Aromatic polyimides containing side azobenzene groups have been synthesized by low-temperature solution polycondensation of certain aromatic dianhydrides with aromatic diamines containing preformed side azobenzene groups followed by chemical imidization at 100 degrees C in the presence of pyridine and acetic anhydride. The weight average molecular weight of these polymers is in the range of 16,000-129,000. The glass transition temperature of these polyimides is in the range of 185-230 degrees C. The polymer architecture presents a special characteristic, one of the azobenzene aromatic units being in the main chain of the polymer. This situation is intermediary between main-chain and side-chain azobenzene-containing polymers. The photochromic behavior, determined by the trans-cis isomerization process of azo-groups, in solution and in solid state, was evaluated. The synthesized polyimides were studied by spectral methods (UV, IR), thermal analysis and molecular modeling. A preliminary study concerning the surface structuration capacity of the polyimides was accomplished. Good results were obtained using Nd:YAG laser at 355 nm, at an incident fluence of 35 mJ/cm(2) (situated below the laser ablation limit). (c) 2008 Elsevier Ltd. All rights reserved.