Double-Helical Dinuclear Bis(dipyrromethene) Complexes Formed by Self-Assembly

• Published in: Journal of organic chemistry 2000-11, Vol.65 (23), p.7870-7877
• Main Authors: Thompson, Alison, Dolphin, David
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo000886p

Bis(dipyrromethene) ligands linked by an alkyl spacer between β and β ‘ positions are shown to give helical dimers or monomers, dependent upon the length of the alkyl linker, upon complexation. Ligands consisting of methylene, ethylene, and propylene linkers −(CH2) n − (n = 1, 2, and 3) give helical dimers, while longer linking chains (n = 4, 5, or 6) give monomers or mixtures of dimers and monomers. X-ray crystal structures of the dimeric zinc complexes (n = 1, 2, and 3) reveal that the angles between dipyrromethene planes and the extent of helicity in the complexes differ as the length of the linker varies. The extent of helicity was assessed and found to be dependent upon the length and, specifically, the conformational preferences of the alkyl spacer unit. The presence of an ethylene linker gave complexes of greatest helicity. The use of a methylene spacer gave less helical structures upon complexation, while propylene spacers gave only slightly helical complexes. Our studies identify the crucial importance that the conformational preferences of the β-β ‘ alkyl spacer group plays in the coordination algorithm of self-assembly to form dipyrromethene based complexes.