TY - JOUR

T1 - Adjustable coordination of a hybrid phosphine-phosphine oxide ligand in luminescent Cu, Ag and Au complexes

AU - Dau, Thuy Minh

AU - Asamoah, Benjamin Darko

AU - Belyaev, Andrey

AU - Chakkaradhari, Gomathy

AU - Hirva, Pipsa

AU - Jänis, Janne

AU - Grachova, Elena V.

AU - Tunik, Sergey P.

AU - Koshevoy, Igor O.

N1 - Funding Information: The financial support from the Academy of Finland (grant 268993, I. O. K.) and the Russian Science Foundation (grant 16-13-10064, E. V. G.) is gratefully acknowledged. The computational work has been facilitated and made available by the Finnish Grid Infrastructure (FGI) resources. The photophysical measurements were performed using core facilities of St. Petersburg State University Research Park: Center for Optical and Laser Materials Research Publisher Copyright: © The Royal Society of Chemistry 2016. Copyright: Copyright 2017 Elsevier B.V., All rights reserved.

PY - 2016

Y1 - 2016

N2 - A potentially tridentate hemilabile ligand, PPh2-C6H4-PPh(O)-C6H4-PPh2 (P3O), has been used for the construction of a family of bimetallic complexes [MM′(P3O)2]2+ (M = M′ = Cu (1), Ag (2), Au (3); M = Au, M′ = Cu (4)) and their mononuclear halide congeners M(P3O)Hal (M = Cu (5-7), Ag (8-10)). Compounds 1-10 have been characterized in the solid state by single-crystal X-ray diffraction analysis to reveal a variable coordination mode of the phosphine-oxide group of the P3O ligand depending on the preferable number of coordination vacancies on the metal center. According to the theoretical studies, the interaction of the hard donor PO moiety with d10 ions becomes less effective in the order Cu > Ag > Au. 1-10 exhibit room temperature luminescence in the solid state, and the intensity and energy of emission are mostly determined by the nature of metal atoms. The photophysical characteristics of the monometallic species were compared with those of the related compounds M(P3)Hal (11-16) with the non-oxidized ligand P3. It was found that in the case of the copper complexes 5-7 the P3O hybrid ligand introduces effective non-radiative pathways of the excited state relaxation leading to poor emission, while for the silver luminophores the PO group leads mainly to the modulation of luminescence wavelength.

AB - A potentially tridentate hemilabile ligand, PPh2-C6H4-PPh(O)-C6H4-PPh2 (P3O), has been used for the construction of a family of bimetallic complexes [MM′(P3O)2]2+ (M = M′ = Cu (1), Ag (2), Au (3); M = Au, M′ = Cu (4)) and their mononuclear halide congeners M(P3O)Hal (M = Cu (5-7), Ag (8-10)). Compounds 1-10 have been characterized in the solid state by single-crystal X-ray diffraction analysis to reveal a variable coordination mode of the phosphine-oxide group of the P3O ligand depending on the preferable number of coordination vacancies on the metal center. According to the theoretical studies, the interaction of the hard donor PO moiety with d10 ions becomes less effective in the order Cu > Ag > Au. 1-10 exhibit room temperature luminescence in the solid state, and the intensity and energy of emission are mostly determined by the nature of metal atoms. The photophysical characteristics of the monometallic species were compared with those of the related compounds M(P3)Hal (11-16) with the non-oxidized ligand P3. It was found that in the case of the copper complexes 5-7 the P3O hybrid ligand introduces effective non-radiative pathways of the excited state relaxation leading to poor emission, while for the silver luminophores the PO group leads mainly to the modulation of luminescence wavelength.

UR - http://www.scopus.com/inward/record.url?scp=84987829278&partnerID=8YFLogxK

U2 - 10.1039/c6dt02435a

DO - 10.1039/c6dt02435a

M3 - Article

VL - 45

SP - 14160

EP - 14173

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 36

ER -