The nature of selenium hydrogen bonding: gas phase spectroscopy and quantum chemistry calculations

Abstract

Subsequent to the recent re-definition of hydrogen bonding by the IUPAC committee, there has been a growing search for finding the presence of this ever interesting non-covalent interaction between a hydrogen atom in an X-H group and any other atom in the periodic table. In recent gas phase experiments, it has been observed that hydrogen bonding interactions involving S and Se are of similar strength to those with an O atom. However, there is no clear explanation for the unusual strength of this interaction in the case of hydrogen bond acceptors which are not conventional electronegative atoms. In this work, we have explored the nature of Se hydrogen bonding by studying indoledimethyl selenide (indmse) and phenoldimethyl selenide (phdmse) complexes using gas phase IR spectroscopy and quantum chemistry calculations. We have found through various energy decomposition analysis (EDA) methods and natural bond orbital (NBO) calculations that, along with electrostatics and polarization, charge transfer interactions are important to understand Se/S hydrogen bonding and there is a delicate balance between the various interactions that plays the crucial role rather than a single component of the interaction energy. An in-depth understanding of this type of non-covalent interaction has immense significance in biology as amino acids containing S and Se are widely present in proteins and hence hydrogen bonding interactions involving S and Se atoms contribute to the folding of proteins.

Divalent Anionic Doping in Perovskite Solar Cells for Enhanced Chemical Stability

“…N–H stretching modes at 3201 cm −1 in MAPbI 3 redshifts to 3114 cm −1 in 10% w/w PbSe:CH 3 NH 3 PbI 3 films due to the electrostatic attraction between Se 2− and cationic CH 3 NH 3 + . Our IR study follows the observation that Se interacts with H in N–H and retard stretching modes of N–H . Also, significant band broadening is witnessed on N–H stretch in 10% w/w PbSe:MAPbI 3 , relative to the peak of N–H stretch in MAPbI 3 , matching the pattern of strong electrostatic interaction .…”

Selenoamides modulate dipole–dipole interactions in hydrogen bonded supramolecular polymers of 1,3,5-substituted benzenes

“…The entropic penalty of the supramolecular polymerization of c-SeBTA (DS e = À97 J mole À1 K À1 ) was comparable to that of c-SBTA 30,36 (DS e = À102.6 J mole À1 K À1 ), instead, and we speculate similar ordering between the homopolymers of c-SeBTA and c-SBTA. We rationalize these thermodynamic parameters with an increased dipole-dipole and charge transfer character of the diffuse Se-NH hydrogen bond, 21,37 which ultimately affords the increased thermal stability of the supramolecular polymers of c-SeBTA (more favorable DH e and very similar DS e compared to c-SBTA). Interestingly, the nucleation penalty, and hence cooperativity, of the supramolecular polymers of c-SBTA and c-SeBTA were comparable (s = 1.9 Â 10 À3 for c-SBTA, 30,36 and 3 Â 10 À4 for c-SeBTA).…”

“…We compare its self-assembly behavior to that of OBTA/c-OBTA 20 and SBTA/c-SBTA. 21 The different nature of the selenoamide hydrogen bond is illustrated by our finding that c-SeBTA polymers have an increased stability towards thermal denaturation yet enhanced lability towards polar solventsinduced denaturation.…”

“…[17][18][19][20] In addition, it has been observed both theoretically and experimentally that NHÁ Á ÁS or NHÁ Á ÁSe hydrogen bonds can be as strong as those of NHÁ Á ÁO, despite the lower electronegativity of S and Se. 21,22 In proteins and peptides, the introduction of thioamide or selenoamide bonds has allowed to tune their structure, stability, and -in case of enzymes -activity. [23][24][25][26] Interestingly, as the chalcogen atom in the amide in peptides changes from O to S to Se, the increasing polarizability was found to increasingly dominate the electronic properties of the amides.…”

The Se…S/N interactions as a possible mechanism of δ-aminolevulinic acid dehydratase enzyme inhibition by organoselenium compounds: A computational study

“…The simulation of DPDS with the Dmδ-AlaD demonstrated that this organoselenium compound could access the active site making hydrophobic interactions with Arg205, Pro212 (alkyl and phenyl groups), Phe204 and Tyr201 (phenyl and phenyl moieties), besides interacting with Arg217 via H-bond (selenyl and guanidinyl groups [95,96]) (Fig. 4C).…”