Supramolecular Complexes of Oxoporphyrinogens with Organic Molecules

Cover
Springer Theses Series
Supramolecular Complexes of Oxoporphyrinogens with Organic Molecules
Copyright
Supervisor’s Foreword
Abstract
Acknowledgments
Contents
Abbreviations
1. Introduction
	1.1 Overview of Tetrapyrroles
	1.2 Properties and Applications of Oxoporphyrinogens
	1.3 Aims and Structure of This Work
	References
2. Quantitative Description of Supramolecular Binding
	2.1 Description of Chemical Reactions
		2.1.1 Equilibrium Constant
		2.1.2 Meaning of Activity Coefficients
		2.1.3 The Rate Law
		2.1.4 Eyring Equation
	2.2 Host-Guest Binding
		2.2.1 H:G 1:1 Binding Model
		2.2.2 Aspects of Multiple Binding Sites
		2.2.3 Competitive Host-Ligand Binding
		2.2.4 Cooperativity
	References
3. Nuclear Magnetic Resonance Spectroscopy
	3.1 Basic Phenomena in NMR
		3.1.1 Nuclei in Magnetic Field
		3.1.2 Chemical Shift
		3.1.3 Relaxation
		3.1.4 J-Coupling
		3.1.5 Bloch Equations
		3.1.6 Effect of Radiofrequency Field
	3.2 Measurement of NMR
		3.2.1 NMR Spectrometer
		3.2.2 Pulsed NMR Experiment
		3.2.3 Lorentzian Spectral Lineshape
	3.3 Chemical Exchange
		3.3.1 Kinetics of Spin States
		3.3.2 Kinetics of Two-State Exchange
		3.3.3 Kinetics of Three-State Exchange
		3.3.4 Bloch-McConnell Equations
		3.3.5 Solution of Bloch-McConnell Equations
		3.3.6 Two-State Exchange Spectral Lineshape
		3.3.7 Three-State Exchange Spectral Lineshape
		3.3.8 Exchange Schemes Containing a Fast Process
	3.4 NMR of Host-Guest Systems
		3.4.1 Chemical Exchange in Host-Guest Complexes
		3.4.2 NMR Titration Binding Isotherms
		3.4.3 Determination of Enantiomeric Excess
	References
4. UV/vis Spectroscopy
	4.1 Absorbance Measurement
	4.2 Beer-Lambert Law of Absorption
	4.3 UV/vis Titration Experiment
	4.4 Isosbestic Points
	4.5 Halochromism and Solvatochromism
	References
5. Singular Value Decomposition
	5.1 Mathematical Properties
		5.1.1 Basics of SVD
		5.1.2 Pseudoinverse and Linear Regression
	5.2 Analysis of UV/vis Spectral Series via SVD
		5.2.1 Linear Combination of Absorbing Components
		5.2.2 Determining the Number of Absorbing Species
		5.2.3 Transformation from Abstract to Real Spectra
		5.2.4 Combination Coefficients
		5.2.5 Decomposition to the Absorbing Components Without SVD
		5.2.6 SVD Analysis–Summary
	5.3 Analogy with Principal Component Analysis
		5.3.1 Calculation of Principal Components
		5.3.2 Comparison to SVD
		5.3.3 Application
	References
6. Chromic and Binding Properties of OxP Derivatives
	6.1 Halochromism of OxP
	6.2 Halochromism of upper B z 2Bz2OxP
	6.3 Chromism of upper B z 4Bz4OxP
	6.4 Mechanism of Halochromism
	6.5 NMR Analysis of Host-Guest Binding
	6.6 Solvatochromism of OxP
	6.7 Solvatochromism of upper B z 2Bz2OxP
	6.8 Solvatochromism of Bz4OxP
	6.9 Chromism and Binding–Summary
	References
7. Dynamic Processes and Chemical Exchange in OxP Derivatives
	7.1 Dynamics of OxP
		7.1.1 Prototropic Tautomerization
		7.1.2 Anion Binding at the Porphyrinogen Center
		7.1.3 Macrocyclic Inversion
	7.2 Dynamics of upper B z 2Bz2OxP
		7.2.1 Topomerization at Hemiquinonoid Groups
		7.2.2 Anion Binding at the Porphyrinogen Center
		7.2.3 Prototropic Tautomerization
	7.3 Dynamic Processes Summary
	References
8. Conclusion
Appendix A. Overview of Binding Models
	A.1  Binding Model 1:1
	A.2  Binding Model 1:2
	A.3  Binding Model 1:3
	A.4  Binding Model 1:4
	A.5  Competitive Binding 1:1 Host-Ligand Binding
		A.5.1  First Solution
		A.5.2  Second Solution
Appendix B. Overview of NMR Spectral Lineshapes
	B.1  Lineshape Formulae and Mathematica Codes
		B.1.1  Lorentzian Lineshape
		B.1.2  Two-State Exchange Lineshape
		B.1.3  Three-State Exchange Lineshape
		B.1.4  Spectral Lineshape of Two J-coupled Spins
	B.2  Rapid Derivation of upper NN-State Exchange Lineshape in Mathematica
	B.3  Rapid Derivation of Three-State Populations
Appendix C. Experimental Details, Models and Data Analysis
	C.1  Properties of Used Chemicals
	C.2  UV/vis Spectroscopy Measurements
	C.3  RGB Coordinates of UV/vis Spectra
	C.4  NMR Spectroscopy Measurements
	C.5  NMR Analysis of Host-Guest Binding
	C.6  Fitting of Exchange Lineshapes
	C.7  Fitting of Experimental Data in Bz2OxP + (R)-CSA System
	C.8  Kinetic Models of Bz2OxP + (R)-CSA System
	C.9  Prototropic Tautomerization Processes in Bz2OxP
Appendix D. SVD Analysis
	D.1  Bz2OxP + (R)-CSA Titration
	D.2  OxP + TFA Titration
	D.3  Bz2OxP + DFA Titration
	D.4  Bz4OxP + DFA Titration
	D.5  OxP + DMF Titration
	D.6  Bz2OxP + DMF at Different vol.f.
	D.7  Bz4OxP + DMF at Different vol.f.
Appendix E. NMR Spectra
	E.1  Spectra of Acids
	E.2  OxP + DFA Titration
	E.3  OxP + (R)-CSA Titration
	E.4  Bz2OxP + DFA Titration
	E.5  Bz2OxP + (R)-CSA Titration
	E.6  Bz2OxP + (rac)-CSA Titration
	E.7  Bz4OxP + DFA Titration
	E.8  OxP + DFA 1.1 equiv. Variable Temperature
	E.9  OxP + DFA 18 equiv.Variable Temperature
	E.10  Bz2OxP Variable Temperature
	E.11  Bz2OxP + DFA 35 equiv. Variable Temperature
	E.12  Bz2OxP + (R)-CSA 0.59 equiv. Variable Temperature
	E.13  Bz2OxP + (R)-CSA 14 equiv. Variable Temperature
	E.14  Bz2OxP + (rac)-CSA 0.5 equiv. Variable Temperature
	E.15  Bz2OxP + (rac)-CSA 17 equiv. Variable Temperature
	E.16  OxP + DMF Titration
	E.17  Detection of OH Signal in Bz2OxP
	E.18  Bz4OxP Assignment—HMBC
	References
Curriculum Vitae