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Three-Component Self-Assembly of a Series of Triply Interlocked Pd12 Coordination Prisms and Their Non-Interlocked Pd6 Analogues

  1. Arun Kumar Bar1,
  2. Dr. Srinivasarao Raghothama2,
  3. Dr. Dohyun Moon3,
  4. Prof. Partha Sarathi Mukherjee1,*

Article first published online: 7 FEB 2012

DOI: 10.1002/chem.201102963

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 18, Issue 11, pages 3199–3209, March 12, 2012

Additional Information

How to Cite

Bar, A. K., Raghothama, S., Moon, D. and Mukherjee, P. S. (2012), Three-Component Self-Assembly of a Series of Triply Interlocked Pd12 Coordination Prisms and Their Non-Interlocked Pd6 Analogues. Chem. Eur. J., 18: 3199–3209. doi: 10.1002/chem.201102963

Author Information

  1. 1

    Department of Inorganic and Physical Chemistry, Indian Institution of Science, Bangalore 560 012 (India), Fax: (+91) 8023601552

  2. 2

    NMR Research Centre, Indian Institution of Science, Bangalore 560 012 (India)

  3. 3

    Pohang Accelerator Laboratory, Pohang, Kyungbook-790784 (Korea)

*Department of Inorganic and Physical Chemistry, Indian Institution of Science, Bangalore 560 012 (India), Fax: (+91) 8023601552

Publication History

  1. Issue published online: 2 MAR 2012
  2. Article first published online: 7 FEB 2012
  3. Manuscript Received: 21 SEP 2011

Funded by

  • DST
  • CSIR

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Keywords:

  • cage compounds;
  • host–guest systems;
  • metal–ligand coordination;
  • prisms;
  • self-assembly

Abstract

Template-assisted formation of multicomponent Pd6 coordination prisms and formation of their self-templated triply interlocked Pd12 analogues in the absence of an external template have been established in a single step through Pd[BOND]N/Pd[BOND]O coordination. Treatment of cis-[Pd(en)(NO3)2] with K3tma and linear pillar 4,4′-bpy (en=ethylenediamine, H3tma=benzene-1,3,5-tricarboxylic acid, 4,4′-bpy=4,4′-bipyridine) gave intercalated coordination cage [{Pd(en)}6(bpy)3(tma)2]2[NO3]12 (1) exclusively, whereas the same reaction in the presence of H3tma as an aromatic guest gave a H3tma-encapsulating non-interlocked discrete Pd6 molecular prism [{Pd(en)}6(bpy)3(tma)2(H3tma)2][NO3]6 (2). Though the same reaction using cis-[Pd(NO3)2(pn)] (pn=propane-1,2-diamine) instead of cis-[Pd(en)(NO3)2] gave triply interlocked coordination cage [{Pd(pn)}6(bpy)3(tma)2]2[NO3]12 (3) along with non-interlocked Pd6 analogue [{Pd(pn)}6(bpy)3(tma)2](NO3)6 (3′), and the presence of H3tma as a guest gave H3tma-encapsulating molecular prism [{Pd(pn)}6(bpy)3(tma)2(H3tma)2][NO3]6 (4) exclusively. In solution, the amount of 3′ decreases as the temperature is decreased, and in the solid state 3 is the sole product. Notably, an analogous reaction using the relatively short pillar pz (pz=pyrazine) instead of 4,4′-bpy gave triply interlocked coordination cage [{Pd(pn)}6(pz)3(tma)2]2[NO3]12 (5) as the single product. Interestingly, the same reaction using slightly more bulky cis-[Pd(NO3)2(tmen)] (tmen=N,N,N′,N′-tetramethylethylene diamine) instead of cis-[Pd(NO3)2(pn)] gave non-interlocked [{Pd(tmen)}6(pz)3(tma)2][NO3]6 (6) exclusively. Complexes 1, 3, and 5 represent the first examples of template-free triply interlocked molecular prisms obtained through multicomponent self-assembly. Formation of the complexes was supported by IR and multinuclear NMR (1H and 13C) spectroscopy. Formation of guest-encapsulating complexes (2 and 4) was confirmed by 2D DOSY and ROESY NMR spectroscopic analyses, whereas for complexes 1, 3, 5, and 6 single-crystal X-ray diffraction techniques unambiguously confirmed their formation. The gross geometries of H3tma-encapsulating complexes 2 and 4 were obtained by universal force field (UFF) simulations.

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