Conformational Analysis of Molecules in

* Calculations of excited state conformational properties

JACEK WALUK, PhD, is Professor of Chemistry at the Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland.

Preface

xi

Contributors

xv

Conformational Changes Accompanying Intramolecular Excited State Electron Transfer

1

(56)

Wolfgang Rettig

Michael Maus

Introduction

1

(3)

Twisting of Amino Groups

2

(1)

Biaromatic Compounds

3

(1)

Compounds with Several Flexible Bonds: Stilbenes, Polyenes, Cyanines

4

(1)

Basic Principles

4

(4)

Mesomeric Interaction

4

(1)

Self-Decoupling Biradicaloid Interaction with the Ground State

5

(1)

Interaction with Locally Excited States

6

(1)

Steric Interaction

6

(1)

Pyramidalization at the Amino Nitrogen

6

(2)

Rehybridization in Nitrogen-Containing Acceptor Groups

8

(1)

Acceptor-Substituted Anilines: Evidence for Excited-State Twisting in DMABN and Derivatives

8

(9)

Pretwisted and Planarized Model Compounds

11

(3)

The Dynamic Approach

14

(1)

The Emission Transition Moment

15

(1)

Open Questions

16

(1)

Aryl-Aryl Systems

17

(32)

From Biphenyl to Donor-Acceptor Biaryls

18

(4)

Tools for a Conformational Analysis Using Optical Spectroscopy

22

(5)

Analysis of Different Charge Transfer Biaryl Compounds

27

(22)

Concluding Remarks

49

(8)

Conformational Aspects of Intra- and Intermolecular Excited-State Proton Transfer

57

(56)

Jacek Waluk

Introduction

57

(3)

The Never-Ending Story of 7-Azaindole and Its Relatives

60

(14)

Excited State Double-Proton Transfer (ESPDT) in 7-Azaindole Dimers

60

(6)

7-Azaindole and 1-Azacarbazole: Similarities and Differences

66

(1)

Excited-State Double Proton Transfer in Alcohol and Water Complexes of 7-Azaindole

66

(5)

Excited-State Double-Proton Transfer in 2-(2-Pyridyl) Indoles, 1H-pyrrolo[3, 2-h] Quinoline and Related Structures

71

(3)

7-Hydroxyquinoline: The Case of Proton Relay

74

(4)

Rotational Isomerism and Proton Transfer

78

(8)

Salicylic Acid and Its Derivatives

78

(5)

2-(2-Hydroxyphenyl) Benzazoles

83

(2)

2-(2-Hydroxyphenyl)Benzotriazoles

85

(1)

Photochromic and Thermochromic Substances

86

(4)

Salicylideneanilines

86

(2)

Dinitrobenzylpyridines and Derivatives

88

(2)

Solvent Control of the Excited-State Proton Transfer

90

(8)

Solvent Interference with the Excited-State Intramolecular Proton Transfer

90

(3)

Solvent-Assisted Excited-State Proton Transfer

93

(3)

Non-specific Solvent Effects

96

(2)

Excited-State Proton Transfer in Clusters

98

(1)

Concluding Remarks

98

(15)

The Role of Solute-Solvent Friction in Large-Amplitude Motions

113

(64)

David H. Waldeck

Introduction

113

(2)

Rotational Relaxation

115

(20)

Continuum Models for the Friction

118

(7)

Molecular Models for the Friction

125

(3)

Experimental Studies of Solute-Solvent Frictional Coupling

128

(7)

Orientational Relaxation of Bimolecular Complexes

135

(13)

Theoretical Models

137

(5)

Experimental Examples

142

(6)

Isomerization and the Importance of Frictional Coupling

148

(16)

Models for the Rate Constant

150

(4)

Identifying an Intrinsic Barrier

154

(2)

Modeling the Friction

156

(6)

The Importance of Other Degrees of Freedom

162

(1)

Barrierless Reactions

163

(1)

Conclusion

164

(13)

Structural Aspects of Exciplex Formation

177

(60)

Fred Brouwer

Exciplexes and Other Excited-State Complexes

177

(4)

Formation and Decay of Exciplexes

181

(23)

Formation of Exciplexes

181

(3)

Rates of Electron Transfer Quenching

184

(6)

Fluorescence Solvatochromic Shift

190

(2)

Decay of Exciplexes

192

(12)

Electronic and Geometric Structure of Exciplexes

204

(13)

Basic Considerations

204

(1)

Electronic Structure of Exciplexes

205

(3)

Singlet vs. Triplet Exciplexes

208

(2)

Exciplex Geometry

210

(2)

Exciplex Formation in Supersonic Jets

212

(4)

The Solvent-Separated Ion Pair: What Is It?

216

(1)

Intramolecular Exciplexes

217

(20)

Photoinduced Charge Separation in Linked Electron Donor-Acceptor Systems

217

(3)

Intramolecular Exciplexes in Isolated Molecules

220

(3)

Conformational Changes Following Intramolecular Charge Separation in Solution

223

(14)

Conformational Aspects of Organic Photochemistry

237

(60)

Giampiero Bartocci

Anna Spalletti

Ugo Mazzucato

Introduction

237

(2)

Internal Rotation and Conformational Equilibria

237

(1)

Restricted Rotation About sp2-sp2 Carbon--Carbon Single Bonds

237

(2)

Methods of Investigation

239

(15)

Experimental Evidence of Ground-State Rotamers

239

(2)

Computational Techniques

241

(1)

Methods Based on Fluorimetry

242

(10)

Evidences of Rotamer Interconversion in the Excited State (Non-NEER Behavior)

252

(2)

Typical Examples of Rotamerism in some Selected Series of Olefins

254

(24)

Two-Component Systems: The Case of trans-Anthryl Derivatives

255

(12)

Three-Component Systems: The Case of trans-1-(2-Naphthyl),2-(6-Quinolyl) Ethene

267

(6)

Rotamerism in α, ω-Diarylpolyenes

273

(5)

Conformational Control of Photochemistry

278

(13)

Effect on the Photoreaction Quantum Yield

278

(6)

Effect on the Direction of Photoreaction (Multiway Cyclization of cis Isomers)

284

(7)

Concluding Remarks

291

(6)

Calculations of Excited-State Conformational Properties

297

(70)

Massimo Olivucci

Michael A. Robb

Fernando Bernardi

Introduction

297

(3)

The Case of Buta-1, 3-diene

300

(21)

The Structure of the S1 Buta-1, 3-diene Energy Surface

307

(4)

Conical Intersection Conformers and Reaction Selectivity

311

(4)

Excited-State Conformations and Stereoselectivity of the Photochemical s-cis Buta-1, 3-diene Ring Closure

315

(4)

The Nonstereospecific Ring Opening of Cyclobutene

319

(1)

Ultrafast Photochemistry of Buta-1, 3-diene

319

(1)

Buta-1, 3-diene Triplet Conformers and Triplet Photochemistry

320

(1)

Methods for Excited-State Computations

321

(10)

The Potential Energy Surface Computation: The CAS-SCF Method

322

(4)

Search and Computation of Excited-State Reaction Paths

326

(5)

Excited-State Conformations of Organic Chromophores

331

(30)

Linear Conjugated Hydrocarbons (Polyenes and Polyenyl Radicals)

333

(3)

Adiabatic vs. Nonadiabatic Paths and Photochemical Stereoselectivity

336

(8)

Photochemical Chemoselectivity and Regioselectivity: The Case of Z-hexa-1, 3, 5-triene

344

(2)

Cyclic Conjugated Hydrocarbons

346

(2)

Conformational Effects of Conjugated Heteroatoms: Protonated Schiff Bases

348

(2)

Conformational Effects of Conjugated Heteroatoms: α, β-Enones

350

(6)

π vs σ Conjugation: Oligosilanes

356

(5)

Conclusions

361

(6)

Index

367

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Conformational Analysis of Molecules in Excited States

Summary

Author Biography

Table of Contents

Supplemental Materials

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Conformational Analysis of Molecules in Excited States

Summary

Author Biography

Table of Contents

Supplemental Materials

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