X-shaped Electro-Optic Chromophore with Remarkably Blue-Shifted Optical Absorption. Synthesis, Characterization, Linear/Nonlinear Optical Properties, Self-Assembly, and Thin Film Microstructural Characteristics

A novel type of 'X-shaped' two-dimensional electro-optic (EO) chromophore with extended conjugation has been synthesized and characterized. This chromophore is found to exhibit a remarkably blue-shifted optical maximum (357 nm in CH2Cl2) while maintaining a very large first hyperpolarizability (β). Hyper-Rayleigh Scattering (HRS) measurements at 800 nm provide a βzzz value of 1840 x 10-30 esu. Self-assembled thin films of this chromophore were fabricated via a layer-by-layer chemisorptive siloxane-based approach. The chromophoric multilayers have been characterized by transmission optical spectroscopy, advancing contact angle measurements, synchrotron X-ray reflectivity, atomic force microscopy, and angle-dependent polarized second harmonic generation spectroscopy. The self-assembled chromophoric films exhibit a dramatically blue-shifted optical maximum (325 nm) while maintaining a large EO response (χ(2)333 ∼ 232 pm/V at 1064 nm; r33 ∼ 45 pm/V at 1310 nm). This work demonstrates an attractive approach to developing EO materials offering improved nonlinearity-transparency trade-offs