Straight Versus Branched Chain Substituents in 4'-(Butoxyphenyl)-3,2':6',3″-terpyridines: Effects on (4,4) Coordination Network Assemblies.

The preparation and characterization of the isomers rac-4'-(4-butan-2-yloxyphenyl)-3,2':6',3″-terpyridine (rac-2), 4'-(2-methylpropoxyphenyl)-3,2':6',3″-terpyridine (3) and 4'-(tert-butoxyphenyl)-3,2':6',3″-terpyridine (4) are reported. The compounds react with Co(NCS)2 under conditions of crystal growth at room temperature to give single crystals of [{Co(rac-2)2(NCS)2}·CHCl3]n, [Co(3)2(NCS)2]n and [{Co(4)2(NCS)2}·CHCl3]n which possess (4,4) networks, with the Co centers acting as 4-connecting nodes. Powder X-ray diffraction (PXRD) was used to confirm that the crystals chosen for single crystal X-ray diffraction were representative of the bulk samples. The detailed structures of the three networks have been compared with that of the previously reported [{Co(1)2(NCS)2}·4CHCl3]n in which 1 is 4'-(butoxyphenyl)-3,2':6',3″-terpyridine. Whereas the switch from 1 with the straight-chain butoxy substituent to rac-2, 3 and 4 with branched chains causes significant structural perturbation, changes in the spatial properties of the branched substituents are accommodated with subtle conformational changes in the 3,2':6',3″-tpy domain.