Partitioning of interaction-induced nonlinear optical properties of molecular complexes. II. Halogen-bonded systems

Medveď, Miroslav; Iglesias-Reguant, Alex; Reis, Heribert; Góra, Robert W.; Luis, Josep M.; Zaleśny, Robert

doi:10.1039/c9cp06620a

Cited by 12 publications

(17 citation statements)

References 81 publications

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“…In addition to participating in hydrogen-bonding interactions, the heavier halides (Cl, Br, and I) are also known to form halogen bonds (XB): attractive interactions between the electrophilic region, or σ-hole, of a halogen atom and a nucleophile . Nitrogen is a common XB acceptor, and a few computational studies have reported linear, halogen-bonded configurations of the form HCN···XH for X = Br and I. − Studies of the HCN/HX heterogeneous dimer focus exclusively on either the HB or the XB configurations, and to date no studies have looked more broadly at both possiblilities for these systems. Both halogen and hydrogen bonds are important to many fields, such as supramolecular chemistry and biochemistry, and extensive research has been done to investigate the relationship between these two noncovalent interactions. − Taking a look at how they compete in a relatively simple dimer system that is both computationally and experimentally accessible can give researchers insight into their roles in more complex systems.…”

Section: Introductionmentioning

confidence: 99%

Characterization of Competing Halogen- and Hydrogen-Bonding Motifs in Simple Mixed Dimers of HCN and HX (X = F, Cl, Br, and I)

Perkins

Tschumper

2022

J. Phys. Chem. A

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This work performs the first systematic comparison of hydrogen-and halogen-bonded configurations of the HCN/HX mixed dimer, where X = F, Cl, Br, and I. Eleven different minima have been characterized for these four heterogeneous dimers near the CCSD(T) complete basis set (CBS) limit. For each complex, two different hydrogen-bonded minima were identified: the global minimum where HX acts as the hydrogen bond donor and a local minimum where HX acts as the hydrogen bond acceptor. A halogenbonded local minimum was also identified for all but the fluorine mixed dimer. To the best of our knowledge, three of the minima are identified here for the first time. The hydrogen-and halogen-bonded local minima of each complex become more energetically competitive with the global minimum as the atomic radius of the halogen atom increases. CCSD(T) relative energies of the hydrogen-bonded local minima computed near the CBS limit decrease from 4.5 kcal mol −1 for HCN/HF to 2.9, 2.4, and 1.2 kcal mol −1 for X = Cl, Br, and I, respectively. Corresponding relative energies for the halogen-bonded local minima range from 4.0 kcal mol −1 for X = Cl to 2.7 kcal mol −1 for X = Br and to as little as 0.5 kcal mol −1 X = I. Harmonic vibrational frequency shifts reported here suggest that it may be feasible to differentiate between the various minima for X = Cl, Br, and I via spectroscopic analysis, as was the case for the HCN/HF dimer.

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Section: Introductionmentioning

confidence: 99%

Characterization of Competing Halogen- and Hydrogen-Bonding Motifs in Simple Mixed Dimers of HCN and HX (X = F, Cl, Br, and I)

Perkins

Tschumper

2022

J. Phys. Chem. A

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“…Interaction induced properties of Watson-Crick amino acid pairs have also been studied with higher orders of SAPT 68 and also with taking into account nuclear relaxation effects for small hydrogenand halogen-bonded dimers in the order up to interaction first hyperpolarizabilities. 69,70 The SAPT0 mean absolute errors for the interaction energy, dipole moment, and polarizability are, respectively, 0.50 kcal mol −1 , 0.039 D, and 0.15 Å 3 . Hence, SAPT0 is in qualitative agreement with the coupled cluster reference.…”

Section: B Sapt0 Decomposition Of the Interaction-induced Properties ...mentioning

confidence: 98%

Non-covalent interactions between molecular dimers (S66) in electric fields

Schwilk¹,

Mezei²,

Tahchieva³

et al. 2021

Preprint

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Fine tuning and microscopic control of van der Waals interactions through oriented external electric fields (OEEF) mandates an accurate and systematic understanding of intermolecular response properties. Having taken exploratory steps into this direction, we present a systematic study of interaction induced dipole electric properties of all molecular dimers in the S66 set, relying on CCSD(T)-F12b/aug-cc-pVDZ-F12 as reference level of theory. For field strengths up to ≈5 GV m −1 the interaction induced electric response beyond second order is found to be insignificant. Large interaction dipole moments are observed in the case of hydrogen bonding oriented along the intermolecular axis, and mostly small interaction dipole moments are found in dimers bonded by π-stacking or London dispersion. The interaction polarizabilities were generally found to be small but always with a positive-valued principal component approximately aligned with the intermolecular axis, and two other negative-valued components. Energy decompositions according to symmetry adapted perturbation theory (SAPT0/jun-cc-pVDZ) suggest that electrostatics dominates the interaction dipole moment, with exchange and induction contributing on a smaller scale, and with dispersion having the smallest effect. First-order SAPT0 decomposition into monomer-resolved contributions enables us to establish a quantitative link between electric properties of monomers and dimers, which is found to be in qualitative agreement with the coupled cluster reference method. Using the aug-cc-pVQZ basis and non-empirical PBE semilocal exchange-correlation kernels, we also assess how density functional approximations in the nonlocal exchange and correlation parts affect the predictive accuracy: While dRPA@PBE0 based predictions are in excellent overall agreement with coupled cluster results, the computationally more affordable LC-ωPBE0-D3 level of theory also yields reliable results with relative errors below 5%. PBE alone, even when dispersion corrected, produces larger errors in interaction dipole moments (≈ 10%) and polarizabilities (≈ 20%). We also resolve the mutual impact of the three dimensions of the OEEF, and we present a discussion of the intermolecular distance dependence of the perturbations.

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“…The addition of two fluorine atoms to the aromatic backbone, 24DF, increases the σ-hole potential but does not add any competing XB acceptors. Consequently, the main XB is an I••• OC; 2.891(2) Å and 173.51 (11)°.…”

mentioning

confidence: 98%

“…σ-Hole interactions, resulting from an attraction between an electron-deficient σ-hole on a halogen atom, and an electron-rich region on a Lewis base, can offer high directionality and tunability, which make them well-suited for the directed assembly of desired and robust supramolecular architectures . These properties have provided a foundation for halogen-bond-based structural chemistry with applications in a wide range of fields, fromcatalysis, , luminescence, nonlinear optics, , energetics, gels, and polymers, to molecular recognition, self-assembly, , and drug discovery . The strength of the halogen bond is directly related to the magnitude of the σ-hole, for which molecular electrostatic potentials are frequently used as a yardstick. , Stronger halogen bonds lead to synthon robustness, which means that we need access to an extensive library of molecules possessing large σ-hole potentials in order to impart supramolecular synthetic reliability.…”

mentioning

confidence: 99%

“Triply Activated” Phenyl 3-Iodopropiolates: Halogen-Bond Donors with Remarkable σ-Hole Potentials

Panikkattu

Huber

Sinha

et al. 2022

Crystal Growth & Design

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The ability of halogen-bond donors to form strong and directional intermolecular interactions remains integral to their prospects of becoming reliable synthetic tools for the bottom-up assembly of functional materials. An activation strategy involving three different electron-withdrawing groups in parallel, was employed in order to develop new halogen-bond donors possessing some of the highest σ-hole potentials reported to date.

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Partitioning of interaction-induced nonlinear optical properties of molecular complexes. II. Halogen-bonded systems

Abstract: Interaction-induced electronic and vibrational (hyper)polarizabilities of halogen-bonded complexes were decomposed into different interaction types (electrostatic, exchange, induction and dispersion).

Cited by 12 publications

References 81 publications

Characterization of Competing Halogen- and Hydrogen-Bonding Motifs in Simple Mixed Dimers of HCN and HX (X = F, Cl, Br, and I)

Characterization of Competing Halogen- and Hydrogen-Bonding Motifs in Simple Mixed Dimers of HCN and HX (X = F, Cl, Br, and I)

Non-covalent interactions between molecular dimers (S66) in electric fields

“Triply Activated” Phenyl 3-Iodopropiolates: Halogen-Bond Donors with Remarkable σ-Hole Potentials

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