Unconventional Langmuir-Blodgett films:: alignment of an optically nonlinear dye where the donor and π-electron bridge are hydrophobic and the acceptor is hydrophilic

The optically nonlinear dye, 5-{4-[2-(4-dibutylaminophenyl)vinyl]benzylidene-2-(1-ethylpropyl)-5,6,7,8-tetrahydroisoquinolinium bromide (1a), differs from other Langmuir-Blodgett (LB) film-forming materials. The molecule is amphiphilic and, therefore, may be aligned at the air-water interface but, instead of a conventional aliphatic tail, has an extended pi-electron bridge. It forms non-centrosymmetric LB films which exhibit second-harmonic generation (SHG) and have a high second-order susceptibility: chi(zzz)((2)) == 40 pm V-1 at 1.064 mum for a monolayer thickness of 1.8 nm and chromophore tilt angle of 55degrees from the substrate normal. The octadecyl sulfate salt (1b) also forms non-centrosymmetric films but with improved properties: chi(zzz)((2)) = 90 pm V-1 at 1.064 mum for d = 2.4 nm and phi = 33degrees. Both films exhibit charge-transfer bands at 360 nm but with absorbance cut-off above 560 nm for 1a and 530 nm for 1b. The latter is fully transparent at the fundamental and harmonic wavelengths and its susceptibility is the highest to date for such a film. This results from an optimised packing arrangement, a conjugation enhanced molecular hyperpolarisability of beta 4.3 x 10(-38) m(4) V-1, and the proximity of the absorption band, albeit non-overlapping at 532 rim. The properties are compared with those of conventional long alkyl tailed materials (2 and 3) of the same chromophore.