Combined Cation–π and Anion–π Interactions for Zwitterion Recognition

Perraud, Olivier; Robert, Vincent; Gornitzka, Heinz; Martinez, Alexandre; Dutasta, Jean‐Pierre

doi:10.1002/anie.201106934

Cited by 78 publications

(41 citation statements)

References 69 publications

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“…[43][44][45] These correspond to instantaneous dipole-dipole interactions resulting from the local charge excitations g I → u I and g II → u II [see Eq. (4.6)], with the excitation energy E. The dispersion interaction can be evaluated as ∼−I 2 / E, and the typical amplitudes of the dispersion interaction are in the range −0.1 to −0.01 eV.…”

Section: E Resultsmentioning

confidence: 99%

Ab initio derivation of multi-orbital extended Hubbard model for molecular crystals

Tsuchiizu

Omori

Suzumura

et al. 2012

The Journal of Chemical Physics

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From configuration interaction (CI) ab initio calculations, we derive an effective two-orbital extended Hubbard model based on the gerade (g) and ungerade (u) molecular orbitals (MOs) of the chargetransfer molecular conductor (TTM-TTP)I-3 and the single-component molecular conductor Au(tmdt)(2)]. First, by focusing on the isolated molecule, we determine the parameters for the model Hamiltonian so as to reproduce the CI Hamiltonian matrix. Next, we extend the analysis to two neighboring molecule pairs in the crystal and we perform similar calculations to evaluate the intermolecular interactions. From the resulting tight-binding parameters, we analyze the band structure to confirm that two bands overlap and mix in together, supporting the multi-band feature. Furthermore, using a fragment decomposition, we derive the effective model based on the fragment MOs and show that the staking TTM-TTP molecules can be described by the zig-zag two-leg ladder with the inter-molecular transfer integral being larger than the intra-fragment transfer integral within the molecule. The inter-site interactions between the fragments follow a Coulomb law, supporting the fragment decomposition strategy. . First, by focusing on the isolated molecule, we determine the parameters for the model Hamiltonian so as to reproduce the CI Hamiltonian matrix. Next, we extend the analysis to two neighboring molecule pairs in the crystal and we perform similar calculations to evaluate the intermolecular interactions. From the resulting tight-binding parameters, we analyze the band structure to confirm that two bands overlap and mix in together, supporting the multi-band feature. Furthermore, using a fragment decomposition, we derive the effective model based on the fragment MOs and show that the staking TTM-TTP molecules can be described by the zig-zag two-leg ladder with the inter-molecular transfer integral being larger than the intra-fragment transfer integral within the molecule. The inter-site interactions between the fragments follow a Coulomb law, supporting the fragment decomposition strategy.

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Section: E Resultsmentioning

confidence: 99%

Ab initio derivation of multi-orbital extended Hubbard model for molecular crystals

Tsuchiizu

Omori

Suzumura

et al. 2012

The Journal of Chemical Physics

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“…Enantiopure hemicryptophanes can be obtained either by resolution of the racemic mixture or by diastereoselective synthesis . Besides their use as enantioselective receptors for carbohydrates and neurotransmitters, their C 3 symmetry has allowed to build molecular cages presenting a triple‐helical arrangement of the linkers . Indeed, the CTV unit is able to control the chirality of triple helices since the CTV with P (respectively M ) configuration induces a Δ (respectively, Λ ) propeller‐like arrangement of the linkers.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, resolution, and chiroptical properties of hemicryptophane cage controlling the chirality of propeller arrangement of a C₃ triamide unit

et al. 2019

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The five‐steps synthesis of a hemicryptophane cage combining a benzene‐1,3,5‐tricarboxamide unit and a cyclotriveratrylene (CTV) moiety is described. Chiral high‐performance liquid chromatography (HPLC) was used to resolve the racemic mixture. The absolute configuration of the isolated enantiomers was assigned by comparison of the experimental electronic circular dichroism (ECD) spectra with the calculated ones. X‐ray molecular structures reveal that the capped benzene‐1,3,5‐tricarboxamide unit adopts a structurally chiral conformation in solid state: the chirality of CTV moiety controls the Λ or Δ orientation of the three amides.

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“…It is also noteworthy that, among the reported zwitterion receptors,7, 9–11 only a few examples describe the selective complexation of betaines,9, 11 with most of the systems being devoted to the binding of amino acids 7. 10a,c…”

Section: Resultsmentioning

confidence: 99%

A Biomimetic Heteroditopic Receptor for Zwitterions in Protic Media

Cornut

Moerkerke

Bruylants

et al. 2014

Chemistry An Asian Journal

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The efficient synthesis of calix[6]cryptothiourea 6 was achieved through a two-step sequence that involves a key [1+1] macrocyclization step. It was shown by NMR spectroscopy that this heteroditopic receptor can bind zwitterions in protic media with an outstanding selectivity for β-alanine betaine G5, which is likely due to a high complementarity between the two partners. This result constitutes a rare example of cavity complexation of a zwitterion by a calix[6]arene. In comparison with the parent urea-based receptors, 6 behaves as a much more efficient host for betaines. This strengthening of the binding properties is due to the better preorganization of the tripodal hydrogen-bonding cap as well as to the higher acidity of the thiourea groups and their poor ability to self-associate. Remarkably, host 6 is able to perform solid-liquid as well as liquid-liquid extraction of G5. Finally, 6 provides an excellent structural model for the binding site of glycine betaine G4 encountered in natural systems.

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Combined Cation–π and Anion–π Interactions for Zwitterion Recognition

Cited by 78 publications

References 69 publications

Ab initio derivation of multi-orbital extended Hubbard model for molecular crystals

Ab initio derivation of multi-orbital extended Hubbard model for molecular crystals

Synthesis, resolution, and chiroptical properties of hemicryptophane cage controlling the chirality of propeller arrangement of a C₃ triamide unit

A Biomimetic Heteroditopic Receptor for Zwitterions in Protic Media

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Combined Cation–π and Anion–π Interactions for Zwitterion Recognition

Cited by 78 publications

References 69 publications

Ab initio derivation of multi-orbital extended Hubbard model for molecular crystals

Ab initio derivation of multi-orbital extended Hubbard model for molecular crystals

Synthesis, resolution, and chiroptical properties of hemicryptophane cage controlling the chirality of propeller arrangement of a C3 triamide unit

A Biomimetic Heteroditopic Receptor for Zwitterions in Protic Media

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Synthesis, resolution, and chiroptical properties of hemicryptophane cage controlling the chirality of propeller arrangement of a C₃ triamide unit