Journal
CRYSTENGCOMM
Volume 16, Issue 14, Pages 3029-3039Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3ce42027b
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Funding
- CSIR, India [09/028 (0805)/2010-EMR-I]
- DST-FIST
- India
- Department of Science and Technology (DST), New Delhi, India [SR/S1/IC/0034/2012]
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Three new hetero-metallic Cu(II)-Zn(II) compounds [(CuL1)(2)Zn(N(CN)(2))(2)] (1), (2)(infinity)[(CuL2)(2)Zn(mu(1,5)-N(CN)(2))(2)](n) (2A) and (3)(infinity)[(CuL2)(2)Zn(mu(1,5)-N(CN)(2))(2)](n) (2B) have been synthesized by reacting a [CuL1] or [CuL2] metalloligand (where H2L1 = N, N'-bis(alpha-methylsalicylidene)-1,3-propanediamine and H2L2 = N, N'-bis(salicylidene)-1,3-propanediamine) with zinc perchlorate hexahydrate and sodium dicyanamide, using various molar ratios of the reactants. All three products have been characterized by IR and UV-Vis spectroscopies, ESI-MS, elemental, powder and single crystal X-ray diffraction analyses. Complex 1 is a discrete 0D trinuclear species in which two metalloligands coordinate to a zinc(II) ion through phenoxido oxygen atoms along with two terminal dicyanamido ligands. In contrast, products 2A and 2B are 2D and 3D coordination polymers, respectively, which bear a common [(CuL2)(2)Zn(N(CN)(2))(2)] trinuclear unit wherein, however, dicyanamido moieties adopt a mu(1,5)-bridging coordination mode. The coordination networks have been formed via the linkage, in different manners, of the trinuclear nodes [(CuL2)(2)Zn](2+) through Zn and Cu centres with the help of divergent dicyanamido spacers. These two isomeric coordination polymers represent a rare example of genuine supramolecular isomerism. The coordination networks in 2A and 2B have been classified from the topological viewpoint, revealing a binodal 3,4-connected underlying net with the 3,4L21 topology in 2A and a uninodal 4-connected underlying net with the qtz (quartz, 4/6/h1) topology in 2B. Electronic spectra and ESI mass spectra show that all three complexes lose their solid state identity in solution.
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