Design and Synthesis of Push−Pull Chromophores for Second-Order Nonlinear Optics Derived from Rigidified Thiophene-Based π-Conjugating Spacers
TL;DR: In this paper, two series of push-pull chromophores built around thiophene-based π-conjugating spacers rigidified either by covalent bonds or by noncovalent intramolecular interactions have been synthesized and characterized by UV−vis spectroscopy, electric field induced second harmonic generation (EFISH) and differential scanning calorimetry.
Abstract: Two series of push−pull chromophores built around thiophene-based π-conjugating spacers rigidified either by covalent bonds or by noncovalent intramolecular interactions have been synthesized and characterized by UV−vis spectroscopy, electric field induced second harmonic generation (EFISH) and differential scanning calorimetry. Comparison of the linear and second-order nonlinear optical properties of chromophores based on a covalently bridged dithienylethylene (DTE) spacer with those of their analogues based on open chain DTE shows that the rigidification of the spacer produces a considerable bathochromic shift of the absorption maximum together with a dramatic enhancement of the molecular quadratic hyperpolarizability (μβ) which reaches values among the highest reported so far. A second series of NLO-phores has been derived from a 2,2‘-bi(3,4-ethylenedioxythiophene) (BEDOT) π-conjugating spacer. As indicated by X-ray and UV−vis data, rigidification of the spacer originates in that case, from noncovalent...
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TL;DR: Dithieno[3,2-b:2′3′-d]thiophene-4,4-dioxides 1221 3.3.1.
Abstract: 3.2. Thienothiophenes 1216 3.2.1. Thieno[3,4-b]thiophene Analogues 1216 3.2.2. Thieno[3,2-b]thiophene Analogues 1217 3.2.3. Thieno[2,3-b]thiophene Analogues 1218 3.3. , ′-Bridged Bithiophenes 1219 3.3.1. Dithienothiophene (DTT) Analogues 1220 3.3.2. Dithieno[3,2-b:2′3′-d]thiophene-4,4-dioxides 1221 3.3.3. Dithienosilole (DTS) Analogues 1221 3.3.4. Cyclopentadithiophene (CPDT) Analogues 1221 3.3.5. Nitrogen and Phosphor Atom Bridged Bithiophenes 1222
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TL;DR: In this short review various classes of molecular donors are discussed with the aim of defining possible basic molecular structures that can combine structural simplicity, low molecular weight, synthetic accessibility, scalability and that can represent possible starting points for the development of simple and cost-effective OPV materials.
Abstract: An overview of some recent developments of the chemistry of molecular donor materials for organic photovoltaics (OPV) is presented. Although molecular materials have been used for the fabrication of OPV cells from the very beginning of the field, the design of molecular donors specifically designed for OPV is a relatively recent research area. In the past few years, molecular donors have been used in both vacuum-deposited and solution-processed OPV cells and both fields have witnessed impressive progress with power conversion efficiencies crossing the symbolic limit of 10 %. However, this progress has been achieved at the price of an increasing complexity of the chemistry of active materials and of the technology of device fabrication. This evolution probably inherent to the progress of research is difficult to reconcile with the necessity for OPV to demonstrate a decisive economic advantage over existing silicon technology. In this short review various classes of molecular donors are discussed with the aim of defining possible basic molecular structures that can combine structural simplicity, low molecular weight, synthetic accessibility, scalability and that can represent possible starting points for the development of simple and cost-effective OPV materials.
525 citations
TL;DR: This Review highlights fundamental synthetic strategies for the preparation of such oligomers with n repeat units and the rules that govern their linear and nonlinear optical properties (absorption, frequency doubling and tripling).
Abstract: Conjugated oligomers represent a prominent class of compounds from a viewpoint of their theory, synthesis, and applications in materials science. Push-pull substitution with an electron donor D at one end of the conjugation and an electron acceptor A at the other end results in them having outstanding optical and electronical properties. This Review highlights fundamental synthetic strategies for the preparation of such oligomers with n repeat units (n=1, 2, 3, 4, ..) and the rules that govern their linear and nonlinear optical properties (absorption, frequency doubling and tripling). The unification of chemical, physical, and theoretical aspects with an interdisciplinary image of this class of compounds is attempted herein.
477 citations
TL;DR: The potentialities of EDOT as a building block for the synthesis of functional π-conjugated systems are reviewed in this article, where some recent examples of polymers with specific electrochemical properties and/or a reduced band gap are illustrated.
Abstract: The potentialities offered by EDOT as a building block for the synthesis of functional π-conjugated systems are reviewed. The first part underlines the specific advantages of the EDOT unit for the design of precursors of electrogenerated functional conducting polymers combining high reactivity and low polymerization potential. This topic is illustrated by some recent examples of polymers with specific electrochemical properties and/or a reduced band gap. The second part is focused on the interest of EDOT as a building block for the synthesis of various classes of molecular functional π-conjugated systems. Examples of fluorophores, push–pull chromophores for nonlinear optics and extended π-donors are presented. Emphasis is placed on the optical and crystallographic structure of these compounds, which shows that a major advantage of the EDOT building block lies in an unique combination of strong electron donor properties and self-structuring effects related to intramolecular non-covalent interactions between oxygen and sulfur. Such intramolecular interactions also exert a determining influence on the structure and electronic properties of π-conjugated oligomers incorporating EDOT units which represent some of the more recent uses of the EDOT building block. The structure–property relationships of various classes of EDOT-containing conjugated oligomers are discussed in relation to their potential use as organic semi-conductors. In a brief last section, various synthetic approaches devoted to the chemistry of EDOT itself, or to the modification of its chemical structure, are discussed in relation with possible future research directions.
402 citations
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2,000 citations
TL;DR: Numerical simulations of a simple reaction-diffusion model reveal a surprising variety of irregular spatiotemporal patterns, some of which resemble the steady irregular patterns recently observed in thin gel reactor experiments.
Abstract: Numerical simulations of a simple reaction-diffusion model reveal a surprising variety of irregular spatiotemporal patterns. These patterns arise in response to finite-amplitude perturbations. Some of them resemble the steady irregular patterns recently observed in thin gel reactor experiments. Others consist of spots that grow until they reach a critical size, at which time they divide in two. If in some region the spots become overcrowded, all of the spots in that region decay into the uniform background.
862 citations
TL;DR: In this paper, the microstructural and optical properties of second-order nonlinear optical materials built from noncentrosymmetric assemblies of chromophores having large molecular hyperpolarizabilities are surveyed.
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.
649 citations
TL;DR: These derivative relations provide a unified picture of the dependence of the polarizability and hyperpolarizabilities on the structure in linear polymethine dyes and allow for predictions of structure-property relations of higher order hyperp polarizabilities.
Abstract: An internal or external electric field F can drive the chemical structure, bond order alternation, and electronic structure of linear polymethine dyes from a neutral, bond-alternated, polyene-like structure, through a cyanine-like structure, and ultimately to a zwitterionic (charge-separated) bond-alternated structure. As the structure evolves under the influence of F, the linear polarizability α, the first hyperpolarizability β, and the second hyperpolarizability γ are seen to be derivatives, with respect to F, of their next lower order polarization (for α) or polarizability (for β and γ). These derivative relations provide a unified picture of the dependence of the polarizability and hyperpolarizabilities on the structure in linear polymethine dyes. In addition, they allow for predictions of structure-property relations of higher order hyperpolarizabilities.
585 citations
TL;DR: In this article, the authors deal with recent and important developments in the field of organic materials for second-order nonlinear optics, focusing on current trends in chromophore design with a discussion of current progress and problems.
Abstract: This paper deals with recent and important developments in the field of organic materials for second-order nonlinear optics. Attention is drawn to current trends in chromophore design with a discussion of current progress and problems in this field. A number of important classes of chromophores, such as one-dimensional charge-transfer molecules, octopolar compounds, ionic materials, multichromophore systems and organometallics, are discussed.
545 citations