Stars and stripes: hexatopic tris(3,2':6',3''-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers.

The hexatopic ligands 1,3,5-tris(4,2':6',4''-terpyridin-4'-yl)benzene (1), 1,3,5-tris(3,2':6',3''-terpyridin-4'-yl)benzene (2), 1,3,5-tris{4-(4,2':6',4''-terpyridin-4'-yl)phenyl}benzene (3), 1,3,5-tris{4-(3,2':6',3''-terpyridin-4'-yl)phenyl}benzene (4) and 1,3,5-trimethyl-2,4,6-tris{4-(3,2':6',3''-terpyridin-4'-yl)phenyl}benzene (5) have been prepared and characterized. The single crystal structure of 1·1.75DMF was determined; 1 exhibits a propeller-shaped geometry with each of the three 4,2':6',4''-tpy domains being crystallographically independent. Packing of molecules of 1 is dominated by face-to-face π-stacking interactions which is consistent with the low solubility of 1 in common organic solvents. Reaction of 5 with [Cu(hfacac) 2 ]·H 2 O (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) under conditions of crystal growth by layering resulted in the formation of [Cu 3 (hfacac) 6 (5)] n ·2.8 n C 7 H 8 ·0.4 n CHCl 3 . Single-crystal X-ray diffraction reveals an unusual 1D-coordination polymer consisting of a series of alternating single and double loops. Each of the three crystallographically independent Cu atoms is octahedrally sited with cis -arrangements two N-donors from two different ligands 1 and, therefore, cis -arrangements of coordinated [hfacac] - ligands; this observation is unusual among compounds in the Cambridge Structural Database containing {Cu(hfacac) 2 N 2 } coordination units in which the two N-donors are in a non-chelating ligand.