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Structure and Function

:	Peter Comba
:	Peter Comba
:	Structure and Function
:	Springer-Verlag
:	9789048128884
:	1
:	CHF 90.20
:

:	Anorganische Chemie
:	English

:	260
:	Wasserzeichen
:	PC/MAC/eReader/Tablet
:	PDF

The art of chemistry is to thoroughly understand the properties of molecular compounds and materials and to be able to prepare novel compounds with p- dicted and desirable properties. The basis for progress is to fully appreciate and fundamentally understand the intimate relation between structure and function. The thermodynamic properties (stability, selectivity, redox potential), reactivities (bond breaking and formation, catalysis, electron transfer) and electronic properties (spectroscopy, magnetism) depend on the structure of a compound. Nevertheless, the discovery of novel molecular compounds and materials with exciting prop- ties is often and to a large extent based on serendipity. For compounds with novel and exciting properties, a thorough analysis of experimental data - state-of-the-art spectroscopy, magnetism, thermodynamic properties and/or detailed mechanistic information - combined with sophisticated electronic structure calculations is p- formed to interpret the results and fully understand the structure, properties and their interrelation. From these analyses, new models and theories may emerge, and this has led to the development of ef cient models for the design and interpre- tion of new materials and important new experiments. The chapters in this book therefore describe various fundamental aspects of structures, dynamics and physics of molecules and materials. The approaches, data and models discussed include new theoretical developments, computational studies and experimental work from molecular chemistry to biology and materials science.

	Structure and Function	1
	Jan C.A. Boeyens – A Holistic Scientist	4
	Root	8
	Preface	10
	Contents	12
	Contributors	14
	1 Molecular Associations Determined from Free Energy Calculations	16
	1.1 Introduction	16
	1.2 Statistical Mechanics of Molecular Association	18
	1.3 Condensed Phase Molecular Dynamics Simulations	20
	1.4 Free Energies from Adaptive Reaction Coordinate Forces	20
	1.5 Associative Solvents	22
	1.5.1 Water	23
	1.5.2 Methanol	25
	1.6 Ions in Associative Solvents	29
	1.7 Reactions in Associative Solvents	32
	References	34
	2 Molecular Modelling for Systems Containing Transition Metal Centres	36
	2.1 Introduction	36
	2.2 Molecular Mechanics	39
	2.2.1 Shortcomings of MM for TM Systems	41
	2.2.2 Ligand Field Molecular Mechanics	42
	2.3 Applications of LFMM	44
	2.3.1 Simple Coordination Complexes: Cu(II) Amines	45
	2.3.2 [MCl4]2- Complexes	46
	2.3.3 Cu(II) Bis-oxazoline Complexes	48
	2.3.4 Jahn–Teller Effects in Six-Coordinate Cu(II) Complexes	49
	2.3.4.1 The Mexican Hat Potential Energy Surface	49
	2.3.4.2 The Warped Mexican Hat	50
	2.3.4.3 Theoretical Treatment of the Jahn–Teller Effect in Cu(II) Species	52
	2.3.4.4 Barriers Between Successive Elongations	54
	2.3.4.5 Truly Compressed Complexes	56
	2.3.5 Spin-State Effects	56
	2.3.6 Type 1 Copper Enzymes	57
	2.3.7 Dinuclear Copper Centres	60
	2.4 Conclusions	64
	References	65
	3 Magnetic Anisotropy in Cyanide Complexes of First Row Transition Metal Ions	67
	3.1 Introduction	67
	3.2 Jahn–Teller Coupling Versus Spin-Orbit Coupling in the Ground State of [Fe(CN)6]3-	69
	3.3 Modeling of the Magnetic Anisotropy in Ni-NC-FeIII Pairs	77
	3.3.1 Theory	77
	3.3.2 Regular (C4v) Versus Distorted (Cs) [Fe(CN)63-] and Its Influence on the Magnetic Anisotropy of the Fe-Ni Pair	79
	3.3.3 Effect of Combined Spin-Orbit Coupling and Strain at the FeIII Subunit	82
	3.4 Magnetic Anisotropy in Linear Trinuclear Cu-NC-Fe-CN-Cu complexes	85
	3.5 Computation of the Magnetic Anisotropy in Oligonuclear Complexes with Nearly Degenerate Ground States	88
	3.5.1 Theory	88
	3.5.2 Applications to Various Cyanide-Bridged MnFem Complexes (M = CuII, NiIII)	93
	3.6 Conclusions	96
	References	97
	4 Structure and Function: Insights into Bioinorganic Systems from Molecular Mechanics Calculations	100
	4.1 Introduction	100
	4.2 The MM Method	101
	4.3 Handling Metal Ions	102
	4.4 Extending the Force Field	103
	4.5 Applications of the Corrin Force Field: Structure and Function of B12 Derivatives	106
	4.6 Applications of the Corrin Force Field: The Structure of the Cobalt Corrins in Solution	107
	4.7 Applications of the Porphyrin Force Field: The Solution Structures of the Complexes Formed Between Ferriprotoporphyrin IX and Arylmethanol Antimalarials	109
	References	118
	5 Artificial Photosynthetic Reaction Center	123
	5.1 Introduction	123
	5.2 Electron Donor–Acceptor Ensembles with Covalent Bonding	125
	5.2.1 Multi-step Electron Transfer	125
	5.2.2 Nanocarbon Materials Linked with Multiple Porphyrins	128
	5.2.3 Simple Electron Donor–Acceptor Dyads with Long CS Lifetimes	130
	5.3 Electron Donor–Acceptor Ensembles with Non-covalent Bonding	133
	5.3.1 – Interaction	133
	5.3.2 Porphyrin Nanochannels	136
	5.3.3 Supramolecular Electron Donor–Acceptor Complexes of Phthalocyanines	139
	5.4 Summary	142
	References	142
	6 Multifrequency EPR Spectroscopy: A Toolkitfor the Characterization of Mono- and Di-nuclear MetalIon Centers in Complex Biological Systems	145
	6.1 Introduction	145
	6.2 Multifrequency EPR Toolkit	146
	6.2.1 g-Value Resolution and Orientation Selection	148
	6.2.2 Magnitude of the Microwave Frequency	150
	6.2.3 State Mixing	150
	6.2.4 Angular Anomalies	150
	6.2.5 Distribution of Spin Hamiltonian Parameters	151
	6.2.6 Numerical Differentiation and Fourier Filtering	153