Synthesis of an NO2S3-macrocycle (L, see below) incorporating a pyridine subunit and its anion and/or mole ratio-dependent coordination modes in the formations of mercury(II)1 and cadmium(II) complexes are reported. When the mercury(II) salts with different anions (ClO4- or Br-) were reacted with L, the Hg(ClO4)2 afforded a typical endocyclic complex [Hg(L)](ClO4)2 (1). Meanwhile, the HgBr2 gave an exocyclic complex [Hg(L)Br2] (2) in which the metal ion exists outside the macrocyclic cavity. The observed anion effect on the coordination modes can be explained by the anion coordination ability toward the metal cation. In the mole ratio variation experiments, notably, the use of 1.5 equiv or above amount of HgBr2 in the same reaction condition gave a unique endo/exocyclic dumbbell-type complex [Hg4(L)2Br6][Hg2Br6] (3) (see below). In cadmium(II) halides (Br- or I-) system, the reaction of L with CdBr2 afforded a bromo-complex, [Cd(L)Br]2[Cd2Br6] (4), showing three separated units: two macrocyclic complex cation units and one cadmium cluster complex anion unit. The complex 4 was filtered and the filtrate was collected. Complex [Cd(L)Br]2[CdBr4] (5) was formed by the slow diffusion into this resulting solution after a day. When CdI2 was used instead of CdBr2, two endocyclic complexes, [Cd(L)I]2[CdI4]·CH2Cl2 (6) and [Cd(L)I]2[Cd2I6]·CH2Cl2 (7), with different cadmium cluster complex anion unit were isolated as a kinetic (6) and thermodynamic controlled (7) products in neutral condition. In the mole ratio variation experiments, notably, the use of three equivalents or above amount of CdI2 in the same reaction condition gave a unique endo/exocyclic dumbbell-type complex, [Cd6(L)2I12] (8). To monitor the observed mole ratio-dependent endo-coordination products as well as their reactivities, the systematic powder X-ray diffraction (PXRD) analysis has also been applied. Reference 1. H.-H. Lee, I.-H. Park, S. S. Lee, Inorg. Chem. 2014, 53, 4763.

Anion and mole ratio effects on the coordination modes of an NO2S3donor macrocycle

249th National Meeting (2015)

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