The moderately phosphorescent platinum(II)complexes[Pt(ppy)(acac)](1;ppyH=2-phenylpyridine,acacH=acetylacetone),[Pt(ppy)(hd)](2;hdH=heptanedione-3,5),[Pt(ppy)(tmhd)](3;tmhdH=2,2,6,6-tetramethylheptanedione-3,5),[Pt(df...The moderately phosphorescent platinum(II)complexes[Pt(ppy)(acac)](1;ppyH=2-phenylpyridine,acacH=acetylacetone),[Pt(ppy)(hd)](2;hdH=heptanedione-3,5),[Pt(ppy)(tmhd)](3;tmhdH=2,2,6,6-tetramethylheptanedione-3,5),[Pt(dfppy)(acac)](4;dfppyH=2-(2’,4’-difluorophenyl)pyridine),and[Pt(dfppy)(tmhd)](5)were precipitated on cocrystallization with anticrown Hg_(3)(1,2-C_(6)F_(4))_(3)(Hg_(3))to give Hg^(II)-Pt^(II)stacked heteroplanar architectures(1-3)·Hg_(3)and(4-5)·Hg_(3)·Me_(2)CO.Synchrotron X-ray diffraction studies of these cocrystals along with in-depth theoretical density functional theory(DFT;PBE0-D3BJ)calculations,employing a set of computational tools(QTAIM,ELF,IGMH,MEP,CDF,ETS-NOCV,and SAPT methods),allowed the recognition of the spodium bonds Hg…Pt and Hg…C(the former is significantly stronger than the latter)as the stacking-directing contacts.The major part(57%)of the total interaction energy between 3 and Hg_(3)(-32.9 kcal mol^(-1)),as a model system,comes from Hg…Pt bonding.Heteroplanar stacking is mostly controlled by dispersion and electrostatic forces,but the d_(z)2(Pt)→σ*(Hg-C)charge transfer also provides a noticeable contribution;Hg^(II)functions as an electrophilic component of the Hg…Pt and Hg…C contacts.The spodium bond-driven supramolecular integration provides enhanced phosphorescence lifetimes and up to 6-fold solid-state quantum yield enhancement for all cocrystals compared to the parent Pt^(II)species.Appropriate DFT studies along with the analysis of calculated radiative and nonradiative decay rate constants indicate that the heteroplanar stacking reduces the population of the^(3)MC state,thus increasing the quantum yield.展开更多
The cyclometalated square-planar platinum(Ⅱ)complex 1,bearing a 2-mercaptopyridine 1-oxide chelate ligand,was cocrystallized with any one of the planarπ-hole donating tetrahalo-1,4-benzoquinones QX(X=F,Cl,Br,I)to gi...The cyclometalated square-planar platinum(Ⅱ)complex 1,bearing a 2-mercaptopyridine 1-oxide chelate ligand,was cocrystallized with any one of the planarπ-hole donating tetrahalo-1,4-benzoquinones QX(X=F,Cl,Br,I)to give a series of cocrystals 1·QX;the latter were studied by X-ray crystallography and^(195)Pt MAS-NMR spectroscopy.These studies revealed that all four cocrystals exhibit almost the sameπ-stacked organic-inorganic structural pattern.展开更多
The solid-state structures of co-crystals of chalcogenadiazoles(ChDAs)with planar half-lantern Pt_(2)^(Ⅱ) and mononuclear Pt^(Ⅱ)complexes exhibit short Ch…Pt^(Ⅱ)(Ch=Se,Te)contacts that occur between a metal site a...The solid-state structures of co-crystals of chalcogenadiazoles(ChDAs)with planar half-lantern Pt_(2)^(Ⅱ) and mononuclear Pt^(Ⅱ)complexes exhibit short Ch…Pt^(Ⅱ)(Ch=Se,Te)contacts that occur between a metal site and the ChDA.The structures demonstrate a unique geometric feature whereby the two deepσ-holes of ChDA are turned away from a d_(z^(2))-nucleophilic PtII site.展开更多
基金support from the Russian Science Foundation(Project 21-73-10030)is gratefully acknowledgedthe Center for Magnetic Resonance,the Center for Optical and Laser Materials Research,and the Center for Chemical Analysis and Materials Research,while theoretical calculations were performed at the Computational Center(all belonging to Saint Petersburg State University)the Fundação para a Ciência e a Tecnologia(FCT),Portugal,projects UIDB/00100/2020 and UIDP/00100/2020 of Centro de Química Estrutural and LA/P/0056/2020 of the Institute of Molecular Sciences for providing facilities at his disposal.
文摘The moderately phosphorescent platinum(II)complexes[Pt(ppy)(acac)](1;ppyH=2-phenylpyridine,acacH=acetylacetone),[Pt(ppy)(hd)](2;hdH=heptanedione-3,5),[Pt(ppy)(tmhd)](3;tmhdH=2,2,6,6-tetramethylheptanedione-3,5),[Pt(dfppy)(acac)](4;dfppyH=2-(2’,4’-difluorophenyl)pyridine),and[Pt(dfppy)(tmhd)](5)were precipitated on cocrystallization with anticrown Hg_(3)(1,2-C_(6)F_(4))_(3)(Hg_(3))to give Hg^(II)-Pt^(II)stacked heteroplanar architectures(1-3)·Hg_(3)and(4-5)·Hg_(3)·Me_(2)CO.Synchrotron X-ray diffraction studies of these cocrystals along with in-depth theoretical density functional theory(DFT;PBE0-D3BJ)calculations,employing a set of computational tools(QTAIM,ELF,IGMH,MEP,CDF,ETS-NOCV,and SAPT methods),allowed the recognition of the spodium bonds Hg…Pt and Hg…C(the former is significantly stronger than the latter)as the stacking-directing contacts.The major part(57%)of the total interaction energy between 3 and Hg_(3)(-32.9 kcal mol^(-1)),as a model system,comes from Hg…Pt bonding.Heteroplanar stacking is mostly controlled by dispersion and electrostatic forces,but the d_(z)2(Pt)→σ*(Hg-C)charge transfer also provides a noticeable contribution;Hg^(II)functions as an electrophilic component of the Hg…Pt and Hg…C contacts.The spodium bond-driven supramolecular integration provides enhanced phosphorescence lifetimes and up to 6-fold solid-state quantum yield enhancement for all cocrystals compared to the parent Pt^(II)species.Appropriate DFT studies along with the analysis of calculated radiative and nonradiative decay rate constants indicate that the heteroplanar stacking reduces the population of the^(3)MC state,thus increasing the quantum yield.
基金support of the Russian Science Foundation(project 23-73-01074)is gratefully acknowledged.
文摘The cyclometalated square-planar platinum(Ⅱ)complex 1,bearing a 2-mercaptopyridine 1-oxide chelate ligand,was cocrystallized with any one of the planarπ-hole donating tetrahalo-1,4-benzoquinones QX(X=F,Cl,Br,I)to give a series of cocrystals 1·QX;the latter were studied by X-ray crystallography and^(195)Pt MAS-NMR spectroscopy.These studies revealed that all four cocrystals exhibit almost the sameπ-stacked organic-inorganic structural pattern.
基金support of the Russian Science Foundation(project 21-73-00056)is gratefully acknowledged.Physicochemical studies were performed at the Center for Magnetic Resonance,Center for X-ray Diffraction Studies and Center for Chemical Analysis and Materials Research,while theoretical calculations were performed at the Computational Center(all belonging to Saint Petersburg State University)M.L.K.thanks the Fundação para a Ciência e a Tecnologia(FCT),Portugal,projects UIDB/00100/2020 and UIDP/00100/2020 of Centro de Química Estrutural and LA/P/0056/2020 of the Institute of Molecular Sciences for putting facilities at his disposal.The authors express their gratitude to Dr A.V.Rozhkov for his kind assistance with glove-box manipulations.
文摘The solid-state structures of co-crystals of chalcogenadiazoles(ChDAs)with planar half-lantern Pt_(2)^(Ⅱ) and mononuclear Pt^(Ⅱ)complexes exhibit short Ch…Pt^(Ⅱ)(Ch=Se,Te)contacts that occur between a metal site and the ChDA.The structures demonstrate a unique geometric feature whereby the two deepσ-holes of ChDA are turned away from a d_(z^(2))-nucleophilic PtII site.
