TY - JOUR

T1 - Ditopic Phosphide Oxide Group

T2 - A Rigidifying Lewis Base to Switch Luminescence and Reactivity of a Disilver Complex

AU - Beliaeva, Mariia

AU - Belyaev, Andrey

AU - Grachova, Elena V.

AU - Steffen, Andreas

AU - Koshevoy, Igor O.

N1 - Publisher Copyright: © 2021 The Authors. Published by American Chemical Society.

PY - 2021/9/22

Y1 - 2021/9/22

N2 - Heterodentate phosphines containing anionic organophosphorus groups remain virtually unexplored ligands in the coordination chemistry of coinage metals. A hybrid phosphine-phosphine oxide (o-Ph2PC6H4)2P(O)H (HP3O) readily forms the disilver complex [Ag2(P3O)2] (1) upon deprotonation of the (O)P-H fragment. Due to the electron-rich nature, the anionic phosphide oxide unit in 1 takes part in efficient intermolecular hydrogen bonding, which has an unusual and remarkably strong impact on the photoluminescence of 1, changing the emission from red (644 nm) to green-yellow (539 nm) in the solid. The basicity of the R2(O)P- group and its affinity for both inter- and intramolecular donor-acceptor interactions allow converting 1 into hydrohalogenated (2, 3) and boronated (4) derivatives, which reveal a gradual hypsochromic shift of luminescence, reaching the wavelength of 489 nm. Systematic variable-temperature analysis of the excited state properties suggests that thermally activated delayed fluorescence is involved in the emission process. The long-lived excited states for 1-4, the energy of which is largely regulated by means of the phosphide oxide unit, are potentially suitable for triplet energy transfer photocatalysis. With the highest T1 energy among 1-4, complex 4 demonstrates excellent photocatalytic activity in a [2+2] cycloaddition reaction, which has been realized for the first time for silver(I) compounds.

AB - Heterodentate phosphines containing anionic organophosphorus groups remain virtually unexplored ligands in the coordination chemistry of coinage metals. A hybrid phosphine-phosphine oxide (o-Ph2PC6H4)2P(O)H (HP3O) readily forms the disilver complex [Ag2(P3O)2] (1) upon deprotonation of the (O)P-H fragment. Due to the electron-rich nature, the anionic phosphide oxide unit in 1 takes part in efficient intermolecular hydrogen bonding, which has an unusual and remarkably strong impact on the photoluminescence of 1, changing the emission from red (644 nm) to green-yellow (539 nm) in the solid. The basicity of the R2(O)P- group and its affinity for both inter- and intramolecular donor-acceptor interactions allow converting 1 into hydrohalogenated (2, 3) and boronated (4) derivatives, which reveal a gradual hypsochromic shift of luminescence, reaching the wavelength of 489 nm. Systematic variable-temperature analysis of the excited state properties suggests that thermally activated delayed fluorescence is involved in the emission process. The long-lived excited states for 1-4, the energy of which is largely regulated by means of the phosphide oxide unit, are potentially suitable for triplet energy transfer photocatalysis. With the highest T1 energy among 1-4, complex 4 demonstrates excellent photocatalytic activity in a [2+2] cycloaddition reaction, which has been realized for the first time for silver(I) compounds.

KW - VISIBLE-LIGHT PHOTOCATALYSIS

KW - SILVER(I) COMPLEXES

KW - PHOTOLUMINESCENCE PROPERTIES

KW - DIPHOSPHINE LIGANDS

KW - CRYSTAL

KW - CLUSTERS

KW - MECHANOCHROMISM

KW - FLUORESCENCE

KW - TRANSITION

KW - IRIDIUM

UR - http://www.scopus.com/inward/record.url?scp=85115807249&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/5644c395-98f8-3924-9fb3-b60490a40679/

U2 - 10.1021/jacs.1c04413

DO - 10.1021/jacs.1c04413

M3 - Article

AN - SCOPUS:85115807249

VL - 143

SP - 15045

EP - 15055

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 37

ER -