Crystal Engineering of Schiff Base Zn(II) and Cd(II) Homo- and Zn(II)M(II) (M = Mn or Cd) Heterometallic Coordination Polymers and Their Ability to Accommodate Solvent Guest Molecules

Based on solvothermal synthesis, self-assembly of the heptadentate 2,6-diacetylpyridine bis(nicotinoylhydrazone) Schiff base ligand (H2L) and Zn(II) and/or Cd(II) salts has led to the formation of three homometallic [CdL](n) (1), {[CdL]center dot 0.5dmf center dot H2O}(n) (2) and {[ZnL]center dot 0.5dmf center dot 1.5H(2)O}(n) (3), as well as two heterometallic {[Zn0.75Cd1.25L2]center dot dmf center dot 0.5H(2)O}(n) (4) and {[MnZnL2]center dot dmf center dot 3H(2)O}(n) coordination polymers. Compound 1 represents a 1D chain, whereas 2-5 are isostructural and isomorphous two-dimensional structures. The entire series was characterized by IR spectroscopy, thermogravimetric analysis, single-crystal X-ray diffraction and emission measurements. 2D coordination polymers accommodate water and dmf molecules in their cage-shaped interlayer spaces, which are released when the samples are heated. Thus, three solvated crystals were degassed at two temperatures and their photoluminescent and adsorption-desorption properties were recorded in order to validate this assumption. Solvent-free samples reveal an increase in volume pore, adsorption specific surface area and photoluminescence with regard to synthesized crystals.

Automated summary

Solvent-assisted synthesis of coordination polymers with different metal compositions resulted in variations in structure and properties, as characterized through spectroscopic and thermal analysis methods. The presence of solvents played a role in the properties of the coordination polymers, impacting their adsorption and luminescence properties.