Construction of a square-planar molecular box: self-assembly of palladium(II) complexes of 3,6,9,16,19,22-hexaazatricyclo[22.2.2.2(11,14)]triacon-11,13,24,26(1),27,29-hexaene through hydrogen-bonding interactions.
Binuclear palladium(II) complexes of the macrocyclic polyamine 3,6,9,16,19,22-hexaazatricyclo[22.2.2.2(11,14)]triacon-11,13,24,26(1),2 7,29-hexaene (L) are used to construct molecules having special shapes. In this study two binuclear palladium(II) complexes [Pd(2)LI(2)]I(2)and [Pd(2)LCl(2)](NO(3))(2).H(2)O are synthesized and structurally characterized. X-ray crystallography shows that both complexes exist as one-dimensional chains formed via intermolecular hydrogen-bonding N(3)-H(3C)---X in which X is I and Cl. Moreover, the ligands in both complexes adopt a boatlike conformation that may facilitate the formation of the tetranuclear complex. The cationic aqua complex [Pd(2)L(H(2)O)(m)(NO(3))(n)]((4-n)+, obtained by the treatment of [Pd(2)LI(2)]I(2)and [Pd(2)LCl(2)]Cl(2) with AgNO(3), is used as a building block for the construction of a tetranuclear palladium(II) complex [Pd(4)L(2)(C(2)O(4))(2)](NO(3))(4).6H(2)O. X-ray crystallography shows that the tetranuclear complex forms an open, hydrophobic box. These molecular boxes are connected via the hydrogen bond N(3)-H(3C)---O(4B) (symmetry code B: x, 1 + y, z) into a one-dimensional chain. A two-dimensional structure is formed via pi-pi stacking of the plane defined by C6 to C11 in the one chain and its symmetry-related plane (symmetry code C: -x, -1 - y, 2 - z) in another chain. This study exemplifies a new method for the assembly of molecular boxes using a macrocyclic ligand.
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State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, Nanjing University, Nanjing 210093, P. R. China.
Liu
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F
Duan
C
C
Guo
Z
Z
Zhou
S
S
Liu
Y
Y
Zhu
L
L