Annabelle Scarpaci

OFS (United States)

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Errol Blart

Chimie et Interdisciplinarité, Synthèse, Analyse, Modélisation

Fabrice Odobel

Chimie et Interdisciplinarité, Synthèse, Analyse, Modélisation

Vincent Rodriguez

Université de Bordeaux

Laurent Fontaine

Institut des Molécules et Matériaux du Mans

Koen Clays

KU Leuven

Seth R. Marder

University of Colorado Boulder

Stephen Barlow

University of Colorado Boulder

Inge Asselberghs

KU Leuven

Stéphanie Legoupy

Centre National de la Recherche Scientifique

Clément Cabanetos

Institut des Sciences et Technologies Moléculaires d'Angers

Cooperative Institutions

Georgia Institute of Technology

Centre National de la Recherche Scientifique

Nantes Université

Chimie et Interdisciplinarité, Synthèse, Analyse, Modélisation

Université Nantes Angers Le Mans

Le Mans Université

AID Atlanta

Chinese Academy of Sciences

Laboratoire de Synthèse Organique

Laboratoire de Chimie Moléculaire

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Charge‐Transfer State and Large First Hyperpolarizability Constant in a Highly Electronically Coupled Zinc and Gold Porphyrin Dyad

Chemistry - A European Journal (2009)

Jérôme Fortage Annabelle Scarpaci Lydie Viau Yann Pellegrin Errol Blart

Abstract We report the synthesis and the characterizations of a novel dyad composed of a zinc porphyrin (ZnP) linked to a gold porphyrin (AuP) through an ethynyl spacer. The UV/Vis absorption spectrum and the electrochemical properties clearly reveal that this dyad exhibits a strong electronic coupling in the ground state as evidenced by shifted redox potentials and the appearance of an intense charge‐transfer band localized at λ =739 nm in dichloromethane. A spectroelectrochemical study of the dyad along with the parent homometallic system (i.e., ZnP–ZnP and AuP–AuP) was undertaken to determine the spectra of the reduced and oxidized porphyrin units. Femtosecond transient absorption spectroscopic analysis showed that the photoexcitation of the heterometallic dyad leads to an ultrafast formation of a charge‐separated state ( + ZnP–AuP . ) that displays a particularly long lifetime ( τ =4 ns in toluene) for such a short separation distance. The molecular orbitals of the dyad were determined by DFT quantum‐chemical calculations. This theoretical study confirms that the observed intense band at λ =739 nm corresponds to an interporphyrin charge‐transfer transition from the HOMO orbital localized on the zinc porphyrin to LUMO orbitals localized on the gold porphyrin. Finally, a Hyper–Rayleigh scattering study shows that the dyad possesses a large first molecular hyperpolarizability coefficient ( β =2100×10 −30 esu at λ =1064 nm), thus highlighting the valuable nonlinear optical properties of this new type of push–pull porphyrin system.

Hyperpolarizability

Superexchange

HOMO/LUMO

10.1002/chem.200900262

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Citations (34)

Synthesis and nonlinear optical properties of a peripherally functionalized hyperbranched polymer by DR1 chromophores Scarpaci-A, Blart-E, Montembault-V, Fontaine-L, Rodriguez-V, Odobel-F

HAL (Le Centre pour la Communication Scientifique Directe) (2009)

Annabelle Scarpaci Errol Blart V. Montembault Laurent Fontaine Vincent Rodriguez

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Postfunctionalization of poly(propargyl methacrylate) using copper catalyzed 1,3‐dipolar Huisgen cycloaddition: An easy route to electro‐optic materials

Journal of Polymer Science Part A Polymer Chemistry (2009)

Annabelle Scarpaci Clément Cabanetos Errol Blart Véronique Montembault Laurent Fontaine

Abstract A one‐pot synthetic route based on copper‐catalyzed Huisgen reaction has been developed to functionalize a methacrylate propargylic polymer with azido‐substituted moieties. This procedure was used for the preparation of electro‐optic materials containing well‐known Disperse Red One (DR1) chromophores along with bulky adamantyl moieties (Adam). The postfunctionalization of the propargylic polymer was successfully achieved using different molar ratios of DR1/Adam. These novel polymers exhibit high glass transition temperature owing to the rigid structure of adamantyl units. Moreover, the second harmonic generation measurements demonstrated the effectiveness of adamantyl groups to act as insulating shield limiting thus the electrostatic interactions between chromophores. Indeed, higher optimal chromophore concentration (50 mol %) than in conventional DR1‐containing polymers (30 mol %) allowed us to increase the d 33 coefficient up to 92 pm/V. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5652–5660, 2009

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Propargyl

10.1002/pola.23606

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Scope and limitation of the copper free thermal Huisgen cross-linking reaction to stabilize the chromophores orientation in electro-optic polymers

Polymer Chemistry (2010)

Annabelle Scarpaci Clément Cabanetos Errol Blart Yann Pellegrin Véronique Montembault

New methacrylate copolymers incorporating two complementary thermally cross-linkable groups (azide or ethynyl) for implementation in electro-optic devices were synthesized and their nonlinear optical properties were investigated. These copolymers were prepared from a monomer containing Disperse Red 1 (DR1) as active NLO chromophore which is end substituted either by an azide or ethynyl group connected via a rigid (phenyl) or flexible spacer (alkyl chain). The second monomer is either a trimethylsilyl-propargyl methacrylate, or an azidopropyl methacrylate or a trimethylsilyl-phenyl methacrylate. The determination of the reactivity ratios showed that the monomer containing the DR1 chromophore is more reactive than trimethylsilyl-propargyl methacrylate. The cross-linking temperatures of these polymers range from 150 °C to 187 °C depending on the rigidity of the spacers connecting the cross-linkable units. These polymers displayed relatively high macroscopic electro-optic stability, enhanced upon cross-linking by more than 40 °C relative to non-cross-linked polymers. The results underscore the importance of the flexibility of the spacers to achieve the stable bulk electro-optic response. While rigidity is favorable to maintain the orientation of the chromophores, the optimal polymer is the one containing a flexible and a rigid spacer, since the mobility of the reactive groups is a key parameter which guarantees a high cross-linking conversion within the polymer. This study demonstrates the versatility of this new cross-linking process because we showed that the reactive groups (azide or trimethylsilylacetylated groups) can be interconverted (on the chromophore or as polymer side chain) with no change on the overall electro-optic activity and its thermal stability. Furthermore, preliminary kinetic study indicates that the Huisgen reaction rate can be controlled by the substituent on the ethynyl group opening the possibility to tune the cross-linking temperature by the careful choice of this substituent.

Chromophore

Propargyl

Thermal Stability

Side chain

10.1039/c0py00203h

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Citations (19)

Synthesis and Nonlinear Optical Properties of a Peripherally Functionalized Hyperbranched Polymer by DR1 Chromophores

ACS Applied Materials & Interfaces (2009)

Annabelle Scarpaci Errol Blart Véronique Montembault Laurent Fontaine Vincent Rodriguez

The first peripheral postfunctionalization of a hyperbranched polyimide by nonlinear optic chromophores (DR1 derivative) was achieved using two different routes. The first one consists in the esterification of the terminal carboxylic acid groups, whereas the second is based on copper-catalyzed Huisgen reaction of the terminal propargylic ester groups. The resulting polymers display good solubility in classical organic solvents and good filmability because thick films can be prepared (up to 2.7 mum). The second-order nonlinear optical properties were measured by SHG at 1064 nm and we show that these hyperbranched polymers exhibit good poling efficiency and good thermal stability since the electro-optic activity remains stable up to 130 degrees C. These results illustrate the potential of hyperbranched polymers to host second-order nonlinear optical chromophores to replace dendrimers or classical linear polymers generally used in this area.

Chromophore

Poling

Thermal Stability

10.1021/am900319h

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Citations (42)

Élaboration de nouveaux polymères réticulables ou hyperbranchés pour l'optique non linéaire du second ordre

Annabelle Scarpaci

Les travaux decrits dans ce manuscrit concernent la conception et la synthese de nouveaux polymeres pour des applications en optique non lineaire du second ordre. Dans un premier volet, une nouvelle methode de reticulation fondee sur la reaction thermique de Huisgen est developpee. Des polymeres de type methacrylique comportant un chromophore analogue au DR1 substitue par une triple liaison ou un azide et un motif fonctionnalise par un groupement complementaire (azide ou triple liaison, respectivement) ont ete synthetises. Des films d’epaisseurs allant jusqu’a 2,7 µm ont pu etre caracterises par un coefficient electrooptique r33 de l’ordre de 16 pm/V a 1,064 µm stable jusqu’a 137°C. Le deuxieme volet porte sur la synthese de polymeres a haute temperature de transition vitreuse basee sur la post-fonctionnalisation du methacrylate de propargyle par des chromophores DR1 et des groupements rigidifiants de type adamantyle dotes de fonctions azide via la reaction catalytique de Huisgen sous activation micro-ondes. Selon la concentration en chromophores, des coefficients electrooptiques allant jusqu’a 31 pm/V ont pu etre mesures a 1,064 µm. Cependant, la stabilite d’orientation des chromophores n’est pas conservee au-dela de 90°C. Le troisieme volet consiste a appliquer la reaction de Huisgen catalytique classique d’abord a la synthese d’un polymere hyperbranche de type main-chain employant le chromophore DR1. Puis, la synthese de polyimides hyperbranches post-fonctionnalises en peripherie par des chromophores DR1 ou porphyriniques a ete realisee. Leurs coefficients electrooptiques r33 mesures a 1,064 µm s’elevant jusqu’a 18 pm/V se sont reveles stables jusqu’a 130°C

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High-Speed Polymer Optical Modulators

Elsevier eBooks (2013)

Raluca Dinu Eric Miller Guomin Yu Baoquan Chen Annabelle Scarpaci

10.1016/b978-0-12-396958-3.00005-6

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Citations (6)

Efficient green and blue electrophosphorescent light-emitting diodes using a combination of solution- and vacuum-processed materials

Wojciech Haske Sungjin Kim Denke Cai Ehsan Najafabadi Canek Fuentes‐Hernandez

The performance of organic light-emitting diode devices with a spin-coated hole-transporting layer and a thermally deposited emissive layer consisting of a bis-sulfone small molecule, as a host for the blue phosphorescent emitter will be presented.

10.1364/soled.2011.sdwc5

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From a molecule to an electro-optic antenna

HAL (Le Centre pour la Communication Scientifique Directe) (2011)

Annabelle Scarpaci Sylvain Le Tacon Arnaud Gardelein Fabrice Odobel Errol Blart

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Preparation and characterization of second order non-linear optical properties of new “push–pull” platinum complexes

Dalton Transactions (2009)

Annabelle Scarpaci Cyrille Monnereau Noémie Hergué Errol Blart Stéphanie Legoupy

In this contribution, we report the synthesis and characterization of the second order non-linear properties of a series of unconventional terpyridyl and dipyridylphenyl platinum complexes. These new platinum complexes consist of a tridentate ligand substituted by a high electron acceptor, and a chloro or an arylacetylide ligand. The hyper-Rayleigh scattering measurements reveal that these complexes display large quadratic hyperpolarizabilities reaching a dynamic value of 1460 x 10(-30) at 1064 nm esu for the best complex. This investigation also demonstrates that cyclometalated dipyridylphenyl platinum complexes greatly exhibit enhanced first hyperpolarizability with respect to analogous terpyridyl complexes.

Hyperpolarizability

Characterization

10.1039/b900282k

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Citations (37)