Blue-Shifting Hydridic Hydrogen Bonds in Complexes of (Me3Si)3SiH

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00643746" target="_blank" >RIV/61388963:_____/25:00643746 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388955:_____/25:00643746 RIV/61989100:27740/25:10258746

Výsledek na webu

<a href="https://doi.org/10.1021/acs.jpca.5c05765" target="_blank" >https://doi.org/10.1021/acs.jpca.5c05765</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.5c05765" target="_blank" >10.1021/acs.jpca.5c05765</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Blue-Shifting Hydridic Hydrogen Bonds in Complexes of (Me3Si)3SiH

Popis výsledku v původním jazyce

Hydridic hydrogen bonds, formed by X–H···Y interactions with negatively charged hydrogen, expand the conventional view of H-bonding beyond elements that are more electronegative than hydrogen. Using a highly polarizable silane donor (Me3Si)3SiH, we systematically examined various electron acceptors (σ- and π-hole) and observed both red and blue shifts in the X–H stretching frequency. We provide the first experimental evidence of a blue-shifting hydridic bond and report the largest experimental blue shift for any hydrogen-bonded system. Thermodynamic, spectroscopic, and theoretical analyses show that the dispersion energy is crucial for stabilizing these complexes and reproducing their spectral signatures. Notably, the IR band intensity increases for red-shifting bonds and increases or decreases for blue-shifting hydridic bonds, offering a distinct spectroscopic fingerprint. Adiabatic ALMO-EDA calculations indicate that red shifts in hydridic bonds primarily arise from electrostatics and dispersion rather than charge transfer. It can be thus concluded that protonic as well as hydridic hydrogen bonds exhibit similar spectral manifestations, namely, the red or blue shift of the X–H stretching frequency connected with the intensity increase or decrease. These findings broaden hydrogen-bonding paradigms for diverse chemical applications.

Název v anglickém jazyce

Blue-Shifting Hydridic Hydrogen Bonds in Complexes of (Me3Si)3SiH

Popis výsledku anglicky

Hydridic hydrogen bonds, formed by X–H···Y interactions with negatively charged hydrogen, expand the conventional view of H-bonding beyond elements that are more electronegative than hydrogen. Using a highly polarizable silane donor (Me3Si)3SiH, we systematically examined various electron acceptors (σ- and π-hole) and observed both red and blue shifts in the X–H stretching frequency. We provide the first experimental evidence of a blue-shifting hydridic bond and report the largest experimental blue shift for any hydrogen-bonded system. Thermodynamic, spectroscopic, and theoretical analyses show that the dispersion energy is crucial for stabilizing these complexes and reproducing their spectral signatures. Notably, the IR band intensity increases for red-shifting bonds and increases or decreases for blue-shifting hydridic bonds, offering a distinct spectroscopic fingerprint. Adiabatic ALMO-EDA calculations indicate that red shifts in hydridic bonds primarily arise from electrostatics and dispersion rather than charge transfer. It can be thus concluded that protonic as well as hydridic hydrogen bonds exhibit similar spectral manifestations, namely, the red or blue shift of the X–H stretching frequency connected with the intensity increase or decrease. These findings broaden hydrogen-bonding paradigms for diverse chemical applications.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

1520-5215

Svazek periodika

129

Číslo periodika v rámci svazku

50

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

11512-11522

Kód UT WoS článku

001595298100001

EID výsledku v databázi Scopus

2-s2.0-105025147722