Molecules, Vol. 26, Pages 6337: Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2`:6`,3``-Terpyridines (Molecules)

Coordination networks formed between Co(NCS)2 and 4`-substituted-[1,1`-biphenyl]-4-yl-3,2`:6`,3”-terpyridines in which the 4`-group is Me (1), H (2), F (3), Cl (4) or Br (5) are reported. [Co(1)2(NCS)2]n.4.5nCHCl3, [Co(2)2(NCS)2]n.4.3nCHCl3, [Co(3)2(NCS)2]n.4nCHCl3, [Co(4)2(NCS)2]n, and [Co(5)2(NCS)2]n.nCHCl3 are 2D-networks directed by 4-connecting cobalt nodes. Changes in the conformation of the 3,2`:6`,3”-tpy unit coupled with the different peripheral substituents lead to three structure types. In [Co(1)2(NCS)2]n.4.5nCHCl3, [Co(2)2(NCS)2]n.4.3nCHCl3, [Co(3)2(NCS)2]n.4nCHCl3, cone-like arrangements of [1,1`-biphenyl]-4-yl units pack through pyridine...arene π-stacking, whereas Cl...π interactions are dominant in the packing in [Co(4)2(NCS)2]n. The introduction of the Br substituent in ligand 5 switches off both face-to-face π-stacking and halogen...π-interactions, and the packing interactions are more subtly controlled. Assemblies with organic linkers 1–3 are structurally similar and the lattice accommodates CHCl3 molecules in distinct cavities; thermogravimetric analysis confirmed that half the solvent in [Co(3)2(NCS)2]n.4nCHCl3 can be reversibly removed.