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
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.
