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1. An attractive family of cyclometalated Ir(III) dyes functionalized with tryptophan for potential neuroimaging applications

Author

Giulia De Soricellis, Francesco Fagnani, Alessia Colombo, Claudia Dragonetti, Dominique Roberto, Daniele Marinotto, David H. Hartnell, Mark J. Hackett, Massimiliano Massi, Bertrand Carboni, Véronique Guerchais, National Interuniversity Consortium of Materials Science and Technology (INSTM ), Istituto di Scienze e Tecnologie Chimiche 'Giulio Natta' (SCITEC), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Curtin University [Perth], Planning and Transport Research Centre (PATREC), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Interuniversity Consortium of Materials Science and Technology [INSTM21MIROBERTO], Universita degli Studi di Milano [PSR2020_DIP_005_PI_ACOLO], Australian Research Council [DP220103091], Fondazione Cariplo and Regione Lombardia, and CNR

Subjects
Settore CHIM/03 - Chimica Generale e Inorganica, complexes, Optical markers, Cyclometalated iridium(III) phenanthroline, Phosphorescence, Process Chemistry and Technology, General Chemical Engineering, [SDV]Life Sciences [q-bio], Bio-imaging, [CHIM]Chemical Sciences, Iridium dyes, Brain tissue staining
Abstract

International audience; Three novel luminescent iridium(III) dyes functionalized with a tryptophan amino acid and bearing two cyclometalated 2-phenylpyridines, 2-(2,4-difluorophenyl)pyridines or 2-phenylquinolines have been prepared and well characterized. They emit at 522-561 nm with a luminescence quantum yield in the range 0.33-0.98. All the dyes are able to stain neuronal cells in rat cerebellum tissue, as evidenced by fluorescence microscopy, showing affinity for granule neurons. The complexes bearing cyclometalated 2-(2,4-difluorophenyl)pyridines or 2-phenylquinolines also have a good affinity for brain white matter. The dye with two cyclometalated 2-phenylquinolines is characterized by the best luminescence quantum yield (0.98). Besides, giving the greatest image contrast, the dye with two cyclometalated 2-phenylquinolines shows the strongest affinity for a distinct subtype of neurons found in cerebellum tissue, the purkinje neurons (as evidenced with fluorescence microscopy).

Published
2023

2. An excursion in the second-order nonlinear optical properties of platinum complexes

Author

Véronique Guerchais, Claudia Dragonetti, Alessia Colombo, Dominique Roberto, National Interuniversity Consortium of Materials Science and Technology (INSTM ), Università degli Studi di Milano = University of Milan (UNIMI), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), MUR and INSTM (Project INSTM21MIDRAGONETT) for support., Università degli Studi di Milano [Milano] (UNIMI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Platinum(II) complexes, Phenanthroline, Hyperpolarizability, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, Bipyridine, chemistry.chemical_compound, Photochromism, Materials Chemistry, Optical switches, Moiety, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Quadratic hyperpolarizability, 010405 organic chemistry, Nonlinear optics, Acceptor, 0104 chemical sciences, EFISH, Crystallography, chemistry, Platinum
Abstract

International audience; Electrooptical devices and optical communications need compounds with second-order nonlinear optical (NLO) properties as construction blocks. Typically, to show a large quadratic hyperpolarizability, a compound should be asymmetric, be characterized by a large variation between the dipole moments in the excited and ground states, and have low energy electronic transitions. For example, a large quadratic hyperpolarizability can be reached when an electron-donor moiety is linked by means of a p-conjugated spacer to an acceptor group. In the field of second-order nonlinear optics, particularly attractive are coordination metal complexes because they are often characterized by low-energy and high-intensity intralig and (IL), ligand-to-metal (LM), and metal-to-ligand (ML) charge transfer (CT) electronic transitions, that can be regulated by the choice of the metal and ligands. Among them, platinum(II) complexes are captivating. During this excursion, we will see the quadratic hyperpolarizability of many of them. After some basic NLO notions, the review presents various classes of NLO-active platinum compound shaving mono- and bidentate nitrogen ligands (pyridine, bipyridine, phenanthroline), dithiolenes, cyclometalated ligands (imines, phenylpyridine, phenylbipyridine, and dipyridylbenzene), alkynyl ligands. It is shown how to regulate the quadratic hyperpolarizability with suitable ligands and how to photomodulate the NLO properties by means of a dithienylethene (DTE) moiety. Some examples of complexes with redoxswitchable NLO properties are also given. Although the accent is on the quadratic hyperpolarizability measured in solution, it is also shown how some NLO-activeplatinumcomplexes canbenano-organized to afford thinfilmswithnonlinear optical properties. Thereport is notcomprehensive, butit allows to get into the field of NLO-active platinum compounds and to understand their potential.

Published
2021

3. A trip in the nonlinear optical properties of iridium complexes

Author

Véronique Guerchais, Dominique Roberto, Claudia Dragonetti, Eli Zysman-Colman, Alessia Colombo, Claus Hierlinger, Università degli Studi di Milano [Milano] (UNIMI), National Interuniversity Consortium of Materials Science and Technology (INSTM ), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), University of St Andrews [Scotland], MIUR Ministry of Education, Universities and Research (MIUR), National Interuniversity Consortium of Materials Science and Technology [INSTMMI012], Università degli Studi di Milano = University of Milan (UNIMI), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Iridium complexes, Denticity, Nonlinear optics, 010405 organic chemistry, Chemistry, chemistry.chemical_element, Second harmonic generation, 010402 general chemistry, 01 natural sciences, Two-photon absorption, 0104 chemical sciences, Inorganic Chemistry, Oxidation state, Excited state, Materials Chemistry, Physical chemistry, Molecule, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Iridium, Physical and Theoretical Chemistry, Ground state
Abstract

International audience; Molecules with second-order nonlinear optical (NLO) properties have received a lot of attention in the last twenty years due to their potential use in photonic devices. In order to have a large second-order NLO response, a compound should not be centrosymmetric, it should have low energy charge-transfer transitions and there should be a large difference between the excited state and ground state dipole moments. Organic compounds with an electron-donor group and an electron-acceptor group connected via a p-conjugated polarizable spacer can reach a good NLO response. Metal complexes have also shown promise due to their accessible low-energy and high-intensity ligand-to-metal, metal-to-ligand, ligand-to-ligand, and intraligand charge transfer (LMCT, MLCT, LLCT, and ILCT) excited states. The energy of these charge transfer states can be readily tuned as a function of the nature and the oxidation state of the metal centre and by the ligands that surround it. Among them, iridium complexes are particularly fascinating, not only for their attractive second-order NLO properties but also for their remarkable two-photon absorption (TPA) properties, a third-order NLO process which is of interest for a number of photonic and optoelectronic applications. The goal of this review is to show the potential of iridium compounds as molecular materials with NLO-activity. First, the principles of second-order nonlinear optics will be briefly introduced, then the review will illustrate the main families of second-order NLO iridium complexes, producing examples of iridium (I) complexes with monodentate nitrogen donor ligands (substituted pyridines and stilbazoles, azaphenanthrene and azachrysene), iridium(III) complexes with terpyridines, bis-cyclometalated phenylpyridine iridium(III) compounds with beta-diketonate ligands, tris-cyclometalated phenylpyridine iridium(III) compounds, bis-cyclometalated phenylpyridine iridium(III) complexes with diimines or aryl isocyanides. Through this survey of NLO-phores we show how it is possible to tune the second-order NLO response by a suitable choice of the substituents about the ligands. The emphasis is on second-order NLO properties determined in solution at the molecular level, but examples of nanoorganization of some NLO-active iridium complexes in polymeric matrices to give second-order NLO-active thin films are presented as well. Further, some iridium complexes have shown potential as versatile NLO redox-switching materials and these are described in this review. Finally, a few examples of iridium complexes with TPA properties are given in the last section of the review. The coverage is not comprehensive but provides a suitable introduction to NLO-active iridium complexes and a framework for understanding their potential.

Published
2020

4. Photochromic DTE-Substituted-1,3-di(2-pyridyl)benzene Platinum(II) Complexes: Photo-modulation of Luminescence and Second-order Nonlinear Optical Properties

Author

Eleonora Garoni, Alessia Colombo, Julien Boixel, Daniele Marinotto, Véronique Guerchais, Dominique Roberto, Stefania Righetto, Hong Zhao, Denis Jacquemin, Claudia Dragonetti, Thierry Roisnel, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Dipartimento di Chimica, Università degli Studi di Milano [Milano] (UNIMI), ISTM CNR, Milano, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique, INSTMMI012, National Interuniversity Consortium of Materials Science and Technology, Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Università degli studi di Milano [Milano], ISTM CNR, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation ( CEISAM ), Université de Nantes ( UN ) -Centre National de la Recherche Scientifique ( CNRS ), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Università degli Studi di Milano = University of Milan (UNIMI), and Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Photoluminescence, Photoisomerization, 010405 organic chemistry, chemistry.chemical_element, 010402 general chemistry, Ring (chemistry), Photochemistry, Photochromism, 01 natural sciences, [ CHIM ] Chemical Sciences, Fluorescence, 3. Good health, 0104 chemical sciences, Inorganic Chemistry, closed-ring isomer, chemistry, Moiety, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Platinum, Luminescence, Isomerization
Abstract

International audience; We disclose a new family of photochromic cyclometalated platinum(II) complexes (PtDTE1 and PtDTE2), where a dithienylethene (DTE) unit is connected at the para-position of the central phenyl ring of (N^C^N) cyclometalated ligand, through two different linkages. Their syntheses are presented along with the X-ray characterizations of both the open and closed isomers of PtDTE1. The investigation of their photophysical properties is made, including absorption, photochromism, emission, and second-order nonlinear properties. We report a quantitative photo-isomerization for both PtDTE1 and PtDTE2, irrespective of the nature of the connecting mode between the DTE unit and the platinum(II) moiety. The efficient photochromism allows a significant NLO photo-modulation, both in solution and in thin films. In addition, we show that the photoluminescence of the PtDTE1 and PtDTE2 can be controlled by the open/closed isomerization of the DTE unit.

Published
2018

5. Contrasted photochromic and luminescent properties in dinuclear Pt(II) complexes linked through a central dithienylethene unit

Author

Hubert Le Bozec, Yifan Zhu, Keith Man-Chung Wong, Mohamed Ali Benmensour, Abdou Boucekkine, Julien Boixel, Véronique Guerchais, Alessia Colombo, Dominique Roberto, Denis Jacquemin, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), ERC, European Research Council, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry, South University of Science & Technology of China, Dipartimento di Chimica, Università degli Studi di Milano = University of Milan (UNIMI), and Laboratoire CEISAM

Subjects
010405 organic chemistry, Metals and Alloys, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Photochromism, chemistry, Polymer chemistry, Materials Chemistry, Ceramics and Composites, Organic chemistry, [CHIM]Chemical Sciences, Luminescence, Carbon
Abstract

International audience; We disclose two unprecedented complexes built with a central dithienylethene photochrome connecting two cyclometalated Pt(ii) moieties either on the reactive carbon atoms or on the lateral non-reactive carbon atoms of the photochrome. The two systems show vastly different properties that are rationalised thanks to quantum-chemical calculations. © The 2016 The Royal Society of Chemistry.

Published
2016

6. Functionalized styryl iridium(III) complexes as active second-order NLO chromophores and building blocks for SHG polymeric films

Author

Hubert Le Bozec, Adriana Valore, Claudia Dragonetti, Alessia Colombo, Camille Latouche, Daniele Marinotto, Véronique Guerchais, Muriel Escadeillas, Stefania Righetto, Abdou Boucekkine, Dominique Roberto, Dipartimento di Chimica, Università degli Studi di Milano = University of Milan (UNIMI), Istituto di Scienze e Tecnologie Molecolari del CNR, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This work was supported by Fondazione Cariplo (Grant No 2010-0525), by MIUR (FIRB 2003: RBNE033KMA and FIRB 2004: RBPR05JH2P), and by COST D035-0010-05. The authors are grateful to GENCI-IDRIS and GENCI-CINES for an allocation of computing time (Grant No. 2012-080649)., Università degli Studi di Milano [Milano] (UNIMI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Composite number, chemistry.chemical_element, Second-harmonic generation, Chromophore, 010402 general chemistry, Photochemistry, Cyclometallated iridium(III) complexes, 01 natural sciences, Biochemistry, 0104 chemical sciences, EFISH, Second Harmonic Generation, Inorganic Chemistry, Dipole, chemistry, Materials Chemistry, Physical chemistry, Order (group theory), Density functional theory, Iridium, Physical and Theoretical Chemistry, Second-order nonlinear optics
Abstract

International audience; We studied the second-order NLO properties in solution of various Ir(III) acetylacetonate complexes bearing a substituted cyclometallated 4-styryl-2-phenylpyridine (ppy-4-styryl-R, with R = NEt2, OMe, H, NO2) with the EFISH technique. The dipole moments were evaluated by Density Functional Theory (DFT) calculations. We have also investigated the Second Harmonic Generation (SHG) of composite films based on the various cyclometallated Ir(III) complexes dispersed and oriented in a polymethylmethacrylate (PMMA) matrix.

Published
2013

7. Cyclometalated 4-Styryl-2-phenylpyridine Platinum(II) Acetylacetonate Complexes as Second-Order NLO Building Blocks for SHG Active Polymeric Films

Author

Véronique Guerchais, Hubert Le Bozec, Muriel Escadeillas, Stefania Righetto, Camille Latouche, Silvia Tavazzi, Abdou Boucekkine, Alessia Colombo, Daniele Marinotto, Dominique Roberto, Claudia Dragonetti, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Colombo, A, Dragonetti, C, Marinotto, D, Righetto, S, Roberto, D, Tavazzi, S, Escadeillas, M, Guerchais, V, Le Bozec, H, Boucekkine, A, and Latouche, C

Subjects
010405 organic chemistry, Ligand, Organic Chemistry, Poling, Second-harmonic generation, chemistry.chemical_element, Chromophore, Thin Film, NLO, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Second Harmonic Generation, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Dipole, chemistry, 4 - Styryl-2-phenylpyridine Platinum(II) Acetylacetonate Complexes, Physical chemistry, Density functional theory, 2-Phenylpyridine, Physical and Theoretical Chemistry, Platinum
Abstract

The second-order nonlinear optical (NLO) properties of various Pt(II) acetylcetonate complexes bearing a substituted cyclometalated 4-styryl-2-phenylpyridine (ppy-4-styryl-R, with R = NEt2, OMe, H, NO2) were investigated in DMF solution on working with an incident wavelength of 1907 nm by the EFISH technique, whereas the dipole moments were determined by density functional theory (DFT) calculations. In addition, a Pt(II) complex with the ppy-4-styryl-NEt2 ligand, which was the most NLO efficient chromophore due to a particularly high dipole moment, was dispersed in a polymethylmethacrylate matrix and then oriented by poling to give a composite film characterized by a good and quite stable second harmonic generation (SHG) signal. © 2013 American Chemical Society.

Published
2013

8. Linear and nonlinear optical properties of tris-cyclometalated phenylpyridine Ir(III) complexes incorporating π-conjugated substituents

Author

Véronique Guerchais, Hubert Le Bozec, Anu Singh, Moussa Zaarour, J. A. Gareth Williams, Isabelle Ledoux-Rak, Alessia Colombo, Camille Latouche, Adriana Valore, Claudia Dragonetti, Joseph Zyss, Dominique Roberto, Abdou Boucekkine, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), École normale supérieure - Cachan (ENS Cachan)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Tris, 02 engineering and technology, Electronic structure, Conjugated system, Chromophore, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Crystallography, Dipole, Nonlinear optical, chemistry, Pyridine, Physical and Theoretical Chemistry, 0210 nano-technology, Luminescence
Abstract

International audience; The synthesis, luminescence, and nonlinear optical properties of a new series of Ir(ppy)3 (ppy = 2-phenylpyridine) complexes incorporating π-extended vinyl-aryl substituents at the para positions of their pyridine rings are reported. Appropriate substitution of the pyridyl rings allows the tuning of the luminescence properties and the second-order nonlinear optical response of this unusual family of three-dimensional chromophores. Theoretical calculations were performed to evaluate the dipole moments, to gain insight into the electronic structure, and to rationalize the observed optical properties of the investigated complexes.

Published
2013

9. An investigation on the second order nonlinear optical response of tris-cyclometallated Ir(III) complexes with variously substituted 2-phenylpyridines

Author

Moussa Zaarour (a), Véronique Guerchais (a), Hubert Le Bozec (a), Claudia Dragonetti (b), Stefania Righetto (b), Dominique Roberto (b, Filippo De Angelis (d), Simona Fantacci (d), Maria Grazia Lobello (d), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), This work was supported by MIUR (FIRB 2004: RBPR05JH2P and PRIN 2008: 2008FZK5AC_002) and Fondazione Cariplo (Grant No. 2010-0525)., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Tris, Pyridines, Molecular Conformation, Coordination Complexes, Electrons, Iridium, Ligands, Quantum Theory, Inorganic Chemistry, Electronic structure, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Nonlinear optical, Computational chemistry, Order (group theory), Settore CHIM/03 - Chimica Generale e Inorganica, 010405 organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Chromophore, 0104 chemical sciences, Dipole, Crystallography, chemistry, Density functional theory
Abstract

International audience; The second order nonlinear optical (NLO) properties of various simple tris-cyclometallated Ir(III) complexes bearing 2-phenylpyridine ligands have been investigated by means of the EFISH technique, evidencing how appropriate substitution of the cyclometallated ligands may allow the tuning of the second-order NLO response of this unusual family of 3D chromophores. To evaluate the dipole moments and to gain insight into the electronic structure and optical properties of the investigated complexes we also performed Density Functional Theory (DFT) calculations.

Published
2013

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