Department of Inorganic and Physical Chemistry, Indian Institution of Science, Bangalore 560 012, India.
Chemistry. 2012 Jul 27;18(31):9571-9. doi: 10.1002/chem.201201077. Epub 2012 Jun 28.
Three new nanoscopic trigonal prisms, (tmen)(6) Pd(6) (H(2)L)(3)(12) (1), (Meen)(6) Pd(6)(H(2) L)(3)(12) (2), and (2,2'-bipy)(6)Pd(6) (H(2)L)(3)(12) (3), have been synthesized in excellent yields through single-step metal-ligand-coordination-driven self-assembly using 5,10,15,20-tetrakis(3-pyridyl)porphyrin (H(2)L) as a donor and cis-blocked Pd(II) 90° acceptors. These complexes were fully characterized by spectroscopic studies and single-crystal X-ray diffraction. All of these barrels quantitatively bind Zn(II) ions in the N(4) pockets of the porphyrin walls at room temperature. Their corresponding zinc-embedded complexes, (tmen)(6)Pd(6)(ZnL)(3)(12) (1 a), (Meen)(6) Pd(6)(ZnL)(3)(12) (2 a), and (2,2'-bipy)(6)Pd(6)(ZnL)(3)(12) (3 a), were synthesized under ambient conditions by the post-synthetic binding of Zn(II) ions into the H(2)N(4) pockets of the porphyrin walls of these complexes. These zinc-embedded complexes were characterized by electronic absorption, fluorescence emission, (1)H NMR spectroscopy, as well as elemental analysis. Complexes 1-3 exhibited considerable microporosity in their solid state. Complex 1 was an efficient adsorbent for nitrogen gas and EtOH, MeOH, and water vapors.
三种新的纳米三角棱柱，(tmen)(6)Pd(6)(H(2)L)(3)(12) (1)、(Meen)(6)Pd(6)(H(2)L)(3)(12) (2) 和 (2,2'-bipy)(6)Pd(6)(H(2)L)(3)(12) (3)，通过使用 5,10,15,20-四(3-吡啶基)卟啉 (H(2)L) 作为供体和 cis-封锁 Pd(II) 90°受体的单步金属-配体配位驱动自组装，以优异的产率合成。这些配合物通过光谱研究和单晶 X 射线衍射进行了全面表征。所有这些桶在室温下定量地在卟啉壁的 N(4)口袋中结合 Zn(II)离子。它们相应的锌嵌入配合物，(tmen)(6)Pd(6)(ZnL)(3)(12) (1a)、(Meen)(6)Pd(6)(ZnL)(3)(12) (2a) 和 (2,2'-bipy)(6)Pd(6)(ZnL)(3)(12) (3a)，通过在这些配合物的卟啉壁的 H(2)N(4)口袋中后合成结合 Zn(II)离子合成。这些锌嵌入配合物通过电子吸收、荧光发射、(1)H NMR 光谱和元素分析进行了表征。配合物 1-3 在其固态中表现出相当大的微孔性。配合物 1 是氮气和 EtOH、MeOH 和水蒸气的有效吸附剂。
