Supramolecular chirogenesis with bis-chlorin versus bis-porphyrin hosts: peculiarities of chirality induction and modulation of optical activity.
[structure: see text] The complexation behavior, chirality induction and inversion in the achiral host, a racemic mixture of ethane-bridged bis(zinc octaethylchlorin) (1), and optical activity modulation in the chiral hosts, enantiopure 1(R) and 1(S), upon interaction with chiral and achiral amine guests have been investigated by means of the UV-vis, CD, and (1)H NMR techniques and compared with the corresponding spectral data of the bis-porphyrin analogue. It was found that the chirogenesis pathway is strongly dependent upon the structures of both major components (hosts and guests) of these supramolecular systems. Particularly, the distinct orientation of electronic transitions in the chlorin chromophores arisen from the reduced pyrrole ring, which makes it radically different from that of the porphyrin chromophores, and the size of the guest's substituents lead to the remarkable phenomenon of chirality induction-inversion in racemic 1 originating from the process of asymmetry transfer from enantiopure guests of the same homologous type and absolute configuration. This surprising chirogenic behavior is found to be in a sharp contrast to that observed in the analogous porphyrin-based systems. Furthermore, these structural and electronic phenomena also account for the effective optical activity quenching of enantiopure 1(R) and 1(S) upon interaction with chiral and with achiral amines, which results in formation of supramolecular complexes of opposite chirality.
Borovkov
Victor V
VV
Entropy Control Project, ICORP, JST, Toyonaka-shi, Osaka, Japan. inoue@chem.eng.osaka-u.ac.jp
Hembury
Guy A
GA
Inoue
Yoshihisa
Y
D000588:Amines / Q000737:chemistry; D015394:Molecular Structure; D011166:Porphyrins / Q000737:chemistry*; D013057:Spectrum Analysis; D013237:Stereoisomerism
D000588:Amines; D011166:Porphyrins; C006969:chlorin