on the chiroptical behavior of conjugated multichromophoric compounds of a new pseudoaromatic class bicolchicides and biisocolchicideschiroptical共轭multichromophoric化合物的行为的一个新的pseudoaromatic类bicolchicides biisocolchicides.pdfVIP

On the Chiroptical Behavior of Conjugated Multichromophoric Compounds of a New Pseudoaromatic Class: Bicolchicides and Biisocolchicides 1 1 1 2 Tiziana Funaioli *, Marino Cavazza , Maurizio Zandomeneghi , Francesco Pietra ` 1 Dipartimento di Chimica e Chimica Industriale, Universita di Pisa, Pisa, Italy, 2 Accademia Lucchese di Scienze, Lettere e Arti, Lucca, Italy Abstract Background: It is well known that, stemming from the mutual interplay between chromophores, circular dichroism (CD) is a powerful technique to deal with structural problems for both the small organic molecule and the biopolymer. However, quantitative interpretations of the spectroscopic and structural terms that give rise to the exciton couplet are usually presented for ideal cases, or a few CD bands only are taken into account, overlooking the role of the solvent medium. Methodology/Principal Findings: Circular dichroism and UV absorption spectra were carried out for colchicide (3) and isocolchicide (6), as well as their coupling products, 10,109-bicolchicide (2) and 9,99-biisocolchicide (5), in both hydrogen bonding and non hydrogen bonding solvents, as well as MeCN/H2O mixtures. A dramatic control by the solvent emerged, as even tiny changes in the composition of solvent mixtures, at ca 1 water molar fraction, induced a dramatic modification of their CD bands. A mutarotation phenomenon - long known for isocolchicine (8) - was also observed for 5, and can be attributed to the interconversion between atropisomers (R ,7S),(R ,7 9S)-5a and (R ,7S),(S ,7 9S)-5b. a a a a Conclusions/Significance: Our data