Blue-Shifting Hydridic Hydrogen Bonds in Complexes of (Me3Si)3SiH
The result's identifiers
Result code in 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>
Alternative codes found
RIV/61388955:_____/25:00643746 RIV/61989100:27740/25:10258746
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Blue-Shifting Hydridic Hydrogen Bonds in Complexes of (Me3Si)3SiH
Original language description
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.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
—
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Physical Chemistry A
ISSN
1089-5639
e-ISSN
1520-5215
Volume of the periodical
129
Issue of the periodical within the volume
50
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
11512-11522
UT code for WoS article
001595298100001
EID of the result in the Scopus database
2-s2.0-105025147722