Supramolecular chirogenesis in zinc porphyrins: interaction with bidentate ligands, formation of tweezer structures, and the origin of enhanced optical activity.
The complexation behavior, binding properties, and spectral parameters of supramolecular chirality induction in the achiral host molecule, syn (face-to-face conformation) ethane-bridged bis(zinc porphyrin), upon interaction with chiral bidentate guests (diamines and amino alcohols) have been studied by means of UV-vis, CD, fluorescence, (1)H NMR, and ESI MS techniques. It was found that the guest structure plays a decisive role in the chirogenesis pathway. The majority of bidentate ligands (except those geometrically unsuitable) exhibit two major equilibria steps: the first guest ligation leading to formation of the 1:1 host-guest tweezer structure (K(1)) and the second guest molecule ligation (K(2)) forming the anti bis-ligated species (1:2). The second ligation is much weaker (K(1) >> K(2)) due to the optimal geometry and stability of the 1:1 tweezer complex. The enhanced conformational stability of the tweezer complex ensures an efficient chirality transfer from the chiral guest to the achiral host, consequently inducing a remarkably high optical activity in the bis-porphyrin.
Borovkov
Victor V
VV
Entropy Control Project, ICORP, JST, 4-6-3 Kamishinden, Toyonaka-shi, Osaka 560-0085, Japan. victrb@inoue.jst.go.jp
Lintuluoto
Juha M
JM
Hembury
Guy A
GA
Sugiura
Makiko
M
Arakawa
Ryuichi
R
Inoue
Yoshihisa
Y
D008024:Ligands; D008665:Metalloporphyrins / Q000737:chemistry*; D009904:Optical Rotation; D013057:Spectrum Analysis; D013237:Stereoisomerism
D008024:Ligands; D008665:Metalloporphyrins; C017802:zinc hematoporphyrin