Calix[6]tris(thio)ureas: Heteroditopic Receptors for the Cooperative Binding of Organic Ion Pairs

Hamon, Mélanie; Ménand, Mickaël; Gac, Stéphane Le; Luhmer, Michel; Dalla, Vincent; Jabin, Ivan

doi:10.1021/jo800712q

Cited by 79 publications

(54 citation statements)

References 33 publications

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“…34) were also synthesized by the Jabin group in 2003 75. These systems contain three urea or thiourea groups attached to the calix[6]arene skeleton.…”

Section: Ion Pair Receptors That Contain Amide Groups For Anion Rementioning

confidence: 99%

Ion pair receptors

2010

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Compared with simple ion receptors, which are able to bind either a cation or an anion, ion pair receptors bearing both a cation and an anion recognition site offer the promise of binding ion pairs or pairs of ions strongly as the result of direct or indirect cooperative interactions between co-bound ions. This critical review focuses on the recent progress in the design of ion pair receptors and summarizes the various binding modes that have been used to accommodate ion pairs (110 references).

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“…34) were also synthesized by the Jabin group in 2003 75. These systems contain three urea or thiourea groups attached to the calix[6]arene skeleton.…”

Section: Ion Pair Receptors That Contain Amide Groups For Anion Rementioning

confidence: 99%

Ion pair receptors

2010

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“…These groups provide strong and directional hydrogen bonds generating deeply preorganized receptors. Examples of calix[4]‐(thio)ureido‐based anion receptors have been reported, as well as examples of ureidocalix[5]arenes and calix[6]arenes , . Ditopic receptors, simultaneously binding both anion and cation of a given ion pair, may display higher affinity and selectivity compared to simple ion receptors, due to a cooperative binding process.…”

Section: Introductionmentioning

confidence: 99%

Recognition of Anions, Monoamine Neurotransmitter and Trace Amine Hydrochlorides by Ureido‐Hexahomotrioxacalix[3]arene Ditopic Receptors

Teixeira

Ascenso²,

Cragg

et al. 2020

Eur J Org Chem

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Hexahomotrioxacalix[3]arene‐based receptors (phenylurea 4a, phenylthiourea 4b and tert‐butylurea 4c) were synthesised and obtained in the partial cone conformation in solution. Phenylurea 4a was also obtained in the cone conformation and its X‐ray crystal structure is reported. Their binding properties towards several anions of different geometries were studied by 1H NMR titrations. The data showed that phenylurea cone 4a is the best anion receptor, displaying a very high affinity for the carboxylates AcO– and BzO– anions (log Kass = 4.12 and 4.00, respectively). Phenylurea partial cone 4a and phenylthiourea 4b, although weaker, are still reasonably good receptors, showing the same trend as cone 4a. tert‐Butylurea 4c exhibited very low affinity for all the anions, confirming that the association constants strongly depend on the nature of the substituent (aryl/alkyl) at the urea moiety. In addition, cone and partial cone 4a derivatives were also tested in the recognition of n‐alkylammonium salts and cone 4a also as a ditopic receptor for biogenic amine hydrochlorides by 1H NMR titrations. Cone 4a showed an outstanding affinity for the guest alkylammonium and amines, even at 298 K and in a more competitive solvent such as CDCl3/[D6]DMSO mixture. DFT calculations corroborated the NMR observations.

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“…5,6 Calix [4]arenes bearing one or more (thio)urea groups on either the lower or the upper rim, have been the most studied for anion recognition. [7][8][9][10][11] Ureidocalix [5]arene 12 and calix [6]arene 13 derivatives have also been tested as anion receptors. Along with calixarene's development, dihomooxacalix [4]arenes (calix [4]arene analogues in which one CH 2 bridge is replaced by one CH 2 OCH 2 group), 14 have also been investigated.…”

Section: Introductionmentioning

confidence: 99%

Site-Specific Description of the Enhanced Recognition Between Electrogenerated Nitrobenzene Anions and Dihomooxacalix[4]arene Bidentate Ureas

Martínez‐González

Armendáriz-Vidales

Ascenso³

et al. 2015

J. Org. Chem.

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Electron transfer controlled hydrogen bonding was studied for a series of nitrobenzene derivative radical anions, working as large guest anions, and substituted ureas, including dihomooxacalix[4]arene bidentate urea derivatives, in order to estimate binding constants (Kb) for the hydrogen-bonding process. Results showed enhanced Kb values for the interaction with phenyl-substituted bidentate urea, which is significantly larger than for the remaining compounds, e.g., in the case of 4-methoxynitrobenzene a 28-fold larger Kb value was obtained for the urea bearing a phenyl (Kb ∼ 6888) vs tert-butyl (Kb ∼ 247) moieties. The respective nucleophilic and electrophilic characters of the participant anion radical and urea hosts were parametrized with global and local electrodonating (ω(-)) and electroaccepting (ω(+)) powers, derived from DFT calculations. ω(-) data were useful for describing trends in structure–activity relationships when comparing nitrobenzene radical anions. However, ω(+) for the host urea structures lead to unreliable explanations of the experimental data. For the latter case, local descriptors ωk(+)(r) were estimated for the atoms within the urea region in the hosts [∑kωk(+)(r)]. By compiling all the theoretical and experimental data, a Kb-predictive contour plot was built considering ω(-) for the studied anion radicals and ∑kωk(+)(r) which affords good estimations.

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Calix[6]tris(thio)ureas: Heteroditopic Receptors for the Cooperative Binding of Organic Ion Pairs

Cited by 79 publications

References 33 publications

Ion pair receptors

Ion pair receptors

Recognition of Anions, Monoamine Neurotransmitter and Trace Amine Hydrochlorides by Ureido‐Hexahomotrioxacalix[3]arene Ditopic Receptors

Site-Specific Description of the Enhanced Recognition Between Electrogenerated Nitrobenzene Anions and Dihomooxacalix[4]arene Bidentate Ureas

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