TY - JOUR

T1 - P=O Moiety as an Ambidextrous Hydrogen Bond Acceptor

AU - Тупикина, Елена Юрьевна

AU - Bodensteiner, M.

AU - Tolstoy, Peter M.

AU - Денисов, Глеб Семенович

AU - Shenderovich, Ilya G.

N1 - Funding Information: We thank Prof. Dr. Sc. Konstantin A. Lyssenko for helpful discussions. This work was supported by the Russian Foundation of Basic Research (Project 17-03-00590) and the German−Russian Interdisciplinary Science Center (G-RISC) funded by the German Federal Foreign Office via the German Academic Exchange Service (DAAD). The authors gratefully acknowledge the Gauss Centre for Supercomputing e.V. for funding this project by providing computing time on the GCS Supercomputer SuperMUC at Leibniz Supercomputing Centre (LRZ).

PY - 2018/1/25

Y1 - 2018/1/25

N2 - Hydrogen bond patterns of crystals of phosphinic, phosphonic, and phosphoric acids and their cocrystals with phosphine oxides were studied using 31P NMR and single-crystal X-ray diffraction. Two main factors govern these patterns and favor or prevent the formation of cocrystals. The first one is a high proton-accepting ability of the P=O moiety in these acids. As a result, this moiety effectively competes with other proton acceptors for hydrogen bonding. For example, this moiety is a stronger proton acceptor than the C=O moiety of carboxylic acids. The second factor is the inclination of the P=O moiety of both the acids and the oxides to form two hydrogen bonds at once. The peculiarity of these bonds is that they weaken each other to a little degree only. In order to highlight this point, we are using the term "ambidextrous". These two features should govern the interactions of P=O moiety with water and other proton donors and acceptors in molecular clusters, the active sites of enzymes, soft matter, and at surfaces.

AB - Hydrogen bond patterns of crystals of phosphinic, phosphonic, and phosphoric acids and their cocrystals with phosphine oxides were studied using 31P NMR and single-crystal X-ray diffraction. Two main factors govern these patterns and favor or prevent the formation of cocrystals. The first one is a high proton-accepting ability of the P=O moiety in these acids. As a result, this moiety effectively competes with other proton acceptors for hydrogen bonding. For example, this moiety is a stronger proton acceptor than the C=O moiety of carboxylic acids. The second factor is the inclination of the P=O moiety of both the acids and the oxides to form two hydrogen bonds at once. The peculiarity of these bonds is that they weaken each other to a little degree only. In order to highlight this point, we are using the term "ambidextrous". These two features should govern the interactions of P=O moiety with water and other proton donors and acceptors in molecular clusters, the active sites of enzymes, soft matter, and at surfaces.

KW - ACID-BASE COMPLEXES

KW - CHEMICAL-SHIFT TENSOR

KW - CRYSTAL-STRUCTURE

KW - EXPERIMENTAL CHARGE-DENSITY

KW - MOLECULAR-CRYSTALS

KW - PHOSPHINE OXIDES

KW - PROTON-BOUND HOMODIMERS

KW - SOLID-STATE

KW - TRIPHENYLPHOSPHINE OXIDE HEMIHYDRATE

KW - X-RAY-DIFFRACTION

UR - http://www.scopus.com/inward/record.url?scp=85041231291&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/po-moiety-ambidextrous-hydrogen-bond-acceptor

U2 - 10.1021/acs.jpcc.7b11299

DO - 10.1021/acs.jpcc.7b11299

M3 - Article

VL - 122

SP - 1711

EP - 1720

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 3

ER -