Influence of Anion and Mole Ratio on the Coordination Behavior of an NO₂S₃-Macrocycle: The Formation of a Dumbbell-Shaped Macrocyclic Cadmium(II) Iodide Complex

다국어 초록 (Multilingual Abstract)

<P>Anion and mole ratio dependent formations of cadmium(II) complexes with an NO2S3-macrocycle (L) incorporating a pyridine subunit are reported. When the cadmium(II) salts (1-10 equiv) with different halide ions (Br- or I-) were reacted with L, CdBr2 afforded a monomer complex, [Cd(L)Br](2)[Cd2Br6]center dot CH2Cl2 (1), with three separated parts in the whole mole ratio range: two 1:1 stoichiometric complex cation parts and one Cd2Br6 cluster anion part. After separation of 1 by filtration, [Cd(L)Br](2)[CdBr4]center dot CH2Cl2 (2) with similar composition was afforded, except the cluster was isolated from the filtrate. Unlike the CdBr2 complexation, CdI2 afforded the mole ratio dependent products (3-5). Below 2.5 equiv of CdI2, [Cd(L)I](2)[CdI4]center dot CH2Cl2 (3) and [Cd(L)I](2)[Cd2I6].0.5CH(2)Cl(2) (4) with different cadmium(II) iodide clusters were isolated as kinetic (3) and a thermodynamic (4) products. Notably, the use of 3 equiv or above amount of CdI2 gave a dumbbell-shaped complex, {[Cd(L)](2)(mu-Cd4I12)} (5), in which two mononuclear macrocyclic complex units are linked by a (mu-Cd4I12)(4-) cluster. To monitor the mole ratio dependency as well as their reactivities, the systematic powder X-ray diffraction (PXRD) analysis has also been applied.</P>