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

  • Arvind K. Gupta
  • Ashok Yadav
  • Ramamoorthy BoomishankarEmail author
Research Article
  • 161 Downloads

Abstract

A new example of phosphonium cation, [P(NH3Py)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(N3Py)(NH3Py)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(NH3Py)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(NH3Py)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 {[Cu2(PO(NH3Py)3)3](NO3)2}n, 4. Crystallographic studies on all these newly synthesized compounds have shown interesting kinds of supramolecular organization for these molecules.

Graphical Abstract

New examples of a phosphonium cation, [P(NH3Py)4]+, and a phosphine imine, [P(N3Py)(NH3Py)3] featuring 3-pyridyl substituents have been reported. Treatment of the phosphonium cation with various metal salts of copper have resulted in a P–N bond cleavage in which the in situ generated phosphoramide ligand [PO(NH3Py)3], has shown to yield interesting kinds of self-assembled structures in macrocyclic, cage and 2D-coordination polymers.

Keywords

P–N ligands Phosphine imine Phosphonium cation Copper compounds Cationic MOFs 

Notes

Acknowledgments

The authors thank DST, India and IISER, Pune for financial support. AY thanks CSIR, India for a fellowship.

Supplementary material

40010_2014_135_MOESM1_ESM.doc (940 kb)
Supplementary material 1 (DOC 940 kb)

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Copyright information

© The National Academy of Sciences, India 2014

Authors and Affiliations

  • Arvind K. Gupta
    • 1
  • Ashok Yadav
    • 1
  • Ramamoorthy Boomishankar
    • 1
    Email author
  1. 1.Indian Institute of Science Education and Research (IISER), PunePuneIndia

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