The quest for more efficient nonlinear optical materials of increased optical quality is being spurred by the development of optical communication systems that require ultrafast broad band optical signal processing functions. Conversely, nonlinear optical phenomena enlarge traditional spectroscopic approaches to encompass more complex and informative multiphotonic pathways. In this stimulating context, organic nonlinear materials have been recognized as forefront candidates for fundamental and applied investigations involving, in a joint effort, chemists, material scientists and optical physicists. After reviewing the molecular engineering foundations of the domain, specifically with respect to an efficiency-transparency trade-off, the author concentrates on a more specific case that embodies, from the definition of the molecule all the way down to applied physics endgoals, the key concepts and methodological tools in the field. A crucial part of such study is the definition and implementation of crystal growth methods leading to the high optical quality demanded by parametric phenomena. This approach is best exemplified in the paradigmatic case of N-4-nitrophenyl-(L)-prolinol (NPP) which, after almost a decade of effort involving crystal growth and ultrafast time resolved spectroscopy, has recently reached sufficient quality to lead to optical parametric oscillation. Stable coherent tunable oscillation in the near IR from 0.9 to 1.7 mu m has thus been demonstrated for the first time in an organic molecular crystal, with specific advantages over mineral candidates, and room for further performance improvement. The author recalls in conclusion that new molecular and crystalline pathways are still opening up, such as those based on molecular nonlinearities of octupolar origin or organomineral crystals.
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