Hydrogen bond blueshifts in nitrile vibrational spectra are dictated by hydrogen bond geometry and dynamics DOI Creative Commons
Jacob M. Kirsh, Jacek Kozuch

Published: Aug. 26, 2024

Vibrational Stark effect (VSE) spectroscopy has become one of the most important experimental approaches to determine strength noncovalent, electrostatic interactions in chemistry and biology quantify their influence on structure reactivity. Nitriles (C≡N) have been widely used as VSE probes, but application complicated by an anomalous hydrogen bond (HB) blueshift which is not encompassed within framework. We present empirical model describing HB terms H-bonding geometry, i.e. a function distance angle with respect C≡N group. This obtained comparing vibrational observables from density functional theory electrostatics polarizable AMOEBA force field, it provides physical explanation for underlying multipolar Pauli repulsion contributions. Additionally, we compare predicted blueshifts results find our useful, direct framework analyze geometry rigid HBs, such proteins or chemical frameworks. In contrast, nitriles highly dynamic environments like protic solvents are no longer solely geometry; this consequence motional narrowing, demonstrate simulating IR spectra. Overall, when dynamics accounted for, excellent correlation found between observed blueshifts. includes different types donors, suggesting that general can aid understanding wherever be implemented.

Language: Английский

Electrostatic Atlas of Noncovalent Interactions Built in Metal-Organic Frameworks DOI Creative Commons
Zhe Ji, Srijit Mukherjee, Jacopo Andreo

et al.

Published: Aug. 28, 2024

Noncovalent interactions form the basis of matter and life yet are difficult to characterize. Here we devised a platform strategy systematically build noncovalent with selective chemical groups into precisely designed configurations by using metal-organic frameworks (MOF) as molecular scaffold. Using vibrational Stark effect benchmarked against computer models, found electric field provides unifying metric for quantifying diverse in MOFs solutions. By synthetically making spectroscopically testing collection nitrile probe, identified stabilizing fields strong -123 MV/cm produced additively multiple hydrogen bonds, an unusual destabilizing +6 between antiparallel dipoles , anomalous hydrogen-bond blueshifts large 34 cm-1, unique solvation under nanoconfinement. This method opens new avenues exploring universe interactions.

Language: Английский

Citations

3
Hydrogen Bond Blueshifts in Nitrile Vibrational Spectra Are Dictated by Hydrogen Bond Geometry and Dynamics DOI Creative Commons
Jacob M. Kirsh, Jacek Kozuch

JACS Au, Journal Year: 2024, Volume and Issue: 4(12), P. 4844 - 4855

Published: Dec. 5, 2024

Vibrational Stark effect (VSE) spectroscopy has become one of the most important experimental approaches to determine strength noncovalent, electrostatic interactions in chemistry and biology quantify their influence on structure reactivity. Nitriles (C≡N) have been widely used as VSE probes, but application complicated by an anomalous hydrogen bond (HB) blueshift which is not encompassed within framework. We present empirical model describing HB terms H-bonding geometry, i.e., a function distance angle with respect C≡N group. This obtained comparing vibrational observables from density functional theory electrostatics polarizable AMOEBA force field, it provides physical explanation for underlying multipolar Pauli repulsion contributions. Additionally, we compare predicted blueshifts results find our useful, direct framework analyze geometry rigid HBs, such proteins or chemical frameworks. In contrast, nitriles highly dynamic environments like protic solvents are no longer solely geometry; this consequence motional narrowing, demonstrate simulating IR spectra. Overall, when dynamics accounted for, excellent correlation found between observed blueshifts. includes different types donors, suggesting that general can aid understanding wherever be implemented.

Language: Английский

Citations

2
Hydrogen bond blueshifts in nitrile vibrational spectra are dictated by hydrogen bond geometry and dynamics DOI Creative Commons
Jacob M. Kirsh, Jacek Kozuch

Published: Aug. 26, 2024

Vibrational Stark effect (VSE) spectroscopy has become one of the most important experimental approaches to determine strength noncovalent, electrostatic interactions in chemistry and biology quantify their influence on structure reactivity. Nitriles (C≡N) have been widely used as VSE probes, but application complicated by an anomalous hydrogen bond (HB) blueshift which is not encompassed within framework. We present empirical model describing HB terms H-bonding geometry, i.e. a function distance angle with respect C≡N group. This obtained comparing vibrational observables from density functional theory electrostatics polarizable AMOEBA force field, it provides physical explanation for underlying multipolar Pauli repulsion contributions. Additionally, we compare predicted blueshifts results find our useful, direct framework analyze geometry rigid HBs, such proteins or chemical frameworks. In contrast, nitriles highly dynamic environments like protic solvents are no longer solely geometry; this consequence motional narrowing, demonstrate simulating IR spectra. Overall, when dynamics accounted for, excellent correlation found between observed blueshifts. includes different types donors, suggesting that general can aid understanding wherever be implemented.

Language: Английский

Citations

0