Chromophore environmental effects in saltlike nonlinear optical materials. A computational study of architecture/anion second-order response relationships in high-β stilhazolium self-assembled films

Santo Di Bella, Ignazio Fragalà, Mark A Ratner, Tobin J Marks

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33 Citations (Scopus)

Abstract

The very large cation-anion environmental effects on second-order nonlinear optical response observed in self-assembled stilbazolium monolayer ion-exchange experiments are investigated theoretically using the ZINDO/SOS quantum chemical formalism. Ion pairs consisting of the 4′-(dimethylamino)-N-methyl-4-stilbazolium cation with chloride, iodide, and p-aminobenzenesulfonate counteranions in differing mutual orientations, are examined as models to relate calculated ion pair hyperpolarizabilities to anion-exchange-induced changes in macroscopic linear optical and nonlinear optical response. Calculated hyper-polarizabilities depend strongly on the relative cation-anion packing configuration. In accord with anion exchange experiments, enhancements of the second-order nonlinear optical response on passing from Cl- to I- and p-aminobenzenesulfonate can be related to likely displacement of the bulkier I- and p-aminobenzenesulfonate anions from more closely packed structural arrangements originally produced as a consequence of the self-assembly process.

Original languageEnglish
Pages (from-to)400-404
Number of pages5
JournalChemistry of Materials
Volume7
Issue number2
Publication statusPublished - 1995

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Optical materials
Chromophores
Anions
Environmental impact
Negative ions
Cations
Ion exchange
Positive ions
Ions
Iodides
Self assembled monolayers
Self assembly
Chlorides
Experiments

ASJC Scopus subject areas

  • Materials Chemistry
  • Materials Science(all)

Cite this

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title = "Chromophore environmental effects in saltlike nonlinear optical materials. A computational study of architecture/anion second-order response relationships in high-β stilhazolium self-assembled films",
abstract = "The very large cation-anion environmental effects on second-order nonlinear optical response observed in self-assembled stilbazolium monolayer ion-exchange experiments are investigated theoretically using the ZINDO/SOS quantum chemical formalism. Ion pairs consisting of the 4′-(dimethylamino)-N-methyl-4-stilbazolium cation with chloride, iodide, and p-aminobenzenesulfonate counteranions in differing mutual orientations, are examined as models to relate calculated ion pair hyperpolarizabilities to anion-exchange-induced changes in macroscopic linear optical and nonlinear optical response. Calculated hyper-polarizabilities depend strongly on the relative cation-anion packing configuration. In accord with anion exchange experiments, enhancements of the second-order nonlinear optical response on passing from Cl- to I- and p-aminobenzenesulfonate can be related to likely displacement of the bulkier I- and p-aminobenzenesulfonate anions from more closely packed structural arrangements originally produced as a consequence of the self-assembly process.",
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AU - Bella, Santo Di

AU - Fragalà, Ignazio

AU - Ratner, Mark A

AU - Marks, Tobin J

PY - 1995

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