Structural effects on the electronic absorption properties of 5,6-dihydroxyindole oligomers: the potential of an integrated experimental and DFT approach to model eumelanin optical properties.
Elucidation of the relationships between structural features and UV-visible absorption properties of 5,6-dihydroxyindole oligomers is an essential step towards an understanding of the unique optical properties of eumelanins. Herein, we report the first combined experimental and density functional theory (DFT) investigation of the 5,6-dihydroxyindole oligomers so far isolated. 2,2'-Biindolyl 2 and the 2,4'-biindolyl 3 absorb at longer wavelengths relative to 2,7'-biindolyl 4 and their spectra were well predicted by DFT analysis. The absorption bands of 2,4':2',4''- and 2,4':2',7''-triindolyls 5 and 6 also fall at different wavelengths and can be interpreted by DFT simulations as being due to a combination of two main separate transitions. Tetramer 7, in which two 2,4'-biindolyl units are linked through a 2,3'-connection, exhibits a broad chromophore extending over the entire UV range without well defined absorption maxima. Within the dimer-tetramer range examined, three key points emerge: (1) an increase in oligomer chain length does not result in any regular and predictable bathochromic shift; (2) a marked broadening of the absorption bands occurs when going from the monomer to the tetramer structure; and (3) the mode of coupling of the indole units is a crucial, hitherto unrecognized, structural parameter affecting the electronic absorption properties of 5,6-dihydroxyindole oligomers. It is concluded that use of experimentally characterized oligomeric scaffolds as a basis for DFT calculations is a most promising approach to building reliable structural models for studies of eumelanins optical properties.
d'Ischia
Marco
M
Department of Organic Chemistry and Biochemistry, University of Naples Federico II, Naples, Italy. dischia@unina.it
Crescenzi
Orlando
O
Pezzella
Alessandro
A
Arzillo
Marianna
M
Panzella
Lucia
L
Napolitano
Alessandra
A
Barone
Vincenzo
V