Supramolecular Photochemistry - Springer978-94-009-3979-0/1.pdfNATO ASI Series Advanced Science...

Supramolecular Photochemistry

NATO ASI Series Advanced Science Institutes Series

A series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities.

The series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division

A Life Sciences Plenum Publishing Corporation B Physics London and New York

C Mathematical D. Reidel Publishing Company and Physical Sciences Dordrecht, Boston, Lancaster and Tokyo

D Behavioural and Social Sciences Martinus Nijhoff Publishers E Applied Sciences Dordrecht, Boston and Lancaster

F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris, and Tokyo

Series C: Mathematical and Physical Sciences Vol. 214

Supramolecular Photochemistry

edited by

Vincenzo Balzani Department of Chemistry "G. Ciamician", University of Bologna and Institute FRAE-CNR, Bologna, Italy

D. Reidel Publishing Company

Dordrecht / Boston / Lancaster / Tokyo

Published in cooperation with NATO Scientific Affairs Division

Proceedings of the NATO Advanced Research Workshop on Photoinduced Charge Separation and Energy Migration in Supramolecular Species Anacapri, (Isle of Capri), Italy April 5-10,1987

Library of Congress Cataloging in Publication Data

NATO Advanced Research Workshop on Photoinduced Charge Separation and Energy Migration in Supramolecular Species (1987: Anacapri, Italy) Supramolecular photochemistry.

(NATO ASI series. Series C, Mathematical and physical sciences; vol. 214) "Proceedings of the NATO Advanced Research Workshop on Photoinduced Charge

Separation and Energy Migration in Supramolecular Species, Anacapri (Isle of Capri), Italy, April 5-10, 1987"-T.p. verso.

Includes bibliographies and indexes. 1. Photochemistry-Congresses. 2. Macromolecules-Congresses. I. Balzani,

Vincenzo,1936- . II. Title. III. Series: NATO ASI series. Series C, Mathematical and physical sciences; no. 214. QD701.N345 1987 547.7'0455 87-20668 ISBN-13: 978-94-010-8265-5 e-ISBN-13: 978-94-009-3979-0 001: 10.1007/978-94-009-3979-0

Published by D. Reidel Publishing Company P.O. Box 17, 3300 AA Dordrecht, Holland

Sold and distributed in the U.S.A. and Canada by Kluwer Academic Publishers, 101 Philip Drive, Assinippi Park, Norwell, MA 02061, U.S.A.

In all other countries, sold and distributed by Kluwer Academic Publishers Group, P.O. Box 322, 3300 AH Dordrecht, Holland

D. Reidel Publishing Company is a member of the Kluwer Academic Publishers Group

All Rights Reserved © 1987 by D. Reidel Publishing Company, Dordrecht, Holland. Softcover reprint of the hardcover 1 st edition 1987 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without written permission from the copyright owner.

TABLE OF CONTENTS

Preface

Organizing Committee

List of Participants

v. Balzani, L. Moggi, and F. Scandola Towards a supramolecular photochemistry: assembly of molecular components to obtain photochemical molecular devices

J.-M. Lehn Photophysical and photochemical aspects of supramolecular chemistry

R.A. Marcus

N.S. Hush

N. Sutin

Some recent developments in electron transfer: charge separation, long distances, solvent dynamics, and free energy aspects

Photoinduced electron transfer through long rigid non-conjugated bridges: theory and experiment for model systems

The distance and temperature dependence of electron-transfer rates

S. Tazuke, N. Kitamura, and H-B. Kim

T.J. Meyer

Photoinduced looping electron transfer. What occurs between electron transfer and charge separation?

Intramolecular control of light induced electron transfer

F. Scandola and C.A. Bignozzi Cyano-bridge~+supramolecular systems containing the Ru(bpY)2 photosensitizer unit

ix

xi

xiii

1

29

45

53

73

87

103

121

vi TABLE OF ~ONTENTS

J.D. Petersen Intramolecular energy and electron transfer in polymetallic complexes

M.Z. Hoffman and D.R. Prasad Photoinduced charge separation in ion-pair electron donor-acceptor aggregates

J.F. Endicott, R.B. Lessard, Y. Lei, and C.K. Ryu Electronic inefficiencies in inter- and

135

153

intra-molecular energy and electron transfer 167

N. Sabbatini, S. Perathoner, V3+Balzani3+B. Alpha, and J.M. Lehn Antenna effect in Eu and Tb cryptates 187

A. Harriman Energy transfer in synthetic porphyrin arrays 207

F. Wilkinson and S.L. Collins Competitive energy and electron transfer quenching of the triplet states of organic compounds by Cr(tfac)3 and Cr(tfbzac)3 in benzene

J.R. Miller Through-bond electronic couplings in intramolecular

225

electron transfer reactions 241

M.R. Wasielewski, D.G. Johnson, and W.A. Svec Photoinduced electron transfer in fixed distance chlorophyll-quinone donor-acceptor molecules 255

D. Gust and T.A. Moore Electron transfer in model systems for photosynthesis 267

T.A. Moore, D. Gust, A.L. Moore, R.V~ Bensasson, P. Seta, and E. Bienvenue

Transmembrane charge transfer in model systems for photosynthesis

J.S. Connolly, J.K. Hurley, W.L. Bell, and K.L. Marsh Inter- and intramolecular quenching of porphyrin excited states by quinones

Z.R. Grabowski

W. Rettig

Molecular structure in the electron-localized excited states and the radiative electron transfer

Small-overlap charge transfer states in large molecular systems

283

299

319

329

TABLE OF CONTENTS

A. Weller

G. Blasse

Chain effect and magnetic field effect on the photoinduced electron transfer reactions of polymethylene-linked donor acceptor systems

Photoinduced charge separation and energy migration

343

in condensed matter: examples and applications 355

C.A. Backer J.R. Corvan, T.J. Dannhauser, B.R. Suddaby, K. Takagi, G.L. McLendon, and D.G. Whitten

Reactions of delocalized excited states generated in restricted environments

F.C. De Schryver, M. Van der Auweraer, B. Verschuere, and F. Willig Photosensitized hole injection from Langmuir-Blodgett films into molecular crystals; the influence of image

371

potential and through-bond effects 385

M.A. Fox and D.A. Chandler Metal-loaded polymers as materials for photoinduced charge separation 405

N. Serpone, P. Pichat, J.-M. Herrmann, and E. Pelizzetti Inter-particle electron transfer in semiconductor dispersions: a new strategy in photocatalysis 415

M. Gratzel Vectorial electron transfer in organized assemblies and colloidal s.emiconductors 435

N.S. Hush Report on the general discussion on "Future Trends: Theoretical aspects" 455

G. Blasse Report on the general discussion on "Future Trends: Applicative aspects" 459

Author index 461

Subject index 463

vii

PREFACE

The intellectual and utilitarian opportunities that lie at the frontiers

of chemistry have been recently emphasized by the Pimentel Report. Such

report recommends that in the field of chemical research priority should

be given to "understanding chemical reactivity" and proposes initiatives

aimed at the clarification of factors that control the rates of reaction

and the development of new synthetic pathways for chemical change.

In the broad field of chemical reactivity, a discipline that has

grown with an extraordinary rate is photochemistry. Since the knowledge

of the photochemical properties at the molecular level has made a

substantial progress in the last few years, there is currently a trend

to study more and more complex photochemical systems. In particular, an

emerging and rapidly expanding branch of photochemistry is that

concerning studies of assemblies of molecular components properly

combined so as to obtain light-induced functions (supramolecular

photochemistry). Although much of the current work in supramolecular

photochemistry is fundamental in nature, it is clear that progress in

this field will be most rewarding for several applications concerning

the interaction of light with matter. In particular, it will allow us to

pursue research aimed at the photochemical conversion of solar energy by

means of artificial systems and to make progress towards futuristic

branches of science called "photonics" (photo-generated electron

migration processes on a molecular basis) and "chemionics" (design of

components, circuitry, and information treatment at the molecular

level).

In the context of the immaginative and creative area of

supramolecular photochemistry, the purpose of the Nato Advanced Research

Workshop held at Anacapri in April 1987 was to focus the attention of

qualified scientists on the problem of photochemical molecular devices

ix

x PREFACE

capable of performing the important functions of photoinduced charge

separation and energy migration. The workshop offered the opportunity

for a full and informal discussion of recent achievements and problems

with active participation and exchanges of ideas among experts in

photochemistry, theoretical chemistry, preparative chemistry, catalysis,

organic chemistry, and inorganic chemistry.

At the end of the Workshop, problems concerning the role of Science

in the World and the role of the Nato Workshops in Science were also

raised and discussed informally. Beyond the personal (often quite

different) views of the participants, there was a strong, general desire

for friendship and peace.

The Workshop, and consequently this monograph, would not have been

possible without the generous financial support from the Nato Programme

on Selective Activation of Molecules. Financial support was also offered

by Consiglio Nazionale delle Ricerche, ENEA, U.S. Army Research Office

(Europe), and Polaroid. I want to thank the lecturers and all the

participants, whose enthusiastic involvement made the meeting a

scientific success. I would also like to thank my coworkers for their

dedicaded help in the organization of the Workshop and I am deeply

grateful to Dr. S. Perathoner for her precious assistance in the

editorial work.

Vincenzo Balzani

University of Bologna

Bologna, Italy

May 1987

ORGANIZING COMMITTEE

Professor Vincenzo Balzani (director of the Workshop) Dipartimento di Chimica "G. Ciamician", Universita' di Bologna Via Selmi 2, 40126 Bologna I TAL Y

Professor James R. Bolton Department of Chemistry The University of Western Ontario London CANADA

Professor Franz C. De Schryver Katholieke Universiteit Lauven Afdeling Organische Scheikunde Celestijnenlaan 200F Leuven 3030 BEL G I E

Professor Thomas J. Meyer Department of Chemistry University of North Carolina Chapel Hill - North Carolina 27514 USA

Professor Luca Moggi Dipartimento di Chimica "G. Ciamician", Universita' di Bologna Via Selmi 2, 40126 Bologna I TAL Y

Sir George Porter The Royal Institution 21, Albemarle Street, London WIX 4BS ENGLAND

Professor Alexander E. Shilov Institute of Chemical Physics USSR Academy of Sciences 142432, Chernologolovka, Moskow Region U S S R

Professor Shigeo Tazuke Tokyo Institute of Technology Research Laboratory of Resources Utilization 4259 Nagatsuta, Midori-ku, Yokohoma, 227 J A PAN

xi

LIST OF PARTICIPANTS

G. Aloisi

R. Ballardini

V. Balzani

F. Barigelletti

C. Bignozzi

G. Blasse

F. Bolletta

Dipartimento di Chimica Universita' di Perugia Via Elce di Sotto, 10 06100 Perugia I TAL Y

FRAE CNR Via de Castagnoli, 40126 Bologna I TAL Y

Dipartimento di Chimica "G. Ciamician" Universita' di Bologna Via Selmi, 2 40126 Bologna I TAL Y

FRAE CNR Via de Castagnoli, 1 40126 Bologna I TAL Y

Dipartimento di Chimica Universita' di Ferrara Via Borsari, 46 44100 Ferrara I TAL Y

Rijksuniversiteit Utrecht Fysisch Laboratorium Princetonplein 5 Postbus 80.000 3508 TA Utrecht THE NET HER LAN D S

Dipartimento di Chimica "G. Ciamician" Via Selmi, 2 40126 Bologna I TAL Y

xiii

xiv

P. Bortolus

S. Campagna

D. Campbell

C. Chiorboli

J.S. Connolly

J. Davila

L. De Cola

F.C. De Schryver

F. Elisei

FRAE CNR Via de Castagnoli, I 40126 Bologna I TAL Y

Dipartimento di Chimica Universita' di Messina 98100 Messina I TAL Y


Chemistry and Biological Branch European Research Office U.S. Army Edinson House, 223 Old Marylebone Rd. London G REA T B R I T A IN.

Centro di Fotochimica CNR Via Borsari, 46 44100 Ferrara I TAL Y

Solar Research Institute Golden, Colorado 80401 USA

Departamento de Quimica-Fisica Facultad de Quimica Universidad Complutense de Madrid Madrid SPA I N


Katholieke Universiteit Lauven Afdeling Organische Scheikunde Celestijnenlaan 200F Leuven 3030 BEL G I E



J.F. Endicott

M.A. Fox

M.T. Gandolfi

C. Giannotti

Z.R. Grabowski

M. Graetzel

D. Gust

A. Harriman

H. Hennig

Department of Chemistry Wayne State University Detroit, Michigan 48202 USA

Department of Chemistry University of Texas Austin, Texas 78712 - 1167 USA


Institute de Chimie des Substances Naturelles CNRS Gif-Sur-Yvette 91190 FRANCE

Instytut Chemii Fizycznej Pan (Polish Academy of Sciences) Kasprzaka 44/52 POLAND

Department de Chimie Ecole Poly technique Federale Lausanne 1015 SUI SSE

Department of Chemistry Arizona State University Tempe, Arizona 85287 USA

Davy Faraday Research Laboratory The Royal Institution 21, Albemarle Street London, W1X 4BS GREAT BRITAIN

Sekt. Chemie Karl-Marx-Universitaet 7010 Leipzig D D R

xv

xvi

M. Z. Hoffman

N.S. Hush

M.T. lndelli

A. Juris

J.M. Lehn

M. Maestri

R.A. Marcus

U. Mazzucato

Department of Chemistry Boston University 685 Commonwealth Avenue Boston, Massachussetts 02215 USA

Department of Theoretical Chemistry University of Sydney N.S.W. 2006 A U S T R A L I A




Universite' Louis Pasteur lnstitut de Chimie 1, rue Blaise Pascal 67000 Strasbourg F RAN C E


California Institute of Tecnology Division of Chemistry and Chemical Engineering The Chemical Laboratories Pasadena, California 91125 USA

Dipartimento di ·Chimica Universita' di Perugia Via Elce di Sotto, 10 06100 Perugia I TAL Y


T.J. Meyer

J.R. Miller

L. Moggi

S. Monti

A.L. Moore

T.A. Moore

T.L. Netzel

G. Orlandi

S. Perathoner

Department of Chemistry University of North CarolinA CHAPEL HILL - North Carolina 27514 USA

Chemistry Division Argonne National Laboratory Argonne Illinois 60439 USA


FRAE CNR Via de Castagnoli, 40126 Bologna I TAL Y

Department of Chemistry University of Arizona Tempe, Arizona 85287 USA

Department of Chemistry University of Arizona Tempe, Arizona 85287 USA

Amoco Corporation Amoco Research Center P.O.B. 400 Naperville, Illinois, 60566 USA



xvii

xviii

J.D. Petersen

F. Pina

M.A. Rampi

W. Rettig

M.C. Richoux

N. Sabbatini

D. Sandrini

F. Scandola

Clemson University Department of Chemistry and Geology Clemson, South Carolina 29631 USA


Centro de Quimica Estrutural Complexo 1 Instituto Superior Tecnico Av. Rovisco Pais 1096 Lisboa Codex PORTUGAL


Iwan N. Stranski-Institute for Physical and Theoretical Chemistry Technical University of Berlin D-12000 Berlin (W) 12 FEDERAL REPUBLIC OF GERMANY

The Royal Institution 21, Albemarle Street London WIX 4BS G REA T B R I T A I N





N. Serpone

S. Sofen

N. Sutin

S. Tazuke

Department of Chemistry Concordia University 1455 de Maisonneuve Blvd West Montreal - Quebec H3TG IM8 CANADA

Polaroid Corp. 750 Main Street, 4J Cambridge, MA 02139 USA

Department of Chemistry Brookhaven National Laboratories UPTON - Long Island, New York N.Y. 11973 USA

Tokyo Institute of Technology Research Laboratory of Resources Utilization 4259 Nagatsuta, Midori-ku, Yokohama, 227 J A PAN

M. Van der Auveraer Katolieke Universiteit Lauven Afdeling Organische Scheikunde Celestijnenlaan 200f Leven 3030 BEL G I E

A. Vogler Universitaet Regensburg Universitaetstrasse 31 - Postfach 8400 Regensburg FEDERAL REPUBLIC OF GERMANY

A. von Zelewsky Institut de Chimie Inorganique et Analytique Universite' de Fribourg Perolles CH-1700 Fribourg SUI SSE

M.R. Wasielewski Chemistry Division Argonne National Laboratory Argonne, Illinois 60439 USA

A. Weller Max-Planck-Institut fuer Biophysikalische Chemie Postfach 2841 D-3400 Goettingen FEDERAL REPUBLIC OF GERMANY

xix

xx

D.G. Whitten

F. Wilkinson

H. Yersin

E. Zinato

Department of Chemistry University of Rochester Rochester, NY 14627 USA

Chemistry Department


Loughborough University of Technology GB - Loughborough, Leics. LEll 3TU G REA T B R I T A I N

Universitaet Regensburg Universitaetstrasse 31 - Postfach 8400 Regensburg FEDERAL REPUBLIC OF GERMANY


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