Supramolecular Chemistry 3rd ed

2667 Pages·2022·36.404 MB·English

by  Jonathan W. Steed, Jerry L. Atwood

Table of Contents
Cover
Title Page
Copyright Page
About the Authors
Preface to the Third Edition
Acknowledgements
About the Front Cover
About the Companion Website
CHAPTER 1: Concepts
1.1 DEFINITION AND DEVELOPMENT OF SUPRAMOLECULAR CHEMISTRY
1.2 CLASSIFICATION OF SUPERMOLECULE FORMATION
1.3 RECEPTORS, COORDINATION, AND THE LOCK AND KEY ANALOGY
1.4 BINDING CONSTANTS
1.5 COOPERATIVITY, MULTIVALENCY, AND THE CHELATE EFFECT
1.6 PREORGANISATION AND COMPLEMENTARITY
1.7 THERMODYNAMIC AND KINETIC SELECTIVITY, AND DISCRIMINATION
1.8 NATURE OF SUPRAMOLECULAR INTERACTIONS
1.9 SOLVATION EFFECTS
1.10 SUPRAMOLECULAR CONCEPTS AND DESIGN
1.11 PRACTICAL APPLICATIONS OF SUPRAMOLECULAR CHEMISTRY
SUMMARY
STUDY PROBLEMS
REFERENCES
CHAPTER 2: The Supramolecular Chemistry of Life
2.1 BIOLOGICAL INSPIRATION FOR SUPRAMOLECULAR CHEMISTRY
2.2 ALKALI METAL CATIONS IN BIOCHEMISTRY
2.3 PORPHYRINS AND TETRAPYRROLE MACROCYCLES
2.4 SUPRAMOLECULAR FEATURES OF PLANT PHOTOSYNTHESIS
2.5 UPTAKE AND TRANSPORT OF OXYGEN BY HAEMOGLOBIN
2.6 ENZYMES AND COENZYMES
2.7 SIGNALLING: NEUROTRANSMITTERS, HORMONES, AND PHEROMONES
2.8 DNA AND THE GENETIC CODE
2.9 BIOCHEMICAL SELF-ASSEMBLY
2.10 BIOMINERALISATION
2.11 EMERGENCE OF LIFE
SUMMARY
REFERENCES
CHAPTER 3: Cation-Binding Hosts
3.1 INTRODUCTION TO COORDINATION CHEMISTRY
3.2 PODANDS
3.3 THE CROWN AND LARIAT ETHERS
3.4 THE CRYPTANDS
3.5 THE SPHERANDS
3.6 NOMENCLATURE OF CATION-BINDING MACROCYCLES
3.7 SELECTIVITY OF CATION COMPLEXATION
3.8 SOLUTION BEHAVIOUR AND APPLICATIONS OF CROWNS AND CRYPTANDS
3.9 MACROCYCLE SYNTHESIS: THE TEMPLATE EFFECT AND HIGH DILUTION
3.10 SOFT LIGANDS FOR SOFT METAL IONS
3.11 PROTON BINDING: THE SIMPLEST CATION
3.12 COMPLEXATION OF ORGANIC CATIONS
3.13 ALKALIDES AND ELECTRIDES
3.14 THE CALIXARENES
3.15 CARBON DONOR AND π-ACID LIGANDS
3.16 THE SIDEROPHORES
SUMMARY
REFERENCES
CHAPTER 4: Anion Binding
4.1 INTRODUCTION
4.2 BIOLOGICAL ANION RECEPTORS
4.3 CONCEPTS IN ANION HOST DESIGN
4.4 CATIONIC RECEPTORS
4.5 NEUTRAL RECEPTORS
4.6 BORON BASED RECEPTORS AND LEWIS ACID CHELATES
4.7 METAL-CONTAINING RECEPTORS
4.8 ANION-BINDING HELICES
4.9 ANION TRANSPORT
SUMMARY
THOUGHT EXPERIMENTS
REFERENCES
CHAPTER 5: Ion-Pair Receptors
5.1 SIMULTANEOUS ANION AND CATION BINDING
5.2 LABILE COORDINATION COMPLEXES AND CAGES AS ANION HOSTS
5.3 RECEPTORS FOR ZWITTERIONS
SUMMARY
STUDY PROBLEMS
REFERENCES
CHAPTER 6: Molecular Guests in Solution
6.1 MOLECULAR HOSTS AND MOLECULAR GUESTS
6.2 INTRINSIC CURVATURE: GUEST BINDING BY CAVITANDS
6.3 CYCLODEXTRINS
6.4 MOLECULAR TWEEZERS, CLIPS AND CLEFTS
6.5 CYCLOPHANE HOSTS
6.6 CONSTRUCTING A SOLUTION HOST FROM CLATHRATE-FORMING BUILDING BLOCKS: THE
CRYPTOPHANES
6.7 COVALENT CAGES: CARCERANDS AND HEMICARCERANDS
6.8 COORDINATION CAGES
6.9 HALOGEN-BONDED COMPLEXES
SUMMARY
STUDY PROBLEMS
THOUGHT EXPERIMENT
REFERENCES
CHAPTER 7: Solid-State Inclusion Compounds
7.1 NOMENCLATURE AND THERMOCHEMICAL ASPECTS
7.2 POROSITY AND GAS SORPTION
7.3 CLATHRATE HYDRATES
7.4 UREA AND THIOUREA CLATHRATES
7.5 CHANNEL CLATHRATES
7.6 POLARITY FORMATION
7.7 HYDROQUINONE, PHENOL, DIANIN’S COMPOUND, AND THE HEXAHOST STRATEGY
7.8 MACROCYCLIC CLATHRATES
7.9 COVALENT CAGES
7.10 GAS SORPTION BY COORDINATION COMPLEX HOSTS
SUMMARY
STUDY PROBLEMS
REFERENCES
CHAPTER 8: Crystal Engineering
8.1 CONCEPTS
8.2 CRYSTAL NUCLEATION AND GROWTH
8.3 UNDERSTANDING CRYSTAL STRUCTURES
8.4 THE CAMBRIDGE STRUCTURAL DATABASE
8.5 POLYMORPHISM
8.6 CO-CRYSTALS
8.7 SOLID STATE TRANSFORMATIONS
8.8 CRYSTAL STRUCTURE PREDICTION
8.9 COMMON AND EXOTIC SUPRAMOLECULAR SYNTHONS
8.10 HALOGEN BONDING
8.11 BENDING AND JUMPING CRYSTALS
SUMMARY
STUDY PROBLEMS
THOUGHT EXPERIMENT
REFERENCES
CHAPTER 9: Network Solids
9.1 WHAT ARE NETWORK SOLIDS?
9.2 ZEOLITES
9.3 LAYERED SOLIDS AND INTERCALATES
9.4 IN THE BEGINNING: HOFFMAN INCLUSION COMPOUNDS AND WERNER CLATHRATES
9.5 COORDINATION POLYMERS
9.6 POROUS METAL–ORGANIC FRAMEWORKS
9.7 COVALENT ORGANIC FRAMEWORKS
SUMMARY
STUDY PROBLEM
REFERENCES
CHAPTER 10: Self-Assembly
10.1 INTRODUCTION
10.2 PROTEINS AND FOLDAMERS: SINGLE-MOLECULE SELF-ASSEMBLY
10.3 BIOCHEMICAL SELF-ASSEMBLY
10.4 SELF-ASSEMBLY IN SYNTHETIC SYSTEMS: KINETIC AND THERMODYNAMIC CONSIDERATIONS
10.5 HELICATES AND HELICAL ASSEMBLIES
10.6 SELF-ASSEMBLING COORDINATION COMPOUNDS
10.7 SELF-ASSEMBLY OF CLOSED COMPLEXES BY HYDROGEN BONDING
10.8 TEMPLATED ASSEMBLY OF PORPHYRIN ARRAYS
10.9 PROGRAMMED ASSEMBLY WITH BIOMOLECULES
SUMMARY
STUDY PROBLEMS
THOUGHT EXPERIMENT
REFERENCES
CHAPTER 11: The Mechanical Bond
11.1 SCOPE AND IMPORTANCE OF MECHANICAL BONDING AND MECHANOSTEREOCHEMISTRY
11.2 CATENANES AND ROTAXANES
11.3 MOLECULAR KNOTS
11.4 BORROMEAN RINGS AND MULTIPLY INTERLOCKED CATENANES
11.5 INTERPENETRATED CAGES
11.6 AN UNUSUAL THRING
SUMMARY
STUDY PROBLEM
REFERENCES
CHAPTER 12: Molecular Devices and Machines
12.1 INTRODUCTION
12.2 SUPRAMOLECULAR PHOTOCHEMICAL DEVICES
12.3 INFORMATION AND SIGNALS: SEMIOCHEMISTRY AND SENSING
12.4 MOLECULE-BASED ELECTRONICS
12.5 MOLECULAR ANALOGUES OF MECHANICAL MACHINES
SUMMARY
STUDY PROBLEMS
REFERENCES
CHAPTER 13: Biological Mimics and Supramolecular Catalysis
13.1 INTRODUCTION
13.2 CYCLODEXTRINS AS ENZYME MIMICS
13.3 CORANDS AS ATPASE MIMICS
13.4 CATION-BINDING HOSTS AS TRANSACYLASE MIMICS
13.5 METALLOBIOSITES
13.6 ENZYME MIMETIC MATERIALS
13.7 ION CHANNEL MIMICS
13.8 SUPRAMOLECULAR CATALYSIS
SUMMARY
THOUGHT EXPERIMENT
REFERENCES
CHAPTER 14: Interfaces and Liquid Assemblies
14.1 ORDER IN LIQUIDS
14.2 SURFACTANTS AND INTERFACIAL ORDERING
14.3 LIQUID CRYSTALS
14.4 POLYAMORPHOUS LIQUIDS
14.5 IONIC LIQUIDS AND DEEP EUTECTIC SOLVENTS
14.6 LIQUID CLATHRATES
14.7 POROUS LIQUIDS
SUMMARY
STUDY PROBLEMS
REFERENCES
CHAPTER 15: Supramolecular Materials
15.1 INTRODUCTION
15.2 DENDRIMERS
15.3 FRACTAL ASSEMBLIES
15.4 COVALENT POLYMERS WITH SUPRAMOLECULAR PROPERTIES
15.5 SELF-ASSEMBLED SUPRAMOLECULAR POLYMERS
15.6 MECHANICALLY INTERLOCKED MATERIALS
15.7 SUPRAMOLECULAR GELS
15.8 POLYMERIC LIQUID CRYSTALS
15.9 BIOLOGICAL SELF-ASSEMBLED MATERIALS
SUMMARY
STUDY PROBLEMS
REFERENCES
CHAPTER 16: Dynamic Covalent Bonding and Complex Systems
16.1 CHEMISTRY OUT OF EQUILIBRIUM
16.2 DYNAMIC COMBINATORIAL LIBRARIES
16.3 SELF-REPLICATION
16.4 SHAPESHIFTING MOLECULES
16.5 DISSIPATIVE SELF-ASSEMBLY
SUMMARY
REFERENCES
CHAPTER17 Nanochemistry
17.1 WHEN IS NANO REALLY NANO?
17.2 NANOTECHNOLOGY: THE ‘TOP-DOWN’ AND ‘BOTTOM-UP’ APPROACHES
17.3 TEMPLATED AND BIOMIMETIC MORPHOSYNTHESIS
17.4 NANOSCALE PHOTONICS
17.5 MICROFABRICATION, NANOFABRICATION AND SOFT LITHOGRAPHY
17.6 ASSEMBLY AND MANIPULATION ON THE NANOSCALE
17.7 NANOPARTICLES
17.8 ENDOHEDRAL FULLERENES, NANOTUBES AND GRAPHENE
SUMMARY
THOUGHT EXPERIMENT
REFERENCES
Index
End User License Agreement
List of Tables
Chapter 1
TABLE 1.1 Timeline of supramolecular chemistry.
TABLE 1.2 Examples of different types of supramolecular assembly. (a) The h...
TABLE 1.3 Discovery and properties of key macrocyclic receptors.
TABLE 1.4 Binding constants for a range of complexation processes.
TABLE 1.5 Comparison of four different 1 : 2 binding models in the analysis...
TABLE 1.6 Thermodynamic parameters for Zn2+ complexes of 1.7 and 1.8 (298 K...
TABLE 1.7 Properties of hydrogen bonded interactions.
TABLE 1.8 The Hofmeister series.
TABLE 1.9 Influence of solvent on the binding constant of host1.16 for the ...
Chapter 2
TABLE 2.1 Some examples of biochemical Na+ and K+ distributions.
TABLE 2.2 LogK values for alkali metal ion binding by naturally occurrin...
11
TABLE 2.3 Role and distribution for some vitamin and non-vitamin coenzymes.
TABLE 2.4 The genetic code.
TABLE 2.5 Key biominerals.36
Chapter 3
TABLE 3.1 Stability constants (logK) in aqueous solution for metal complexe...
TABLE 3.2 Correlation of ionic charge with affinity for EDTA4−.
TABLE 3.3 Correlation of ionic radius with affinity for EDTA4−; Mg2+ ...
TABLE 3.4 Thermodynamic contributions to the stabilities of podate and crow...
TABLE 3.5 Comparison of the diameters of different crown ethers with the io...
TABLE 3.6 Binding free energies (kcal mol−1; 1 kcal = 4.184 kJ) for a...
TABLE 3.7 Complexation and decomplexation rate constants of picrate salts f...
TABLE 3.8 Dependence of reaction rate with A = CH CO − on added crow...
3 2
TABLE 3.9 Nucleophilicity of various anions (A−) in the presence of [...
TABLE 3.10 Comparative binding constants (logK ) for hard and soft metal i...
1
TABLE 3.11 Thermodynamic parameters for Ag+ binding by various ligands in m...
TABLE 3.12 Binding constants for Ag+, K+, and Tl+ for various cryptands.
TABLE 3.13 Comparison of the binding constants (logK) of cyclam and tetrame...
TABLE 3.14 Basicity constants for some representative polyamines.
TABLE 3.15 Complexation free energies for corand receptors with ammonium io...
TABLE 3.16 Complexation-free energies for spherand-type receptors with ammo...
TABLE 3.17 Free energy of complexation (–∆Go/kJ mol−1) of neutral an...
TABLE 3.18 Selective phase transport of metal cations by calixarenes from b...
TABLE 3.19 pM values and binding constants for Fe3+ chelate ligands in aque...
Chapter 4
TABLE 4.1 Properties of some common anions and cations (ionic radii in part...
TABLE 4.2 Classification and key examples of anion-binding functional group...
TABLE 4.3 Binding constants (logK) for the stepwise formation of ‘supercomp...
TABLE 4.4 Variation of third and fourth pK values with spacer length in m...
a
TABLE 4.5 Differences between carrier and channel transporters.154
Chapter 5
TABLE 5.1 Extraction constants (K ) of K+ salts of various anions either ...
ex
Chapter 6
TABLE 6.1 Dimensions of the CB[n] and iCB[n] families.34
TABLE 6.2 Key developments in glycoluril macrocyclic chemistry.37
TABLE 6.3 Characteristics of α -, β -, and γ -cyclodextrin...
TABLE 6.4 Binding constants (/M−1) of quinone and related guests by h...
TABLE 6.5 Pillarene shape based on van der Waals radii.
TABLE 6.6 Thermodynamic parameters for guest binding by cryptophanes in (CD...
TABLE 6.7 Occupancy factors (ρ) for cryptophane complexes.a
Chapter 7
TABLE 7.1 Hydrate structure types, unit cell contents and cage types (D = d...
TABLE 7.2 Inclusion compounds ofp-t-butylcalix[4]arene.97
Chapter 8
TABLE 8.1 Optimal distances and interactions energies for representative sup...
TABLE 8.2 A representative periodic table of pK values for hydrogen bond b...
HB
TABLE 8.3 Different supersaturation levels lead to different growth mechanis...
TABLE 8.4 Symmetry notation in the Schoenflies and Herman–Maugin systems com...
TABLE 8.5 Common space groups (and hence forms of crystal packing in molecul...
TABLE 8.6 Co-crystals in clinical development and on market.104
TABLE 8.7 Complementary experimental and theoretical techniques in crystal s...
Chapter 9
TABLE 9.1 Characteristics of some common zeolite framework topologies.
TABLE 9.2 Templating cations and the resulting zeolites.
TABLE 9.3 Classes of layered solids.
Chapter 10
TABLE 10.1 Self-assembly parameters for cycles10.6 – 10.8 (room temperature,...
TABLE 10.2 Equilibria, binding constants, extended site binding model parame...
Chapter 12
TABLE 12.1 Common redox transducers in supramolecular voltammetric sensor de...
TABLE 12.2 Truth table and symbols for some common Boolean logic operations ...
Chapter 13
TABLE 13.1 Structure and function of some representative binuclear enzymes s...
TABLE 13.2 Examples showing the scope of metal-containing enzyme mimic mater...
List of Illustrations
Chapter 1
FIGURE 1.1 Comparison between the scope of molecular and supramolecular chem...
FIGURE 1.2 Important early macrocyclic complexes.
FIGURE 1.3 Types of supramolecular assembly process. (a) Synthesis and guest...
FIGURE 1.4 (a) Paul Erhlich (1854–1915) recipient of the 1908 Nobel Prize in...
FIGURE 1.5 (a) Rigid lock and key and (b) induced fit models of enzyme–subst...
FIGURE 1.6 Structures of methylene blue and salvarsan along with a cell from...
FIGURE 1.7 Werner and historical chain formulations of ‘Co(NH ) Cl ’ and ‘Co...
3 4 3
FIGURE 1.8 Simulated Job plots for 1 : 1 (column 2, K = 0) and various ca...
12
FIGURE 1.9 (a) Binding of two Mg2+ cations by a ditopic receptor. (b) Possib...
SCHEME 1.1 Competing equilibria in a potentiometric titration.
FIGURE 1.10 Distribution diagram for the Cu2+–Zn2+–ligand L system determine...
FIGURE 1.11 (a) NMR titration plot (isotherm) and corresponding speciation p...
FIGURE 1.12 UV-monitored titration of diisobutyl-acridono-18-crown-6 with Pb
FIGURE 1.13 ITC data at 25 °C for the binding of by calix[4]pyrrole in ni...
FIGURE 1.14 (a) Aqueous solutions of caesium picrate (top layer) showing how...
FIGURE 1.15 van’t Hoff plot for the encapsulation of aqueous alkylammonium c...
FIGURE 1.16 Mechanism by which multivalent ligands can interact with cell-su...
FIGURE 1.17 Ring size dependence of the stabilisation offered by the chelate...
FIGURE 1.18 Supramolecular host–guest complexation stabilised by positive co...
SCHEME 1.2 Allosteric (cooperative) enhancement of Na+ binding by preorganis...
SCHEME 1.3 Equilibrium constants (K) for multiple ligands (L) binding to a s...
FIGURE 1.19 (a) Hill plot and (b) Scatchard plot for the successive intermol...
SCHEME 1.4 An anion/cation tetratopic receptor exhibits strongly negative co...
SCHEME 1.5 Comparison of preorganisation effects in K+ binding by a macrobic...
FIGURE 1.20 Comparison of the effects of preorganisation and complementarity...
FIGURE 1.21 (a) The NaCl ionic lattice. (b) Supramolecular ion–ion interacti...
FIGURE 1.22 (a) Dipole–dipole interactions in carbonyls. (b) The n–π* in...
FIGURE 1.23 X-ray crystal structure showing C–H⋯N (2.21 Å) and C–H⋯O (2.41 Å...
FIGURE 1.24 Various types of donor (D) acceptor (A) hydrogen bonding geometr...
FIGURE 1.25 (a) Secondary interactions providing attractions between neighbo...
FIGURE 1.26 (a) Primary and secondary hydrogen bond interactions between gua...
FIGURE 1.27 AFM image purporting to show direct hydrogen bonding along with ...
FIGURE 1.28 (a) The electrostatic origin of the cation–π interaction. Top: t...
FIGURE 1.29 Anion-π interactions involving electron-deficient aromatic rings...
FIGURE 1.30 (a) Limiting types of π–π interaction. Note the offset to the fa...
FIGURE 1.31 X-ray crystal structure of the discrete coordination cage [Cd (
16
FIGURE 1.32 Interacting π-quadrupoles.
FIGURE 1.33 Sixfold edge-to-face phenyl embrace in ClGePh .96
3
FIGURE 1.34 X-ray crystal structure of a typical van der Waals inclusion com...
FIGURE 1.35 Molecular electrostatic potential isodensity surface of CF X (fr...
3
FIGURE 1.36 (a) Bromide binding by a tripodal halogen bonding receptor.104 (...
FIGURE 1.37 Halogen and chalcogen bonding in Ph Se ·I .109
2 2 2
FIGURE 1.38 Examples of closed shell interactions: (a) aurophilic interactio...
FIGURE 1.39 Molecular orbital description of secondary bonding and related i...
FIGURE 1.40 A Venn diagram illustrating Stoddart’s classification of differe...
FIGURE 1.41 Hydrophobic binding of organic guests in aqueous solution. (a) T...
FIGURE 1.42 Solvation considerations during host–guest complexation.
FIGURE 1.43 The four isolated isomers of hemicryptophane 1.19 showing the tw...
FIGURE 1.44 Axially and helically chiral systems showing both helical enanti...
FIGURE 1.45 Planar chiral cavicularin, organometallic 1.20 which forms a fou...
FIGURE 1.46 High-yield, chiral auxiliary approach to topologically chiral ca...
FIGURE 1.47 (a) Magnetic field-induced self-assembly of iron oxide nanocubes...
SCHEME 1.6 Experimental resolution of [Co(en) ]3+ using optically pure (+)ta...
3
FIGURE 1.48 The 1935 use of chirality by complexation of the achiral meso-di...
FIGURE 1.49 (a) A termite mound in Australia’s Northern Territory. Termite m...
FIGURE 1.50 (a) TEM micrograph showing gold nanoparticles. Note the regular ...