Design, Synthesis, and Properties of Molecule‐Based Assemblies with Large Second‐Order Optical Nonlinearities

Tobin J. Marks*, Mark A. Ratner

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

756 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)155-173
Number of pages19
JournalAngewandte Chemie International Edition in English
Issue number2
StatePublished - Feb 3 1995


  • NLO materials
  • nonlinear optics
  • polymers
  • self‐assembly
  • thin films

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry


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