José María Montenegro Martos - core.ac.uk .Nucleophile addition to radical cations σ-bonds 41

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Transcript of José María Montenegro Martos - core.ac.uk .Nucleophile addition to radical cations σ-bonds 41

  • Universidad de Mlaga

    Facultad de Ciencias

    Departamento de Bioqumica, Biologa Molecular, Inmunologa y

    Qumica Orgnica

    TRANSFERENCIA ELECTRNICA FOTOINDUCIDA BASADA EN ACEPTORES TIPO N-XIDOS DE ISOQUINOLINAS:

    PROCESOS OXIDATIVOS RADICALARIOS Y OPERADORES LGICOS MOLECULARES

    PHOTOINDUCED ELECTRON TRANSFER BASED ON ISOQUINOLINE N-OXIDES

    AS ELECTRON ACCEPTORS:

    RADICAL OXIDATIVE PROCESSES AND MOLECULAR LOGIC SWITCHES

    Memoria que para optar al grado de

    Doctor en Qumica (Doctorado Europeo) por la Universidad de Mlaga

    Presenta:

    Jos Mara Montenegro Martos

    Mlaga, diciembre de 2009

  • AUTOR: Jos Mara Montenegro MartosEDITA: Servicio de Publicaciones de la Universidad de Mlaga

    Esta obra est sujeta a una licencia Creative Commons:Reconocimiento - No comercial - SinObraDerivada (cc-by-nc-nd):Http://creativecommons.org/licences/by-nc-nd/3.0/esCualquier parte de esta obra se puede reproducir sin autorizacin pero con el reconocimiento y atribucin de los autores.No se puede hacer uso comercial de la obra y no se puede alterar, transformar o hacer obras derivadas.

    Esta Tesis Doctoral est depositada en el Repositorio Institucional de la Universidad de Mlaga (RIUMA): riuma.uma.es

  • D. Rafael Suau Surez, Catedrtico de Qumica Orgnica y D. Ezequiel Prez-Inestrosa, Profesor Titular de Qumica Orgnica de la Facultad de

    Ciencias de la Universidad de Mlaga,

    Certifican:

    Que la memoria adjunta, titulada TRANSFERENCIA ELECTRNICA

    FOTOINDUCIDA BASADA EN ACEPTORES TIPO N-XIDOS DE

    ISOQUINOLINAS: PROCESOS OXIDATIVOS RADICALARIOS Y

    OPERADORES LGICOS MOLECULARES, que para optar al grado de

    Doctor (Doctorado Europeo) presenta Jos Mara Montenegro Martos, ha

    sido realizada bajo nuestra direccin en los laboratorios del

    Departamento de Bioqumica, Biologa Molecular, Inmunologa y Qumica

    Orgnica de la Universidad de Mlaga.

    Considerando que constituye un trabajo de Tesis Doctoral, autorizamos

    su presentacin en la Facultad de Ciencias de la Universidad de Mlaga.

    Y para que conste, firmamos el presente certificado en Mlaga a

    diciembre de 2009.

    Fdo. Dr. Rafael Suau Surez Fdo. Dr. Ezequiel Prez-Inestrosa

  • Acknowledgements

    I would like to express my sincere gratitude to all the people who helped and leant

    me during the execution of the Doctoral Thesis presented here, and especially,

    To the professors Dr. Rafael Suau and Dr. Ezequiel Prez-Inestrosa, both directors

    of my work, for all their efforts, their teachings, their help and their trust in me from

    the beginning of my Ph.D.

    To the Organic Chemistry Department professors and lecturers, Mara Valpuesta,

    Rodrigo Rico, Rafael Garca, Gregorio Torres, M Soledad Pino, Francisco Sarabia,

    Juan Manuel Lpez, Francisco Njera and Amelia Daz for their education during the

    degree and the Ph.D. years.

    Specially, my gratitude to the lecturers, colleagues and friends Daniel Collado and

    Yolanda Vida for their help when I started in the laboratory and for these years full of

    nice moments shared in the laboratory.

    To my laboratory colleagues, Antonio Jess, Isabel and Elena for making easier the

    working hours, especially to Maribel for the time we shared and for her friendship.

    To my colleagues of the plants laboratory, M Carmen, Manuela and Jess.

    To my colleagues of the sugars laboratory, Samy, Francisca, Miguel, Jose, Antonio,

    Carlos and Noe.

    To our laboratory technician, Jos Beltrn and our secretary, Isabel Viola.

    I also feel very grateful to Dr. Dario Bassani, Jean Pierre Desvergne and Nathan

    McClenaghan for their help, kindness and teaching during my stay in the Laboratoire

    de Chimie Organique et Organometallique (LCOO) of the Universit Bordeaux I.

    To the Dr. Juan Casado for its help with the electrochemistry measurements.

    To the Professors Rafael Asenjo and Francisco R. Villatoro for the useful discussions

    about logic gates.

    I would like to thank the Spanish Ministry of Education and Science for the Ph.D.

    fellowship awarded.

  • To my degree colleagues and friends, Francisco Javier Jimnez, Antonio Lucio

    Mancebo, Juan Francisco Agera and Marcos Antonio Guerrero.

    To my colleagues of the Physical Chemistry department, and my friend Alejandro.

    To all my friends, for the moments we have lived together, especially to Dr. Francisco

    Javier Fortes, because he knows how hard is the way to become Doctor.

    I want to show gratitude to all my family for its help and leant, especially to my

    grandparents. Thanks for being there. You are always on my mind.

    My gratitude to my in-laws for being a second family for me.

    To my parents and brother for your help, love and because you have always

    encouraged me to follow my dreams. All Ive got is for you.

    To Roco, for your understanding and patience, and because you have suffered this

    thesis with me trying always to make me smile and making it bearable. Thank you

    for your love and for your life. You are the sunshine of my life.

    Finally I would like to thank all the people that I havent mentioned but have helped

    me these years.

  • To my parents

    To my brother

  • To Roco

  • Abbreviations / Abreviaturas

    A Acceptor / Aceptor

    A-S-D Acceptor-Spacer-Donor / Aceptor-Espaciador-Dador MCPBA m-Chloroperoxybenzoic acid / cido m-cloroperbenzoico

    atm Atmosphere / Atmsfera

    bs Broad singlet / Singlete ancho

    CMOS Complementary Metal Oxide Semiconductor /Semiconductor

    complementario de xido metlico

    CT Charge transfer / Transferencia de carga

    D Donor / Dador

    d Doublet / Doblete

    dd Doble doblete / Double doublet

    DMF N,N-Dimethylformamide / N,N-Dimetilformamida

    dt Double triplet / Doble triplete

    Molar absorption coefficient / Coeficiente de absorcin molar

    EDTA Ethylenediaminetetraacetic acid / cido etilendiaminotetraactico

    ET Electron transfer / Transferencia electrnica

    Fluo Fluorescence quantum yield / Rendimiento cuntico de fluorescencia

    FAB-HRMS Fast atom bombardment - High Resolution Mass Spectrometry /

    Espectrometra de masas de alta resolucin por bombardeo con

    tomo rpido.

    FRET Frster Resonance Energy Transfer / Transferencia de energa de

    resonancia de Frster

    HOMO Highest occupied molecular orbital / Orbital molecular ocupado ms

    alto

    Hz Hertz / Hertzios

    IF Fluorescence intensity / Intensidad de fluorescencia

    ICT Internal charge transfer / Transferencia interna de carga

    In Input

    J Coupling constant / Constante de acoplamiento

    LE Local emission / Emisin local

    LUMO Lowest unoccupied molecular orbital / Orbital molecular no ocupado

    ms bajo

    m Multiplete / Multiplet

    MS-EI Mass spectrometry - Electronic impact / Espectrometra de masas

    por impacto electrnico

  • NBS N-bromosuccinimide / N-bromosuccinimida

    NIH NIH shift / Desplazamiento NIH

    NMM N-metilmorfolina / N-methylmorpholine

    NMR Nuclear magnetic resonance / Resonancia magntica nuclear

    Out Output

    PET Photoinduced electron transfer / Transferencia electrnica

    fotoinducida

    ppm Parts per million / Partes por milln

    q Quartet / Cuadruplete

    qu Quintet / Quintuplete

    S Spacer / Espaciador

    s Singlet / Singlete

    t Triplet / Triplete

    TBAH Tetrabutylammonium hydroxide / Hidrxido de tetrabutil amonio

    TEBA Triethylbenzylammonium chloride / Cloruro de bencil trietilamonio

    TEGDT Tetraethyleneglycol ditosylate / Tetraetilenglicol ditosilato

    TFA Trifluoroacetic acid / cido trifluoroactico

    THF Tetrahidrofurano / Tetrahydrofuran

    TTF Tetratiafulvaleno / Tetrathiafulvalene

  • INDEX

  • Index

    iii

    Index SUMMARY 1 CHAPTER I. GENERAL INTRODUCTION 9 I.1. Electron Transfer 11 I.2. Marcus Theory 15 I.3. Intermolecular electron transfer 19 I.3.1. Radiative processes 19 I.3.2. Thermal electron transfer 20 I.3.3. Photoinduced electron transfer (PET) 20 I.4. Intramolecular Electron Transfer 22 I.4.1. Saturated spacer systems 23 I.4.2. Unsaturated spacer organic systems 25 I.5. Physical and Chemical PET Associated Processes 27

    CHAPTER II. OBJECTIVES 29

    CHAPTER III. ELECTRON ACCEPTOR-SPACER-DONOR SYSTEMS BASED ON ISOQUINOLINE N-OXIDE 35 III.1. Introduction 37 III.1.1. Organic reactivity derived from electron transfer processes 37 III.1.1.1. Bond cleavage 38 III.1.1.2. Electron transfer-initiated nucleophilic substitution 39 III.1.1.3. Rearrangements initiated by bond cleavage in radical cations 40

    III.1.1.4. Nucleophile addition to radical cations -bonds 41

    III.1.1.5. Nucleophile addition to radical cations -bonds 41

    III.1.2. Photochemical reac