Vapochromism induced by intermolecular electron transfer coupled with hydrogen-bond formation in zinc dithiolene complex

<div> <div> <div> <p>We propose, supported by ab-initio calculations, a possible photocatalytic cycle for hydrogen evolution by a prototypical polymer photocatalyst, poly(p-phenylene), in the presence of a sacrificial electron donor. As part of that cycle we also introduce a family of related sites on the polymer that in the absence of a noble metal co-catalyst can facilitate the evolution of molecular hydrogen when the polymer is illuminated. The bottlenecks for hydrogen evolution, electron transfer from the sacrificial electron donor and hydrogen-hydrogen bond formation, are discussed, as well as how they could potentially be improved by tuning the polymer properties and how they change in the presence of a noble-metal co-catalyst. </p> </div> </div> </div>

Download Full-text

Hydrogen Evolution by Polymer Photocatalysts; a Possible Photocatalytic Cycle

10.26434/chemrxiv.13522721.v1 ◽

2021 ◽

Author(s):

Andrew Prentice ◽

Martijn Zwijnenburg

Keyword(s):

Hydrogen Bond ◽

Electron Transfer ◽

Hydrogen Evolution ◽

Noble Metal ◽

Electron Donor ◽

Molecular Hydrogen ◽

Bond Formation ◽

Hydrogen Bond Formation ◽

Co Catalyst ◽

Polymer Properties

<div> <div> <div> <p>We propose, supported by ab-initio calculations, a possible photocatalytic cycle for hydrogen evolution by a prototypical polymer photocatalyst, poly(p-phenylene), in the presence of a sacrificial electron donor. As part of that cycle we also introduce a family of related sites on the polymer that in the absence of a noble metal co-catalyst can facilitate the evolution of molecular hydrogen when the polymer is illuminated. The bottlenecks for hydrogen evolution, electron transfer from the sacrificial electron donor and hydrogen-hydrogen bond formation, are discussed, as well as how they could potentially be improved by tuning the polymer properties and how they change in the presence of a noble-metal co-catalyst. </p> </div> </div> </div>

Download Full-text

Hydrogen Evolution by Polymer Photocatalysts; a Possible Photocatalytic Cycle

10.26434/chemrxiv.13522721.v2 ◽

2021 ◽

Author(s):

Andrew Prentice ◽

Martijn Zwijnenburg

Keyword(s):

Hydrogen Bond ◽

Electron Transfer ◽

Hydrogen Evolution ◽

Noble Metal ◽

Electron Donor ◽

Molecular Hydrogen ◽

Bond Formation ◽

Hydrogen Bond Formation ◽

Co Catalyst ◽

Polymer Properties

<div> <div> <div> <p>We propose, supported by ab-initio calculations, a possible photocatalytic cycle for hydrogen evolution by a prototypical polymer photocatalyst, poly(p-phenylene), in the presence of a sacrificial electron donor. As part of that cycle we also introduce a family of related sites on the polymer that in the absence of a noble metal co-catalyst can facilitate the evolution of molecular hydrogen when the polymer is illuminated. The bottlenecks for hydrogen evolution, electron transfer from the sacrificial electron donor and hydrogen-hydrogen bond formation, are discussed, as well as how they could potentially be improved by tuning the polymer properties and how they change in the presence of a noble-metal co-catalyst. </p> </div> </div> </div>

Download Full-text

Diverse mechanisms of carbon-hydrogen bond formation through binuclear reductive elimination reactions

Journal of the American Chemical Society ◽

10.1021/ja00366a044 ◽

1982 ◽

Vol 104 (2) ◽

pp. 619-621 ◽

Cited By ~ 31

Author(s):

Mario J. Nappa ◽

Roberto Santi ◽

Steven P. Diefenbach ◽

Jack Halpern

Keyword(s):

Hydrogen Bond ◽

Bond Formation ◽

Reductive Elimination ◽

Hydrogen Bond Formation ◽

Elimination Reactions

Download Full-text

Theoretical analysis of the (HNO)2, (HNO···HNS), and (HNS)2 dimers — A case of red and blue shifts of N–H stretching frequency

Canadian Journal of Chemistry ◽

10.1139/v10-048 ◽

2010 ◽

Vol 88 (8) ◽

pp. 849-857 ◽

Cited By ~ 2

Author(s):

Nguyen Tien Trung ◽

Tran Thanh Hue ◽

Minh Tho Nguyen

Keyword(s):

Hydrogen Bond ◽

Quantum Chemical ◽

Bond Formation ◽

Blue Shift ◽

Proton Donor ◽

Basis Sets ◽

Coupled Cluster ◽

Hydrogen Bond Formation ◽

Length Contraction ◽

Moller Plesset

The hydrogen-bonded interactions in the simple (HNZ)2 dimers, with Z = O and S, were investigated using quantum chemical calculations with the second-order Møller–Plesset perturbation (MP2), coupled-cluster with single, double (CCSD), and triple excitations (CCSD(T)) methods in conjunction with the 6-311++G(2d,2p), aug-cc-pVDZ, and aug-cc-pVTZ basis sets. Six-membered cyclic structures were found to be stable complexes for the dimers (HNO)2, (HNS)2, and (HNO–HNS). The pair (HNS)2 has the largest complexation energy (–11 kJ/mol), and (HNO)2 the smallest one (–9 kJ/mol). A bond length contraction and a frequency blue shift of the N–H bond simultaneously occur upon hydrogen bond formation of the N–H···S type, which has rarely been observed before. The stronger the intramolecular hyperconjugation and the lower the polarization of the X–H bond involved as proton donor in the hydrogen bond, the more predominant is the formation of a blue-shifting hydrogen bond.

Download Full-text