A Series of Trifacial Pd6 Molecular Barrels with Porphyrin Walls

作者：Bar Arun Kumar; Mohapatra Sudip; Zangrando Ennio; Mukherjee Partha Sarathi^*

来源：Chemistry - A European Journal, 2012, 18(31): 9571-9579.

DOI：10.1002/chem.201201077

• cage compounds
• metal-ligand coordination
• palladium
• porphyrins
• self-assembly

Three new nanoscopic trigonal prisms, [(tmen)6Pd6(H2L)3](NO3)12 (1), [(Meen)6Pd6(H2L)3](NO3)12 (2), and [(2,2%26apos;-bipy)6Pd6(H2L)3](NO3)12 (3), have been synthesized in excellent yields through single-step metalligand-coordination-driven self-assembly using 5,10,15,20-tetrakis(3-pyridyl)porphyrin (H2L) as a donor and cis-blocked PdII 90 degrees acceptors. These complexes were fully characterized by spectroscopic studies and single-crystal X-ray diffraction. All of these barrels quantitatively bind ZnII ions in the N4 pockets of the porphyrin walls at room temperature. Their corresponding zinc-embedded complexes, [(tmen)6Pd6(ZnL)3](NO3)12 (1?a), [(Meen)6Pd6(ZnL)3](NO3)12 (2?a), and [(2,2%26apos;-bipy)6Pd6(ZnL)3](NO3)12 (3?a), were synthesized under ambient conditions by the post-synthetic binding of ZnII ions into the H2N4 pockets of the porphyrin walls of these complexes. These zinc-embedded complexes were characterized by electronic absorption, fluorescence emission, 1H NMR spectroscopy, as well as elemental analysis. Complexes 13 exhibited considerable microporosity in their solid state. Complex 1 was an efficient adsorbent for nitrogen gas and EtOH, MeOH, and water vapors.

• 出版日期2012-7