2,4-Bis[4-(N,N-dibutylamino)phenyl] squaraine: X-ray crystal structure of a centrosymmetric dye and the second-order non-linear optical properties of its non-centrosymmetric Langmuir–Blodgett films
Crystals of the title compound exist as a green monoclinic phase [space group P21/c with a= 9.046(1), b= 19.615(2), c= 9.055(1)Å, β= 116.107(5)°, Z= 2] and a purple triclinic phase. The chromophore is both planar and centrosymmetric and its dimensions indicate a tendency towards a quinoidal structure with extensive delocalisation. The Langmuir–Blodgett (LB) films show two types of aggregation with absorption maxima at 655 nm and 540 nm. These monolayers also exhibit strong second harmonic generation (SHG) comparable to the intensity from films of hemicyanine dyes. The anomalous non-linear optical properties are attributed to a serendipitous non-centrosymmetric packing arrangement within the films and to an intermolecular charge transfer contribution to the bulk second-order susceptibility.