Self-assembly from the gas-phase: Design and implementation of small-molecule chromophore precursors with large nonlinear optical responses

David Frattarelli, Michele Schiavo, Antonio Facchetti, Mark A Ratner, Tobin J Marks

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

Efficiently organizing molecular nonlinear optical (NLO) chromophores having large first-order hyperpolarizabilities (β) into acentric microstructures for electro-optic (EO) applications represents a significant materials synthesis and processing challenge, in part due to interchromophore dipolar interactions that promote centrosymmetric organization. Here we report the computational modeling, synthesis, and characterization of a series of eight heteroaromatic organic chromophores, designed to self-organize from the vapor phase via directed hydrogen-bond networks, into acentric thin films. Introduction of α,ω-donor-acceptor hydrogen-bonding substituents along the molecular long axes tunes properties such as hyperpolarizability, volatility, thermal stability, film-forming properties, and macroscopic NLO response (χ(2)). DFT-level molecular modeling, INDO/S optical property analysis, and sum-overstates computation indicate that molecular-core fluorination and hydrogen-bond donor incorporation can increase βvec up to 40x versus that of typical fluorine-free chromophores. Furthermore, inclusion of sterically induced biphenyl conjugative decoupling between chromophore π-donor substituents and the hydrogen-bonding donor sites increases β by ∼50%. Experimental thin-film second harmonic generation (SHG) spectroscopy confirms these trends in calculated responses, with χ(2) increasing 7.5x upon chromophore core fluorination and 15x with hydrogen-bonding donor substitution, thereby achieving macroscopic responses as high as 302 pm/V at ωo = 1064 nm. In addition to response trends, cluster calculations also reveal linear additivity in βvec with catenation for all benzoic acid-containing chromophores up to longitudinally aligned trimers. Linear scaling of SHG response with film thickness is observed for benzoic acid-containing chromophores up to 1.0 μm film thickness.

Original languageEnglish
Pages (from-to)12595-12612
Number of pages18
JournalJournal of the American Chemical Society
Volume131
Issue number35
DOIs
Publication statusPublished - Sep 9 2009

Fingerprint

Hydrogen Bonding
Chromophores
Self assembly
Benzoic Acid
Gases
Halogenation
Molecules
Hydrogen bonds
Hydrogen
Molecular Computers
Volatilization
Fluorine
Fluorination
Benzoic acid
Harmonic generation
Spectrum Analysis
Hot Temperature
Film thickness
Thin films
Molecular modeling

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Self-assembly from the gas-phase : Design and implementation of small-molecule chromophore precursors with large nonlinear optical responses. / Frattarelli, David; Schiavo, Michele; Facchetti, Antonio; Ratner, Mark A; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 131, No. 35, 09.09.2009, p. 12595-12612.

Research output: Contribution to journalArticle

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