来源：Proceedings of the National Academy of Sciences India Section A-Physical Sciences, 2014, 84(2): 205-212.

DOI：10.1007/s40010-014-0135-7

• P-N ligands
• Phosphine imine
• Phosphonium cation
• Copper compounds
• Cationic MOFs

A new example of phosphonium cation, [P((NHPy)-Py-3)(4)](+), (2) featuring 3-pyridyl substituents has been reported. Reactivity of 2 with KOH in methanol have resulted in the formation of a neutral phosphine imine [P((NPy)-Py-3)((NHPy)-Py-3)(3)], 2-H. Treatment of 2 with various metal salts of copper have resulted in a P-N bond cleavage in which the in situ generated phosphoramide ligand [PO((NHPy)-Py-3)(3)], 1, has shown to yield interesting kinds of self-assembled structures in macrocyclic, cage and 2D-coordination polymers. Thus, the reaction of 2 with Cu(NO3) 2 in methanol gave the supramolecular [M6L8](12+) type cage reported earlier with the phosphoramide 1. Treatment of 2 with a Cu(I) salt in CHCl3 under ambient conditions have lead to the formation of a 20-membered macrocyclic Cu(II) compound [(PO((NHPy)-Py-3)(3)) CuCl2](2), 3, via the in situ oxidation of Cu(I). In another reaction, treatment of 1 or 2 with Cu(NO3) 2 in a reducing solvent such as dimethylformamide (DMF) under hydrothermal conditions gave a Cu(I) coordination polymer {[Cu-2(PO((NHPy)-Py-3)(3))(3)](NO3)(2)}(n), 4. Crystallographic studies on all these newly synthesized compounds have shown interesting kinds of supramolecular organization for these molecules.

• 出版日期2014-6