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Design, Synthesis, and Properties of Molecule-Based Assemblies with Large Second-Order Optical Nonlinearities
Prof. Tobin J. Marks,
Prof. Mark A. Ratner,
Corresponding Author
Prof. Tobin J. Marks
Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, IL 60208-3113 (USA). Telefax: Int. code + (708)491-2990
Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, IL 60208-3113 (USA). Telefax: Int. code + (708)491-2990Search for more papers by this authorCorresponding Author
Prof. Mark A. Ratner
Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, IL 60208-3113 (USA). Telefax: Int. code + (708)491-2990
Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, IL 60208-3113 (USA). Telefax: Int. code + (708)491-2990Search for more papers by this authorProf. Tobin J. Marks,
Prof. Mark A. Ratner,
Corresponding Author
Prof. Tobin J. Marks
Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, IL 60208-3113 (USA). Telefax: Int. code + (708)491-2990
Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, IL 60208-3113 (USA). Telefax: Int. code + (708)491-2990Search for more papers by this authorCorresponding Author
Prof. Mark A. Ratner
Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, IL 60208-3113 (USA). Telefax: Int. code + (708)491-2990
Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, IL 60208-3113 (USA). Telefax: Int. code + (708)491-2990Search for more papers by this authorGraphical Abstract
The rational construction of supramolecular assemblies with preordained collective properties is an important theme in many areas of contemporary chemistry. The advances made in this respect with regard to polymeric NLO materials, and what problems must still be addressed before technologically viable NLO building blocks become readily available, are surveyed by the authors of this review. Superlattices of the type shown schematically on the right should be among the most promising materials.
Abstract
The design, synthesis, characterization, and understanding of new molecular and macromolecular assemblies with large macroscopic optical nonlinearities represents an active field of research at the interface of modern chemistry, physics, and materials science. Challenges in this area of photonic materials typify an important theme in contemporary chemistry: to create new types of functional materials by the rational construction of supramolecular assemblies exhibiting preordained collective phenomena by virtue of “engineered” molecule–molecule interactions and spatial relationships. This review surveys several approaches to, and the microstructural and optical properties of, second-order nonlinear optical materials built from noncentrosymmetric assemblies of chromophores having large molecular hyperpolarizabilities. Such types of materials can efficiently double the frequency of incident light, exhibit other second-order nonlinear optical effects, and contribute to the knowledge base needed for new photonic device technologies. Systems described include chromophore macromolecule guesthost matrices, chromophore-functionalized glassy macromolecules, thermally crosslinked chromophore-macromolecule matrices, and intrinsically acentric self-assembled chromophoric superlattices.
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