(Thio)urea Resorcinarene Cavitands. Complexation and Membrane Transport of Halide Anions

Boerrigter, Harold; Grave, Lennart; Nissink, J. Willem M.; Chrisstoffels, Lysander A. J.; Maas, J.H. van der; Verboom, Willem; Jong, Feike de; Reinhoudt, David N.

doi:10.1021/jo972127l

Cited by 76 publications

(41 citation statements)

References 40 publications

(43 reference statements)

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“…[7] The simplest resorcinarenes such as 1 (Scheme 1) are held in a cone conformation through OÀH···O hydrogen bonding along the upper rim and are well known to accommodate guest cations inside their cavities, for example, quaternary ammonium ions. [8] For anion binding, [9] more elaborate cavitand receptors have been developed, [10] in which the resorcinarene merely provides the scaffold, while the (thio)urea, N-heterocyclic, or quaternary ammonium binding sites are located in the apical positions on the edge of the cavity. In quite a number of anion receptors, anion binding is supported by additional weaker interactions of the anion with aromatic C À H bonds.…”

mentioning

confidence: 99%

Anion Binding to Resorcinarene‐Based Cavitands: The Importance of CH⋅⋅⋅Anion Interactions

Zhu¹,

Staats²,

Brandhorst³

et al. 2008

Angew Chem Int Ed

137

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mentioning

confidence: 99%

Anion Binding to Resorcinarene‐Based Cavitands: The Importance of CH⋅⋅⋅Anion Interactions

Zhu¹,

Staats²,

Brandhorst³

et al. 2008

Angew Chem Int Ed

137

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“…Also in SLM transport experiments an increased selectivity for chloride over bromide was observed [51]. The tetrafunctionalized cavitands bind ca 9-15 times stronger than the cavitand-based ligands with three (thio)urea groups.…”

Section: Resorcarenes and Anionsmentioning

confidence: 88%

“…The association constants for halide anions, determined independently by 1 H NMR and infrared spectroscopy, are ca 10 2 times higher than for the corresponding tetra(thio)calixarenes [51]. The association constants for halide anions, determined independently by 1 H NMR and infrared spectroscopy, are ca 10 2 times higher than for the corresponding tetra(thio)calixarenes [51].…”

Section: Resorcarenes and Anionsmentioning

confidence: 91%

Resorcarenes: Hollow Building Blocks for the Host-Guest Chemistry

Botta

Cassani

D’Acquarica

et al. 2005

COC

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The continuous search for new qualities and the desirability of controlling the size, shape and the chemical features had led to the successful synthesis of various molecular containers and their complexes starting from resorcarene skeleton. The rigidified cavitands have been extended to capture in their round hug bigger and bigger molecules. By covalent synthesis many kinds of new hosts have been built, that maintain guests in their prison for more and more long time. Self assembly, driven by metal-ligand interaction, van der Waals forces, hydrophobicity and, mainly, hydrogen bonds, is at the base of capsules, a novel type of compounds with a peculiar inner phase, stereochemistry and reactivity. The amazing variety of hollow buildings with a resorcarene-based framework and often unique properties is reviewed. OH HO 1168 Current Organic Chemistry, 2005 Botta et al. RESORCARENES AS CONTAINER 2.1 Resorcarenes and Cations or Charged MoleculesAlso resorcarenes form stable complexes with alkali metal cations (Li I , Na I , K I , Rb I , Cs I ) [14]. The interaction of simple resorcarenes with metal cations and ammonium ions has been extensively studied. The conformational change of the host resorcarene, the most favourable binding locations and the relative binding energies have been investigated by ab initio methods [15]. The same group studied the interaction with cations of resorcarene 3a, (Chart 2) in comparison with its permethylated derivative 3b, by Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FT-ICR-MS) and ab initio calculations [16]. The significance of intramolecular hydrogen bonding for the cone conformation and the presence of intramolecular flip-flop hydrogen bonding in 3a were confirmed by calculations and ND 3 -exchange experiments. Regard to the complexation, the following items were established: i) all the above alkali metal cations formed host-guest complexes by docking inside the cavity of the host; ii) the complexation with larger cations, especially Cs + , was favoured; iii) all the cations formed stable dimer resorcarene capsules. Chart 2. Resorcarenes octol (3a) and octamethyl ether (3b).Conversely, Cu II cations were shown to interact with cyano-4a (Chart 3) and amino-resorcarenes 4b, forming in the latter case a complex with octahedrical geometry, as evidenced by the EPR spectrum; accordingly, the computercalculated structure suggested a three-molecular complex between Cu II and two molecules of 4b, in which the ligands use three of their functionalities at the lower rim to fix the ion with a distorted octahedral coordination [17]. Chart 3. Resorcarenes interacting with metal cations.The interaction of resorc[4]arenes octamethyl ethers such as 4c with Fe III in organic media was analysed by 1 H NMR studies, carried out using Ga III instead of Fe III . As a result, resorcarenes bearing carboalkyloxy groups in the side chains were shown to have two active sites of interaction, the first located at the aromatic upper rim and the other in the vicinity ...

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“…Tripodal urea receptors were synthesized and their binding properties with large terephthalate and trimesylate anions in polar aprotic solvents were investigated using NMR and luminescence titration methods and their association constants were reported [8]. The urea or thiourea groups incorporated receptors as anion recognition were studied in system of various solvents [9][10][11]. Previous theoretical work, the binding energies and thermodynamic properties of the 1,3-bis(4-nitrophenyl)urea complexes with halide anions and oxygen-containing anions were studied [12].…”

Section: Introductionmentioning

confidence: 99%

Molecular structures of 8,8′-dithioureido-2,2′-binaphthalene derivatives and their anions recognition: an ONIOM investigation

et al. 2009

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The structures of 8,8 0 -bis(3-phenylthioureidomethyl)-2,2 0 -binaphthalene (1), 8,8 0 -bis(3-butylthioureidomethyl)-2,2 0 -binaphthalene (2) and their complexes with anionic guests such as carboxylate ions (acetate, oxalate, malonate, succinate, glutarate, adipate, pimelate, suberate, and azelate), inorganic oxygen-containing anions (nitrate, sulfate, bicarbonate, hydrogen phosphate, and dihydrogen phosphate), and halide ions (fluoride, chloride, and bromide) were obtained using the ONIOM approach. The binding abilities of receptors 1 and 2 to anionic species in terms of binding energy, thermodynamic properties, and selectivity coefficient were obtained at the ONIOM(B3LYP/ 6-31G(d):AM1) and BSSE-corrected B3LYP/6-31G(d)// ONIOM(B3LYP/6-31G(d):AM1) levels of theory. The multipoint hydrogen bonding between receptors (either the receptor 1 or 2) and anionic guests were found. The hydrogen phosphate is the most preferable ion to bind with either the receptor 1 or 2.

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(Thio)urea Resorcinarene Cavitands. Complexation and Membrane Transport of Halide Anions

Cited by 76 publications

References 40 publications

Anion Binding to Resorcinarene‐Based Cavitands: The Importance of CH⋅⋅⋅Anion Interactions

Anion Binding to Resorcinarene‐Based Cavitands: The Importance of CH⋅⋅⋅Anion Interactions

Resorcarenes: Hollow Building Blocks for the Host-Guest Chemistry

Molecular structures of 8,8′-dithioureido-2,2′-binaphthalene derivatives and their anions recognition: an ONIOM investigation

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