The dichalcogenides Ph_(2)Ch_(2)(Ch=S,Se,Te)were cocrystallized with perfluorinated chalcogen bond donors Tol_(2)^(F)Te and Py_(2)^(F)Te(Tol^(F)=4-CF_(3)C_(6)F_(4),PyF=4-NC_(5)F_(4))to obtain the 1:1 cocrystals Tol_(2...The dichalcogenides Ph_(2)Ch_(2)(Ch=S,Se,Te)were cocrystallized with perfluorinated chalcogen bond donors Tol_(2)^(F)Te and Py_(2)^(F)Te(Tol^(F)=4-CF_(3)C_(6)F_(4),PyF=4-NC_(5)F_(4))to obtain the 1:1 cocrystals Tol_(2)^(F)Te·Ph_(2)Ch_(2)(Ch=S 1,Se 2,Te 3)and Py_(2)^(F)Te·Ph_(2)Se_(2)(4).In the X-ray structures of 1-4,heterovalent Te^(Ⅱ)…Ch^(Ⅰ)(Ch=S,Se,Te)chalcogen bonding was identified on consideration of the geometrical parameters and,in addition,based on the results of appropriate density functional theory(DFT)calculations including quantum theory of atoms-in-molecules(QTAIM),noncovalent interaction plot(NCIplot)analysis,molecular electrostatic potential surfaces(MEP),and atoms-in-molecules(AIM)charge analysis.The binding energy in the dimeric structure is in the range between -9.7 and -12.9 kcal mol^(-1),where the contribution of the heterovalent chalcogen bonding ranges from -4.7 to -6.5 kcal mol^(-1).In the Te^(Ⅱ)…Ch^(Ⅰ) moiety,the Te^(Ⅱ) center plays the role of an electrophilic partner,while the chalcogens in the lower oxidation state,1+,exhibit nucleophilic properties.The heterovalent Te^(Ⅱ)…Ch^(Ⅰ)(Ch=Se,Te)chalcogen bonding was thus used for the targeted noncovalent integration of two Ch centers in different oxidation states.展开更多
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
Cocrystallization of the palladium acetate cluster Pd_(3)(OAc)_(6)(abbreviated as[Pd_(3)])with electron-deficient iodine(I)-based perfluoroarenes(ArFI:iodopentafluorobenzene,4-iodoheptafluorotoluene,1,4-diiodotetraflu...Cocrystallization of the palladium acetate cluster Pd_(3)(OAc)_(6)(abbreviated as[Pd_(3)])with electron-deficient iodine(I)-based perfluoroarenes(ArFI:iodopentafluorobenzene,4-iodoheptafluorotoluene,1,4-diiodotetrafluorobenzene,1,2-diiodotetrafluorobenzene,and octafluoro-4,4’-diiodo-1,1-biphenyl)and iodinefree octafluoronaphthalene gave a series of six cocrystals[Pd_(3)]·(arene)studied by single-crystal X-ray diffractometry.Significant intermolecular noncovalent interactions were verified by a density functional theory study,molecular electrostatic potential and Hirshfeld surface analyses,a combined QTAIM/NCPlot approach,and NBO and energy framework calculations.In five out of six structures,the aromatic rings coupled with cluster[Pd_(3)]via lone pair-π-(ArF)-hole interactions.The iodine-containing arenes,ArFI,were additionally involved in halogen bonding with carboxylate O centers,but inorganic-organic stacking still remained the structure-determining interaction.In the stacking,the electron-rich PdO_(4)plane behaved as a five-center nucleophile providing oxygen lone pairs in addition to the dz_(2)-PdII orbital;this plane complemented theπ-acidic surface of the arenes,affording highly polar circular stacking,where organics wrapped inorganics.展开更多
基金supported by the Russian Science Foundation(project 21-73-10030:synthetic experiments,project 19-13-00338:crystal engineering studies)funded by MICIU/AEI of Spain(project PID2020-115637GB-I00 FEDER funds).
文摘The dichalcogenides Ph_(2)Ch_(2)(Ch=S,Se,Te)were cocrystallized with perfluorinated chalcogen bond donors Tol_(2)^(F)Te and Py_(2)^(F)Te(Tol^(F)=4-CF_(3)C_(6)F_(4),PyF=4-NC_(5)F_(4))to obtain the 1:1 cocrystals Tol_(2)^(F)Te·Ph_(2)Ch_(2)(Ch=S 1,Se 2,Te 3)and Py_(2)^(F)Te·Ph_(2)Se_(2)(4).In the X-ray structures of 1-4,heterovalent Te^(Ⅱ)…Ch^(Ⅰ)(Ch=S,Se,Te)chalcogen bonding was identified on consideration of the geometrical parameters and,in addition,based on the results of appropriate density functional theory(DFT)calculations including quantum theory of atoms-in-molecules(QTAIM),noncovalent interaction plot(NCIplot)analysis,molecular electrostatic potential surfaces(MEP),and atoms-in-molecules(AIM)charge analysis.The binding energy in the dimeric structure is in the range between -9.7 and -12.9 kcal mol^(-1),where the contribution of the heterovalent chalcogen bonding ranges from -4.7 to -6.5 kcal mol^(-1).In the Te^(Ⅱ)…Ch^(Ⅰ) moiety,the Te^(Ⅱ) center plays the role of an electrophilic partner,while the chalcogens in the lower oxidation state,1+,exhibit nucleophilic properties.The heterovalent Te^(Ⅱ)…Ch^(Ⅰ)(Ch=Se,Te)chalcogen bonding was thus used for the targeted noncovalent integration of two Ch centers in different oxidation states.
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the Russian Science Foundation grants 19-13-00338(crystal engineering study)and 21-73-10030(molecular design ofπ-andσ-hole donors)the equipment of the shared experimental facilities supported by N.S.Kurnakov Institute of General and Inorganic Chemistry RAS.BG and AF acknowledge the MICIU/AEI from Spain for financial support of the computational study(project numbers CTQ2017-85821-R and PID2020-115637GB-I00,FEDER funds)。
文摘Cocrystallization of the palladium acetate cluster Pd_(3)(OAc)_(6)(abbreviated as[Pd_(3)])with electron-deficient iodine(I)-based perfluoroarenes(ArFI:iodopentafluorobenzene,4-iodoheptafluorotoluene,1,4-diiodotetrafluorobenzene,1,2-diiodotetrafluorobenzene,and octafluoro-4,4’-diiodo-1,1-biphenyl)and iodinefree octafluoronaphthalene gave a series of six cocrystals[Pd_(3)]·(arene)studied by single-crystal X-ray diffractometry.Significant intermolecular noncovalent interactions were verified by a density functional theory study,molecular electrostatic potential and Hirshfeld surface analyses,a combined QTAIM/NCPlot approach,and NBO and energy framework calculations.In five out of six structures,the aromatic rings coupled with cluster[Pd_(3)]via lone pair-π-(ArF)-hole interactions.The iodine-containing arenes,ArFI,were additionally involved in halogen bonding with carboxylate O centers,but inorganic-organic stacking still remained the structure-determining interaction.In the stacking,the electron-rich PdO_(4)plane behaved as a five-center nucleophile providing oxygen lone pairs in addition to the dz_(2)-PdII orbital;this plane complemented theπ-acidic surface of the arenes,affording highly polar circular stacking,where organics wrapped inorganics.
