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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 }·CHCl 3 ]  n  , [Co( 3 ) 2 (NCS) 2 ]  n  and [{Co( 4 ) 2 (NCS) 2 }·CHCl 3 ]  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 }·4CHCl 3 ] 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.

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