Water-mediated supramolecular architecture of Co(III)-phenanthroline complexes: organizational control to 2D-layers and 3D-square cavities through substituted aryl carboxylate anions

作者：Singh Ajnesh; Sharma Raj P^*; Aree Thammarat; Venugopalan Paloth

来源：CrystEngComm, 2013, 15(6): 1153-1163.

DOI：10.1039/c2ce26573g

To explore the variation in the supramolecular architecture of cobalt(III)-1,10-phenanthroline-aryl carboxylate complexes in tune with aryl substitution, eight new supramolecular inorganic-organic framework complexes have been synthesized. These have the general formula [Co(phen)(2)CO3]L center dot nH(2)O, where phen = 1,10-phenanthroline, L = 3-nitrobenzoate (P (1) over bar, Z = 2, n = 4; 1), 4-nitrobenzoate (P (1) over bar, Z = 2, n = 5; 2), 2-chloro-4-nitrobenzoate (P (1) over bar, Z = 2, n = 5; 3), 3-methyl-4-nitrobenzoate (P (1) over bar, Z = 2, n = 5; 4), 4-chlorobenzoate (P2(1)/c, Z = 4, n = 7; 5), 2-iodobenzoate (P (1) over bar, Z = 2, n = 7; 6), 2-phenoxybenzoate (P (1) over bar, Z = 2, n = 8; 7) and 2-napthleneacetate (P2(1)/c, Z = 4, n = 7; 8) and were unequivocally characterized by physicochemical methods, spectroscopic techniques and single crystal X-ray crystallography. Solubility, conductivity measurements and X-ray structure determination revealed the ionic nature of complexes 1-8. While the complexes 1-4, 7 and 8 prefer a 2D layer structure; the complexes 5 and 6 favor a 3D square cavity and in all these complexes, water molecules act as stabilizing linkers between anions and cations. The weak non-covalent interactions of the type O-H center dot center dot center dot O (carboxylate/water/carbonato), C-H center dot center dot center dot O (carboxylate/water/carbonato), pi center dot center dot center dot pi, C-H center dot center dot center dot pi and anion center dot center dot center dot pi interactions play a crucial role in stabilizing the crystal lattices.

• 出版日期2013