Front Cover: How the Chalcogen Atom Size Dictates the Hydrogen‐Bond Donor Capability of Carboxamides, Thioamides, and Selenoamides (Chem. Eur. J. 31/2022)

Nieuwland, Celine; Guerra, Célia Fonseca

doi:10.1002/chem.202201308

Cited by 11 publications

(29 citation statements)

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“…The orbital interaction in H-bonds follows mainly from the covalent or charge-transfer component [3,12] which arises for BTAs from the σ donor-acceptor interaction between the filled chalcogen np lone-pair type σ HOMO orbitals on one monomer and the empty σ LUMO orbitals localized on the NH 2 groups of the other monomer. ΔE oi is more stabilizing from O to S to Se as the σ HOMOs are raised in energy while the σ LUMOs are lowered in energy upon descending Group 16 (see Figure 3a and 3b and Supporting Data S3).…”

Section: Resultsmentioning

confidence: 99%

“…We have demonstrated recently that not the electronegativity but the steric atomic size of the chalcogen in the amide bond determines the enhanced H-bond donor strength of thio-and selenoamides compared to carboxamides. [3] As the effective size of the chalcogen atom increases from O to S to Se, the amide C=X bond is elongated due to the increasing steric Pauli repulsion between the two bonded atoms for the heavier chalcogens. As a consequence, the S-3p and Se-4p atomic orbitals (AOs) have less overlap with the 2p-AO of C than the O-2p AO.…”

Section: Introductionmentioning

confidence: 99%

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Chalcogen Atom Size Dictates Stability of Benzene‐1,3,5‐triamide Polymers: Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding

Nieuwland

Deprez

Vries

et al. 2023

Chemistry A European J

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Our quantum chemical analyses elucidated how the replacement of O in the amide bonds of benzene-1,3-5tricarboxamides (OBTAs) with the larger chalcogens S and Se enhances the intermolecular interactions and thereby the stability of the obtained hydrogen-bonded supramolecular polymers due to two unexpected reasons: i) the SBTA and SeBTA monomers have a better geometry for self-assembly and ii) induce stronger covalent (hydrogen-bond) interactions besides enhanced dispersion interactions. In addition, it is shown that the cooperativity in benzene-1,3,5-triamide (BTA) self-assembly is caused by charge separation in the σelectronic system following the covalency in the hydrogen bonds.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Chalcogen Atom Size Dictates Stability of Benzene‐1,3,5‐triamide Polymers: Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding

Nieuwland

Deprez

Vries

et al. 2023

Chemistry A European J

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“…All calculations were performed by using the Amsterdam Density Functional (ADF) program developed by Baerends et al [21] based on dispersion-corrected relativistic density functional theory at the ZORA-BLYP-D3/TZP level for geometry optimizations and ZORA-BLYP-D3/TZ2P for energies. Previous works [22][23][24] have shown that this level of theory gives excellent understanding of bonding mechanism in hydrogen bonding and also in long range interactions within weakly-bound complexes. [11] Furthermore, the use of the TZP basis set for large supramolecular systems has shown to furnish accurate results.…”

Section: Methodsmentioning

confidence: 99%

Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen‐bonded rosettes in supramolecular stacks

Petelski

Guerra

2022

Chemistry An Asian Journal

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Hydrogen‐bonded supramolecular systems are known to obtain extra stabilization from the complexation with ions, like guanine quadruplex (GQ). They experience strong hydrogen bonds due to cooperative effects. To gain deeper understanding of the interplay between ions and hydrogen‐bonding cooperativity, relativistic dispersion‐corrected density functional theory (DFT‐D) computations were performed on triple‐layer hydrogen‐bonded rosettes of ammeline interacting with alkali metal cations and halides. Our results show that when ions are placed between the stacks, the hydrogen bonds are weakened but, at the same time, the cooperativity is strengthened. This phenomenon can be traced back to the shrinkage of the cavity as the ions pull the monomers closer together and therefore the distance between the monomers becomes smaller. On one hand this results in a larger steric repulsion, but on the other hand, the donor‐acceptor interactions are enhanced due to the larger overlap between the donating and accepting orbitals leading to more charge donation and therefore an enhanced electrostatic attraction.

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“…These different hydrogen‐bonding preferences have also been observed in the crystal structures of many of their derivatives and are thought to be responsible for why certain thiourea derivatives were effective components of healable materials whereas their urea analogs were not [8, 9]. The growing interest in noncovalent interactions involving these species [10–29] has led to renewed interest in the conformational energetics of both molecules.…”

Section: Introductionmentioning

confidence: 99%

“…not [8,9]. The growing interest in noncovalent interactions involving these species [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] has led to renewed interest in the conformational energetics of both molecules.…”

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confidence: 99%

Conformational comparison of urea and thiourea near the CCSD(T) complete basis set limit

Barlow

Tschumper

2022

Int J of Quantum Chemistry

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The global minima of urea and thiourea were characterized along with other lowlying stationary points. Each structure was optimized with the CCSD(T) method and triple-ζ correlation consistent basis sets followed by harmonic vibrational frequency computations. Relative energies evaluated near the complete basis set limit with both canonical and explicitly correlated CCSD(T) techniques reveal several subtle but important details about both systems. These computations resolve a discrepancy by demonstrating that the electronic energy of the C 2v second-order saddle point of urea lies at least 1.5 kcal mol À1 above the C 2 global minimum regardless of whether the structures were optimized with MP2, CCSD, or CCSD(T). Additionally, urea effectively has one minimum instead of two because the electronic barrier for inversion at one amino group in the C s local minimum vanishes at the CCSD(T) CBS limit. Characterization of both systems with the same ab initio methods and large basis sets conclusively establishes that the electronic barriers to inversion at one or both NH 2 groups in thiourea are appreciably smaller than in urea. CCSDT(Q)/cc-pVTZ computations show higher-order electron correlation effects have little impact on the relative energies and are consistently offset by core correlation effects of opposite sign and comparable magnitude. | INTRODUCTIONThe first synthesis of urea (O C(NH 2 ) 2 ) from inorganic starting materials was reported in 1828 [1]. Since then, urea and its derivatives have been produced commercially for a wide range of industrial purposes. For example, due to the high nitrogen content of urea, it has become a crucial component utilized by the agricultural industry when manufacturing fertilizers [2] as well as animal feed [3]. In addition, urea is a common synthetic precursor used in both the chemical and pharmaceutical industries to produce various resins [4] and barbiturates [5]. Urea derivatives have also been found to play an instrumental role in drug design by acting as a biological modulator [6]. Thiourea (S C(NH 2 ) 2 ) is the sulfur analog of urea. Although urea and thiourea are isovalent and structurally similar, they can exhibit significantly different properties. An example of such can be seen in their corresponding crystal structures, where the hydrogen-bonding framework experimentally observed for the crystal structure of urea forms linear hydrogen bonds in a head-to-tail manner, while thiourea preferentially adopts a unique zig-zag or ribbon hydrogen-bonding motif [7]. These different hydrogen-bonding preferences have also been observed in the crystal structures of many of their derivatives and are thought to be responsible for why certain thiourea derivatives were effective components of healable materials whereas their urea analogs were

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Front Cover: How the Chalcogen Atom Size Dictates the Hydrogen‐Bond Donor Capability of Carboxamides, Thioamides, and Selenoamides (Chem. Eur. J. 31/2022)

Cited by 11 publications

References 0 publications

Chalcogen Atom Size Dictates Stability of Benzene‐1,3,5‐triamide Polymers: Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding

Chalcogen Atom Size Dictates Stability of Benzene‐1,3,5‐triamide Polymers: Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding

Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen‐bonded rosettes in supramolecular stacks

Conformational comparison of urea and thiourea near the CCSD(T) complete basis set limit

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