Structure-performance relationship for a family of disperse azo dyes having the same D-π-A...

A combinational study of structural chemistry and dyestuff chemistry has been carried out to reveal the structure-performance relationship for eight disperse azo dyes by comparing their structures, electronic spectra, solvatochromism and theoretic computations. All eight structural analogues have the same 4-nitro-4'-amino-azobenzene donor-π-acceptor skeleton but different substituted groups, namely, R1 and R2 in ring A, R3, R4 and R5 in Ring B. X-ray single-crystal diffraction analyses indicate that four azo dyes have severely twisted aminoazobenzene structures because of the steric hindrance of ortho dichloro/dibromo radicals of 4-nitrobenzene moiety, while the other four dyes show essentially planar conformation due to the ortho monosubstituted 4-nitrobenzene amine and 4'-amino-azobenzene units. It is noted that the electronic spectra are closely related to their molecular structures, where the presence of different auxochrome groups and the spatial crowding effects in the aminoazobenzene backbone lead to significant alterations of the bathochromic and hypsochromic shifts.