a few questions - persönliche webseitenhomepage.univie.ac.at/jeanluc.mieusset/supramolecular...
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A few questions
• What are the main supramolecular interactions? What are their properties?
• What is preorganization, complementarity?
• What is a receptor, a carrier?• Example for a receptor for an amino acid.
• How to synthesize a macrocycle? Examples for efficient syntheses of macrocycles.
• How to synthesize a supramolecular cube, a catenane, a rotaxane?
• The properties of dendrimers? • Example for a molecular machine.
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Wires and Related Systems
• Balzani, V.; Venturi, M.; Credi, A.Molecular Devices and Machines, Chapter 2-6
Host Syntheses
• See on the slide
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Wires and Related Systems
• Conductivity measurements on single molecule
• Replacement of some octanethiol molecules with 1,8-octanedithiol molecules and incubation with gold nanoparticles
• Observation with an atomic force microscope
• Resistance of a single octanedithiol molecule: 900 MΩ
.
Moore, Science, 2001, 294, 571
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Photoinduced Electron Transfer
Rate constant: kel α exp(-βelrAB) with
• rAB : distance between A and B
• βel : attenuation factor = ca. 5 Å-1 in vacuum. Less if A and B are separated by matter (ca. 1 Å-1 for saturated compounds and ca. 0.5 Å-1 for oligophenylenes).
• Favorated by a bridge with a low lying LUMO
*A--L--B
A+--L---B
A+--L--B-
Hfe
Hie
E
State diagram illustrating the superexchange interaction between an electron donor A, an acceptor B through a bridge L
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Photoinduced Electron TransferElectronic WiresFrom Ru(II) to Rh(III) through a 3MLCT
excited state• Exponential decrease of the rate constant
for the homogeneous serie 25+-45+.• 15+ slower due to a higher LUMO of the
bridge.
• 55+ slower due to twisting of the central phenylene unit (sterical reasons).
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Photoinduced Electron Transfer
1 and 2 : Distance dependant superexchange mechanism (tunneling)
3 – 5 : Bridge assisted hopping dynamics, wire-like (LUMO of the bridge similar to the LUMO of tetracene).
Wasielewski, Nature, 1998, 396, 60. JACS, 2001, 123, 7877.
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Energy transfer
• Two different mechanisms
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Energy Transfer
Resonance Mechanism
• Also called trough-space, Förster-Type or Coulombicmechanism.
• Long range mechanism based on dipole-dipole coupling (1/r6
dependence on the distance).
• Efficient when both partners have high oscillator strengths, good spectral overlap, and a correct orientation.
• Förster-Radius (50 % transmission): 4.9 nm for Cyan Fluorescent Protein – Yellow Fluorescent Protein
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Energy Transfer
Exchange Mechanism
• Also called Dexter-Type or through-bond mechanism.
• Requires orbital overlap, exponentially dependant on distance.
• Spin selection rule: spin conservation in the reacting pair• Efficient for triplet-triplet energy transfer, for example.
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Energy Transfer
Photonic Wires
• Transfer from Ru(II) to Os(II) by a superexchange mechanism
• Rate constants are higher than the one expected for a resonance mechanism
• Exponential decrease of the rate with increasing length
• A further increase of the number of phenylene unit should lower the triplet state, switching the mechanism to wire-like.
Balzani, JACS, 1999,121,4207.
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Energy Transfer
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Energy Transfer
Cascade hopping mechanism
• The transfer can be slowed down (80 times) by oxidation of the anthracene unit.
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Energy Transfer
• Delocalization in a giant chromophore
• The energy levels of the spacer and the donor are similar mixing occurs.
• The excitation is then trapped by the anthraceneunit.
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Switches
Definition 1 (strict):
• A device incorporated in a molecular wire that can reversibly interrupt the electron or energy transfer.
Definition 2 (large):
• Any molecular system that can be reversibly interconverted between two (or more) different states. (Definition 1 + molecular devices)
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Switches
Switching under thermodynamic control
• e.g., temperature change
• Solvent effects
• Changes in electrochemical potential• pH change, (ph indicators)
no barrier, can not be locked in
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Switches
Switching under kinetic control
• Separated by some kinetic barriers
• Usually controlled photonically (or chemically).
• Ranges from picoseconds (electronic excited states) to years• Exit is usually achieved by a second stimulus
can be locked in
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Switches
A good switch must be:
• Thermally stable,both isomers should not return to the initial state in the dark
• Fully reversible
• Fatigue resistant1000 cycles can be done with the actual switches, it corresponds to a side reaction quantum yield of ca. 0.001
• Show an important change in its electronic properties
Irie, Chem. Rev. 2000, 100, 1685
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Switches
The classical, optimized example:The reversible photoisomerization of 1,2-bis-(3-thienyl)ethene derivatives
• OFF: open-ring isomer aπ- electrons are localized in the thiophene ring
• ON: closed ring isomer bπ-electrons are delocalized through the whole unit.The electronic interaction between the X and Y substituents increases.
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Switches
The stilbene-dihydrophenanthrene system
This parent system is not useful because :
• Returns to stilbene in the dark
• Easily oxidized in the presence of air
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Switches
Photoelectrochemical switching• No electrochemical process in the open isomer 51a• A reversible reduction wave at –230 mV in the closed form 51b
electron flow can be controlled by photoirradiation
352 nm
662 nm
Irie, Chem. Rev. 2000, 100, 1685
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Switches
Switching of photoinduced electron transfer
ON OFF
• ON in the open formDirect electron transfer between the substituents.
• OFF in the closed form
The bridge competes successfully for the energy transfer, but further transfer is thermodynamically forbidden.
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Switches
Switching Energy-Transfer Processes
• Photon inputs
4 different chromophores quite difficult to handle
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Switches
Switching Energy-Transfer Processes
• Redox inputs• The switch must not be in the
main chain
• Oxidation of MgP to MgP.+ (E = +0.34V) quenches the fluorescence.
• Can also be performed chemically (Ferric perchlorate)
BDPY: Boron-dipyrromethene dye
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Multistate-Multifunctional Systems
Write-Lock-Read-Unlock-Erase Cycles
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Computing at the molecular level
Stoddart, Structure and bonding, 2001, 99, 190.
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Photoinduced Charge Separation
A liposome-based proton pump
Moore, Nature, 1997, 385, 239.
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Photoinduced Charge Separation
Light-driven Production of ATP
Moore, Nature, 1998, 392, 479.
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Thiacalixarenes
• A readily accessible cavity, slightly bigger than calix[4]arene
Miyano, Chem. Rev. 2006, 106, 5291
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Thiacalixarenes
• Rotation can be blocked by substituents bulkier than propyl
Miyano, Chem. Rev. 2006, 106, 5291
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Thiacalixarenes
• Toward chiral host compounds
Miyano, Chem. Rev. 2006, 106, 5291
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Dynamic Covalent Synthesis
Warmuth, JACS, 2006, 128, 14120.
• The small capsules are first kinetic products among a mixture of oligomeric(4-9 units) cavitands. (after ca. 1h reaction time).
• No linear oligomersare present; unreactedgroups are disfavored by 4 kcal/mol.
• Slight differences in the solvation lead to different products (a polar solvent lead to a small capsule).
82 %
35 %
65 %
yield
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Dynamic Covalent Synthesis
Warmuth, JACS, 2006, 128, 14120.
The entropically most favorable capsule:
• Use of the flexible or preorganized diamines 9-14 lead almost quantitatively to the dimer.
• Use of ethylene diamine as a bridge does not lead to dimer formation, probably because it prefers an anti conformation
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Synthesis of Macrocycles
Macrocyclic Schiff-Base Synthesis
• Aliphatic dicarbonyl compounds low hydrolytic stability• Aromatic and heteroaromatic dicarbonyl compounds hydrolytically stable,
easier to chromatography
• Aliphatic diamines most nucleophilic and most flexible
• Cycloaliphatic diamines nucleophilic and rigid• Aromatic diamines slightly nucleophilic and rigid
e.g., the reaction of o-phenylenediamine can be stopped after one condensation. The second step requires acid catalysis. Ustynyuk, Chem. Rev. 2007, 107, 46.
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Synthesis of Macrocycles
Macrocyclic Schiff-Base Synthesis• A reversible reaction leading first to a mixture of mainly cyclic oligomers.
• Prolonged stirring lead to the thermodynamically most stable compound(s).• The yields and even the obtained products are strongly dependant of the
reaction conditions (solvent, catalyst, ….): optimization is required
• The dynamic combinatorial library generated requires usually separation by HPLC
• The macrocycles are often reduced to the amine in order to obtain a stable product. After protonation, reversed-phase HPLC may be used.
Often templated by a metal ion
• Pro: really efficient
• Con: The better templates are also difficult to be removed.• Con: Metal ion are small only for small macrocycles
Ustynyuk, Chem. Rev. 2007, 107, 46.
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Synthesis of Macrocycles
And up to [7+7]Realized under high-dilution conditions
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Synthesis of Macrocycles
Macrocyclic Schiff-base synthesis without an efficient template:
• [1+1] condensation only if the two reactants are perfectly matched • Orientation of the end groups
• Size of the reactants
• Rigidity
• [2+2] condensation is obtained in the standard case
• The obtained macrocycle is usually already flexible enough to be free of strain
• It is favored by entropy (minimization of the number of molecules implicated)
Ustynyuk, Chem. Rev. 2007, 107, 46.
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Synthesis of Macrocycles
• [1+1] condensation
y=74-92%
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Synthesis of Macrocycles
[3+3] condensation
• Trans-1,2-diaminocyclohexane possesses a 60o dihedral (angles).
• Connection with rigid linear rods (180o, edges) leads to formation of a triangle.
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Synthesis of Macrocycles
[6+6] condensation
• Reaction performed in dichloromethane
• Macrocyclestabilized by theH-bridges
• Product is insoluble and driven out of the equilibrium
MacLachlan, Chem. Commun., 2006, 2480–2482
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Synthesis of Macrocycles
Anionic template effect
• Usually does not affect the structure of the product nor the yield
• The pyrrol unit is able to build an H-bridge with anions The equilibrium may be shifted.
• But not in MeOH, protic solvents compete for the formation of H-bridges
Ustynyuk, Chem. Rev. 2007, 107, 46
75%
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Synthesis of Macrocycles
• Anionic template effect; rearrangement in MeCN within 5 days
• Strongly binds sulfate and phosphate in MeCN (but not nitrate nor halogenides)
Ustynyuk, Chem. Rev. 2007, 107, 46
quantitative
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Synthesis of Macrocycles
Hydrazone Dynamic Combinatorial Chemistry
• Hydrazone exchange is reversible under acidic conditions
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Synthesis of Macrocycles
Hydrazone Dynamic Combinatorial Chemistry
• Under acidic conditions, the acetal is deprotected and exchange is starting.
Sanders, Org. Biomol. Chem., 2003, 1, 1625.
p
PF
pPF3
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Synthesis of Macrocycles
Hydrazone Dynamic Combinatorial Chemistry
• Amplification of the trimer by a Li or Na template
• pPF3 is a good host for:Li : 10000 M-1
Na: 19000 M-1
in chloroform/methanol 98/2
Sanders, Org. Biomol. Chem., 2003, 1, 1625.
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Synthesis of Macrocycles
Hydrazone Dynamic Combinatorial Chemistry
• Acetylcholin (Ach) amplificates a catenane.y = 67%
Sanders, Science, 2005, 308, 667.
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46
Synthesis of Macrocycles
Hydrazone Dynamic Combinatorial Chemistry
Sanders, Science, 2005, 308, 667.
• A receptor with a 100 nM affinity for acetylcholine:K = 1.4 x 107 M-1 in CHCl3/MeOH 95/5
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47
Synthesis of Macrocycles
• NMR without Ach:Broad signals several conformers slowly interconverting (rotating) on the NMR time scale
• With Ach:Sharp signals Ach selects only one conformation
Sanders, Science, 2005, 308, 667.
Hydrazone Dynamic Combinatorial Chemistry
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48
Synthesis of Macrocycles
Hydrazone Dynamic Combinatorial Chemistry
Sanders, Science, 2005, 308, 667.
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49
Synthesis of Macrocycles
Disulfide exchange
• Quenched by lowering the pH
• Pro: has the potential to be easily decomposed (metabolized).
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50
Synthesis of Macrocycles
Disulfide exchange
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51
Synthesis of Macrocycles
Disulfide Dynamic Combinatorial Library (DCL)
• Use of 3 rigid building blocks suitable for cation-pi interactions
• Soluble in water under basic conditions
• Use of high template concentration leads to a preferred amplification of the small oligomers over the higher ones.
Sanders, JACS, 2005, 127, 9392.
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52
Synthesis of Macrocycles
Induced-Fit Hosts
• Strong amplification high binding constant (4 x 106 M-1 in borate buffer, pH 9)
• The best host may not be the main product.
Sanders, JACS, 2005, 127, 9392.
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53
Synthesis of Macrocycles
Induced-Fit Hosts
Sanders, JACS, 2005, 127, 9392.
Figure 6. a) The host 3 and its guest in an extended conformation, b) the same host and guest in a folded conformation, c) a cartoon representation of b, showing a rationalisation of the observed diastereoisomerism.
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54
Synthesis of Macrocycles
Catalysts from DCLsfor a Diels-Alder reaction
• Use of an analogous of the transition state as a template for the host (catalyst) synthesis
• Product = transition state analogue (very roughly)
• The host accelerates the Diels-Alder reaction (10 times)
• But it has a low turn-overreactant: K = 130000 M-1
product: K = 240000 M-1Sanders, Angew. Chem. IE 2003, 42, 1270.
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55
Synthesis of Macrocycles
DCL of porphyrin disulfides
• Selective amplification of the dimer, trimer and tetramer by using different templates
• Performed in chloroform
• Templating with neutral molecules remains a difficult task lack of strong interactions
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Multivalency
Reinhoudt, Langmuir, 2002, 18, 6988. JACS, 2000, 122, 4963.
• The observed rupture forces are multiples of 55 pN.
• The ferrocenesdecomplex and rebind spontaneously on the AFM time scale. (1 ms).
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57
Multivalency
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58
Molecular Printboards
Multivalency, toward strong interactions• Densely packed SAM due to the reversibility of the interactions
• Kinetically stable assembly, cannot be washed out by CD solutions.
Wolfgang Knoll, Reinhoudt, Langmuir, 2005, 21, 7866.
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59
Molecular Printboards
Layer by layer Assembly
• Mean Au particle size: 2.8 nm (TEM)
• Realized at pH 2 protonation of the PPI dendrimers water soluble dendrimers in their extended conformation
Reinhoudt, Chem. Soc. Rev. 2006, 35, 1122.
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Unidirectional Rotors
An altitudinal rotor on Au(111)
• Molecules immobile over hours as shown by STM.
• Rotates when placed in an alternating electric field. (STM tip)
Michl, JACS, 2004, 126, 4540; Chem. Rev. 2005, 105, 1281.
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61
Artificial Motors
Molecular muscles
• Powered with Fe(ClO4)3/ascorbic acid
Stoddart, JACS, 2005, 127, 9745. Balzani, Chem. Soc. Rev., 2006, 35, 1135
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62
Artificial Motors
Molecular Muscles• Fixed on a flexible gold coated cantilever
(500 x 100 x 1 µm)
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63
Artificial Motors
Single Molecule Force Spectroscopy
• Based on the photoisomerization of cis/trans azobenzenecis-azobenzene: 1.0 nmtrans-azobenzene: 1.1 nm
• Length change: 3% for n= 46
• Can be shortened against a load of 400 pNwith 120 photons of λ = 365 nm Total efficiency = 0.07 %
Gaub, Macromolecules, 2003, 36, 2015.
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Artificial motors
Crowded-alkene based helical motors
• Light-driven
• Unidirectional
Feringa, JACS, 2006, 128, 5127.Chem. Soc. Rev. 2007, 36, 77.
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65
Artificial Motors
• Bulky substituents accelerate the rotation.
• Larger increase of the energy in the ground state than in the transition state. the fastest thus far
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66
Nanocars
• Translation perpendicular to the axles1 min per images at 200°C
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67
Nanocars
Tour, JACS, 2006, 128, 4854.Chem. Soc. Rev. 2006, 35, 1043.
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Motorized Nanocars
Con of fullerene wheels:
• Strong absorbption at 365 nm
• Low solubility
• Difficult to connect• Bind strongly to the Au surface
Replacement by p-carborane
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Molecule Carrier
Anthraquinone as a cargo for CO2
• Transforms the diffusion of CO2 on Cu(111) from isotropic to linear.
• The interaction is mediated by the substrate (0.12 eV).
• 1eV = 96.5 kJ/mol.
Bartels, Science, 2007.
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Molecule Carrier