Supramolecular chemistry II
Supramolecular chemistry is a rapidly growing field, which has had remarkable impact on the life sciences on one hand and on materials sciences on the other. In the life sciences, the networks of noncovalent interactions between the constituents of cells, for example, have shifted into the current focus. Self-assembly, templation, self-sorting and multivalent binding all contribute to setting up the extremely complex architecture of a cell. But the same concepts are useful for generating materials with function, when for example the building blocks are programmed appropriately to find their places in a larger, noncovalent architecture. The basis for all these concepts is molecular recognition. Recently, many studies have been devoted to quantifying host–guest interactions, aiming at a more profound understanding of the subtle entropic and enthalpic effects that govern the interactions between host and guest.
See also the Thematic Series:
Supramolecular chemistry
Superstructures with cyclodextrins: Chemistry and applications IV
- Full Research Paper
- Published 02 Sep 2011
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Figure 1: Anion receptors 1–4 together with their atomic numbering scheme.
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Figure 2: 1H NMR spectra of 1 in the absence of anions (a) and upon addition of one equivalent of the followi...
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Figure 3: Three representative conformational families of rotamers of 1. Notations refer to the orientations ...
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Figure 4: NOE enhancements of 1 in the absence of anions (a) and upon addition of one equivalent of acetate a...
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Figure 5: Surface plot of the relative potential energy of 1 as a function of the two constitutive [C6–C7–N7α...
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Figure 6: Freely optimized structure at the B3LYP/6-311+G(d,p) level of theory and side view showing deviatio...
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Figure 7: 1H NMR chemical shift changes, Δδ = δ (in the presence of anions) – δ (in the absence of anions), i...
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Figure 8: Freely optimized structures at the B3LYP/6-311+G(d,p) level of theory and side view showing deviati...
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Figure 9: Conformational preferences and proposed binding mode for the 3·AcO− 1:1 complex.
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- Full Research Paper
- Published 22 Nov 2011
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Figure 1: Schematic representation of the general structural design of the investigated cyclodextrin derivati...
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Scheme 1: Structure of cyclosarin (GF).
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Scheme 2: Cyclodextrin derivatives tested as potential GF scavengers.
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Scheme 3: General strategies used for the preparation of the investigated cyclodextrin derivatives.
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Scheme 4: Reaction conditions used for the preparation of cyclodextrin derivatives 1a–e from tosylate 3.
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Scheme 5: Synthesis of 3-(aminomethyl)benzaldehyde oxime (5). Reagents and conditions: i. NaBH4, EtOH, 1 h, 2...
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Scheme 6: Synthesis of 3-((hydroxyimino)methyl)-1-(prop-2-ynyl)pyridinium bromide (6). Reagents and condition...
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Scheme 7: Syntheses of 6-ethynyl-formylpyridine oximes (7a–c). Reagents and conditions: i. CuI, (PPh3)2PdCl2,...
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Scheme 8: Reaction conditions used for the preparation of cyclodextrin derivatives 2a–d from azide 4.
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Figure 2: Diagram summarizing the observed Δk1 values for cyclodextrins 1a–e and 2a–d. For comparison, the re...
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Figure 3: Time-dependent decrease of GF concentration in the presence of 1b (top row), 1c (middle row), and 2a...
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Scheme 9: Schematic protocol for the qualitative assay.
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Scheme 10: Schematic protocol of the quantitative assay.
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- Letter
- Published 22 Nov 2011
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Scheme 1: Self-sorting in a six-component library [8].
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Scheme 2: Self-sorting in a five-component library. We used 2 in a slightly different form with Zn2+ (R = 4-C6...
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Figure 1: Ligands used in the present study.
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Scheme 3: Synthesis of the triangular assembly T (only syn shown).
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Figure 2: ESI-MS of triangle T in acetonitrile along with the isotopically resolved peak at 666.8 (black: Exp...
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Figure 3: Partial 1H NMR (400 MHz, 298 K, CD3CN) spectra of an equimolar mixture of 5, 6, and 7 in the presen...
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Figure 4: Differential pulse voltammogram of T in acetonitrile (0.1 M n-Bu4NPF6 as electrolyte, Ag wire as a ...
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Figure 5: Two representations of the energy-minimised structure of the scalene triangle T (anti); copper(I) i...
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- Full Research Paper
- Published 22 Nov 2011
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Scheme 1: Compounds studied with the voltage-clamp experiment.
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Scheme 2: Synthesis of phthalate compounds.
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Figure 1: Channel activities of compound 1. A: Regular “square-top” activity. Conditions: 1 M KCl buffered to...
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Figure 2: Channel activities of compound 2. A: Rapid flickering. Conditions: 1 M CsCl, +100 mV; B: Semiregula...
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Figure 3: Conversion of a current–time profile of compound 5 (top) into conductance–time profile (bottom) by ...
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Figure 4: Single-molecule structure–activity relationships for compounds 1–8. Grids are given in the followin...
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Figure 5: Voltage-dependent opening of compound 1. Inset: Exponential dependence of the mean current on the p...
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- Full Research Paper
- Published 30 Nov 2011
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Scheme 1: Calix[4]arene tetraethers 1–4 and corresponding bridge monosubstituted carboxylic acid derivatives 5...
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Figure 1: A: Four fundamental conformations of a calix[4]arene. B: Arrangement of the methylene group substit...
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Scheme 2: Pathways to the calixarene acids 13 and 14 bearing mixed ether functions in different fashions.
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Figure 2: 1H NMR spectrum (CDCl3, 293 K, 500 MHz) of calixarene ether 12 before (A) and after the addition of...
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Figure 3: Crystal structure of compound 12. For clarity only one of the two crystallographically independent ...
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- Full Research Paper
- Published 02 Jan 2012
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Figure 1: a) The global minimum-energy conformation for hexaethylbenzene reveals the basis for steric gearing...
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Figure 2: Structures of hosts discussed in this manuscript. R = H, Me, or Et.
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Figure 3: Generalized structural fragments used for mining the Cambridge Structure Database. R = Me and Et, X...
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Figure 4: a) Structures used to calculate energy profiles at the starting geometry. b) An example of an energ...
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- Full Research Paper
- Published 03 Jan 2012
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Figure 1: Bi-macrocyclic concave host 1 and its non-macrocyclic model 2.
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Scheme 1: Synthetic scheme for the syntheses of concave host 1 and non-macrocyclic derivative 2. a) Et3N, THF...
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Figure 2: Expansion of a part of the 1H NMR spectra (200 MHz, 298 K) of pure 1 and 2 in CD2Cl2 (bottom) and a...
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Figure 3: Normalized 1H NMR CIS (see text) for concave host 1 with different anionic and neutral guests. The ...
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Figure 4: Normalized 1H NMR CIS (see text) for concave host 2 with different anionic and neutral guests. The ...
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- Full Research Paper
- Published 12 Jan 2012
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Figure 1: Simplified free energy scheme for driving an endergonic condensation (elimination/addition of water...
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Figure 2: Binding motive of a vanadate zinc benzylcyclene complex (left) as suggested by the results of DFT c...
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Figure 3: 51V NMR titration at pH 9.5 ([V]t = 1.5 mM, [1]t = 0 to 7.5 mM (0 to 5 equiv), 100 mM CHES). [V]t a...
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Figure 4: Speciation of vanadium in a solution containing 1.5 mM Na3VO4, 100 mM CHES (pH = 9.5) and a Zn-benz...
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Figure 5: 51V EXSY NMR spectrum (tmix = 1 ms) of a solution containing 1.5 mM Na3VO4, 3 mM Zn-benzylcyclene a...
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- Full Research Paper
- Published 16 Jan 2012
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Figure 1: Chemical structure of gated molecular basket 1 and 1,1,1-trichloroethane (2). Electrostatic potenti...
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Figure 2: (Left): 1H NMR spectra (400 MHZ, CD2Cl2) of 1 (0.67 mM) obtained upon incremental addition of 1,1,1...
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Figure 3: Chemically equivalent CH3 protons (black) in 1,1,1-trichloroethane (2) alter their magnetic environ...
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Figure 4: Nonlinear least-squares fitting (SigmaPlot) of magnetization rate constants k*in (2-D EXSY, 250.0 ±...
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Figure 5: (A): Nonlinear least-squares fitting of 1H NMR signal intensities (Iin/out) of [CH3CCl3]in/out as f...
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Figure 6: (A) Four different trajectories were used for examining the departure of CH3CCl3 guest from basket 1...
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Figure 7: (A) The interconversion of conformational enantiomers 1A and 1B, having anticlockwise and clockwise...
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Figure 8: The departure of CH3CCl3 from 1A–CH3CCl3 gives rise to the less stable 1–CD2Cl2, which upon entrapm...
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Figure 9: (A): Kinetic and thermodynamic parameters [13,14] characterizing the departure of isosteric guests 3–7 fro...
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- Review
- Published 07 Feb 2012
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Figure 1: Calixarenes and expanded calixarenes: p-tert-Butylcalix[4]arene (1), p-tert-butyldihomooxacalix[4]a...
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Figure 2: Conventional nomenclature for oxacalix[n]arenes.
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Scheme 1: Synthesis of oxacalix[3]arenes: (i) Formaldehyde (37% aq), NaOH (aq), 1,4-dioxane; glacial acetic a...
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Figure 3: p-tert-Butyloctahomotetraoxacalix[4]arene (4a) [16].
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Figure 4: X-ray crystal structure of 3a showing phenolic hydrogen bonding (IUCr ID AS0508) [17].
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Scheme 2: Stepwise synthesis of asymmetric oxacalix[3]arenes: (i) MOMCl, Adogen®464; (ii) 2,2-dimethoxypropan...
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Figure 5: X-ray crystal structure of heptahomotetraoxacalix[3]arene 5 (CCDC ID 166088) [21].
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Scheme 3: Oxacalix[3]arene synthesis by reductive coupling: (i) Me3SiOTf, Et3SiH, CH2Cl2; R1, R2 = I, Br, ben...
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Scheme 4: Oxacalix[3]naphthalene: (i) HClO4 (aq), wet CHCl3 (R = tert-butyl, 6a, H, 6b) [20].
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Figure 6: Conformers of 3a.
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Scheme 5: Origin of the 25:75 cone:partial-cone statistical distribution of O-substituted oxacalix[3]arenes (p...
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Scheme 6: Synthesis of alkyl ethers 7–10: (i) Alkyl halide, NaH, DMF [24].
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Scheme 7: Synthesis of a pyridyl derivative 11a: (i) Picolyl chloride hydrochloride, NaH, DMF [26,27].
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Figure 7: X-ray crystal structure of partial-cone 11a (CCDC ID 150580) [26].
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Scheme 8: Lower-rim ethyl ester synthesis: (i) Ethyl bromoacetate, NaH, t-BuOK or alkali metal carbonate, THF...
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Scheme 9: Forming chiral receptor 13: (i) Ethyl bromoacetate, NaH, THF; (ii) NaOH, H2O/1,4-dioxane; (iii) S-P...
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Figure 8: X-ray crystal structure of 16 (IUCr ID PA1110) [32].
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Scheme 10: Lower rim N,N-diethylamide 17a: (i) N,N-Diethylchloroacetamide, NaH, t-BuOK or alkali metal carbona...
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Scheme 11: Capping the lower rim: (i) N,N-Diethylchloroacetamide, NaH, THF; (ii) NaOH, H2O/1,4-dioxane; (iii) ...
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Figure 9: X-ray crystal structure of 18 (CCDC ID 142599) [33].
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Scheme 12: Extending the lower rim: (i) Glycine methyl ester, HOBt, dicyclohexycarbodiimide (DCC), CH2Cl2; (ii...
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Scheme 13: Synthesis of N-hydroxypyrazinone derivative 23: (i) 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide...
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Scheme 14: Synthesis of 24: (i) 1-Adamantyl bromomethyl ketone, NaH, THF [39].
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Scheme 15: Synthesis of 25 and 26: (i) (Diphenylphosphino)methyl tosylate, NaH, toluene; (ii) phenylsilane, to...
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Figure 10: X-ray crystal structure of 27 in the partial-cone conformer (CCDC ID SUP 90399) [41].
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Scheme 16: Synthesis of strapped oxacalix[3]arene derivatives 28 and 29: (i) N,N’-Bis(chloroacetyl)-1,2-ethyle...
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Figure 11: A chiral oxacalix[3]arene [45].
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Figure 12: X-ray crystal structure of asymmetric oxacalix[3]arene 30 incorporating t-Bu, iPr and Et groups (CC...
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Scheme 17: Reactions of an oxacalix[3]arene incorporating an upper-rim Br atom with (i) Pd(OAc)2, PPh3, HCO2H,...
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Scheme 18: Synthesis of acid 39: (i) NaOH, EtOH/H2O, HCl (aq) [47].
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Figure 13: Two forms of dimeric oxacalix[3]arene 40 [47].
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Scheme 19: Capping the upper rim: (i) t-BuLi, THF, −78 °C; (ii) NaBH4, THF/EtOH; (iii) 1,3,5-tris(bromomethyl)...
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Figure 14: Oxacalix[3]arene capsules 46 and 47 formed through coordination chemistry [52,53].
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Figure 15: X-ray crystal structure of the 3b-vanadyl complex (CCDC ID 240185) [57].
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Scheme 20: Effect of Ti(IV)/SiO2 on 3a: (i) Ti(OiPr)4, toluene; (ii) triphenylsilanol, toluene; (iii) partiall...
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Figure 16: X-ray crystal structures of oxacalix[3]arene complexes with rhenium: 3b∙Re(CO)3 (CCDC ID 620981, le...
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Figure 17: X-ray crystal structure of the La2·3a2 complex (CSD ID TIXXUT) [60].
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Figure 18: X-ray crystal structures of [3a∙UO2]− with a cavity-bound cation (CCDC ID 135575, left) and without...
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Figure 19: X-ray crystal structure of a supramolecule comprising two [3g·UO2]− complexes that encapsulate a di...
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Figure 20: X-ray crystal structure of oxacalix[3]arene 49 capable of chiral selectivity (CSD ID HIGMUF) [65].
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Figure 21: The structure of derivative 50 incorporating a Reichardt dye [66].
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Figure 22: Phosphorylated oxacalix[3]arene complexes with transition metals: (Left to right) 26∙Au, 26∙Mo(CO)3...
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Figure 23: X-ray crystal structure of [17a·HgCl2]2 (CCDC ID 168653) [69].
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Figure 24: X-ray crystal structures of 3f with C60 (CCDC ID 182801, left) [76] and a 1,4-bis(9-fluorenyl) C60 deri...
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Figure 25: X-Ray crystal structure of 3i and 6a encapsulating C60 (CCDC ID 102473 and 166077) [23,79].
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Figure 26: A C60 complexing cationic oxacalix[3]arene 51 [81].
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Figure 27: An oxacalix[3]arene-C60 self-associating system 53 [87].
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Scheme 21: Synthesis of fluorescent pyrene derivative 55: (i) Propargyl bromide, acetone; (ii) CuI, 1-azidomet...
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Scheme 22: Synthesis of responsive rhodamine derivative 57: (i) DCC, CH2Cl2 [91].
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Scheme 23: Synthesis of nitrobenzyl derivative 58: (i) 1-Bromo-4-nitrobenzyl acetate, K2CO3, refluxing acetone...
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Figure 28: X-ray crystal structure of [Na2∙17a](PF6)2 (CCDC ID 116656) [97].
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- Full Research Paper
- Published 09 Feb 2012
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Figure 1: Hunter/Vögtle-type tetralactam macrocycle 1 bearing an iodo substituent at one of the isophthaloyl ...
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Scheme 1: Synthesis of the monovalent diamide axle 2, which was used for Sonogashira coupling to the appropri...
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Scheme 2: Synthesis of divalent wheels from TLM 1: (a), (b) (Ph3P)2PdCl2, CuI, PPh3, NEt3, DMF, 25 °C, 24 h, ...
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Scheme 3: Synthesis of trivalent wheel 14 from TLM 1: (a) (Ph3P)2PdCl2, CuI, PPh3, NEt3, DMF, 25 °C, 24 h, 40...
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Scheme 4: (a) Pd2(dba)3, AsPh3, NEt3, DMF, 120 °C, 12 h, 7% (16).
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Scheme 5: Synthesis of a series of multivalent guests starting from the axle 2. (a), (b), (c), (d): Pd2(dba)3...
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Scheme 6: Synthesis of the tetravalent axle 23 and its divalent side product: (a) Pd2(dba)3, AsPh3, NEt3, DMF...
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Figure 2: Aliphatic regions of the 1H NMR spectra (CD2Cl2, 500 MHz, 298 K, 2.3 mM) of (a) 10 (top), 17@10 (ce...
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- Published 13 Feb 2012
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Scheme 1: Synthesis of bis(triazole) macrocycle 3 and tetra(triazole) macrocycle 4. Conditions and reagents: ...
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Scheme 2: Synthesis of bis(triazolium) macrocycle, 5. Conditions and reagents: (i) (a) (Me3O)(BF4), CH2Cl2, (...
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Figure 1: Solid-state structure of 3 (left) and 4 (right). Hydrogen atoms omitted for clarity, ellipsoids are...
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Figure 2: 1H NMR spectra of 5·2PF6 after the addition of 0, 1.0, 2.0 and 5.0 equiv of TBA·Cl (500 MHz, 293 K,...
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Figure 3: Titration data (solid points) and fitted binding isotherms (curves) monitoring the triazolium proto...
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Figure 4: CV of 5·2PF6 upon the addition of TBA·Cl (electrolyte: 0.1 M TBA·PF6/CH3CN, [5·2PF6] = 0.50 mM, 293...
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- Published 28 Feb 2012
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Scheme 1: Possible octanuclear prism and tetranuclear macrocycle resulting from the combination of a tetraden...
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Scheme 2: Formation of the tetranuclear complexes (2a and 2b) upon the reaction of Ru(II)2 based acceptors 1a...
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Figure 1: 1H (left) and 19F (right) NMR spectra of tetranuclear macrocycle 2a recorded in CD2Cl2–CD3OD with p...
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Figure 2: ESIMS spectrum of the macrocycle 2a recorded in acetonitrile. Inset: Experimentally observed isotop...
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Figure 3: A ball and stick representation of 2a with atom numbering. Color code: Ru = green; O = red; N = blu...
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Scheme 3: Formation of an octanuclear macrocycle 2c upon reaction of Ru(II)2-based acceptors 1c with imidazol...
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Figure 4: 1H (left) and 19F (right) NMR spectrum of the macrocycle 2c recorded in CD3CN with the peak assignm...
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Figure 5: Side (left) and top (right) view of the energy-minimized structures of the octanuclear macrocycle 2c...
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Figure 6: UV–vis absorption spectrum (left) of macrocycles (2a–2c) recorded in CH3CN at 298 K, and cyclic vol...
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- Published 02 Apr 2012
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Figure 1: Chemical structures of UPy dimer and DAN complexes with UG and DeUG.
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Figure 2: Illustration of the use of DeUG-Dye and DAN-Dye as colorimetric indicators for supramolecular inter...
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Scheme 1: Synthesis of azobenzene-dye-coupled DAN 5.
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Scheme 2: Synthesis of azobenzene-dye-coupled DAN 8 and 10.
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Scheme 3: Synthesis of azobenzene dye-coupled DeUG 12.
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Scheme 4: Synthesis of azobenzene dye-coupled DeUG 18.
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Figure 3: Solution (20 mmol) of azobenzene-dye-coupled DAN and DeUG in CH2Cl2; a = compound 5, b = compound 8...
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Figure 4: Structure of DAN-modified PS and Upy-modified PBA.
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Figure 5: Physical appearance of DAN-modified PS and UPy-modified PBA. Left: A0 = PS, A1 = PS-DAN 2.0 mol %, ...
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Figure 6: Color change after the interaction of azo-benzene dye-coupled DeUG modules with different DAN modif...
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Figure 7: Color change after the interaction of azobenzene dye-coupled DAN modules with different UPy-modifie...
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- Published 12 Apr 2012
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Figure 1: Examples of monoexponential decay: The slope of the line directly provides the reaction pseudo-firs...
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Figure 2: Example of biexponential decay.
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Figure 3: Amidoresorcin[4]arene YS.
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Scheme 1: Studied (a) peptidoresorcin[4]arenes and (b) dipeptidic guests.
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Figure 4: Catharanthine and vindoline, monomers constituting the anticancer vinblastine and the analogous vin...
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Figure 5: Stable conformers of catharanthine.
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Figure 6: Global minima of (a) [VS∙H∙T]+ and (b) [VR∙H∙T]+ complexes.
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Figure 7: Guests studied in [47].
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Figure 8: Selected nucleosides.
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Figure 9: Example of molecular logic gate.
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Figure 10: Cyclochiral resorcin[4]arenes.
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- Published 25 Apr 2012
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Figure 1: (a) Helical wheel representation of the tetrameric Acid-pp/B3β2γ helix bundle, (b) sequences of Aci...
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Figure 2: (a) Sequence for random mutation resulting in 1764 spots. The randomized positions are denoted by Xa...
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Figure 3: Glycine scanning of Acid-pp sequences. The substituted glycines are highlighted in red. Each sequen...
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Figure 4: Heat-map diagrams depicting the quantitatively measured SIs for Acid-pp sequences containing mutati...
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Figure 5: (a) The complete sequences of the selected α-mutants. (b) CD and (c) thermal denaturation spectra o...
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Figure 6: Size-exclusion chromatograms of equimolar mixtures of B3β2γ with (a) Acid-pp, (b) VaVdEeEg, (c) LaLd...
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