In the structures of the isostructural cocrystals[Cu^(I)_(3)(CNXyl)_(3)]·CHX_(3)(X=Br,I),two adjacent Cu^(I)-bound isocyanide groups,whose carbon lone pairs are blocked by ligation,exhibit nucleophilic properties...In the structures of the isostructural cocrystals[Cu^(I)_(3)(CNXyl)_(3)]·CHX_(3)(X=Br,I),two adjacent Cu^(I)-bound isocyanide groups,whose carbon lone pairs are blocked by ligation,exhibit nucleophilic properties induced by aπ-donating d10[Cu^(I)]center and function as an integrated two-center halogen bond acceptor forming bifurcatedμ_(2)-X⋯(C,C)halogen bonds.展开更多
Cocrystallization of the dithiocarbamate complexes[M(S_(2)CNEt_(2))_(2)](M=Ni 1,Pd 2,Pt 3)and X-substituted perfluoroarenes(X=I,Br;1,2-dibromoperfluorobenzene FBrB and 1,2-diiodoperfluorobenzene FIB)gives isomorphous ...Cocrystallization of the dithiocarbamate complexes[M(S_(2)CNEt_(2))_(2)](M=Ni 1,Pd 2,Pt 3)and X-substituted perfluoroarenes(X=I,Br;1,2-dibromoperfluorobenzene FBrB and 1,2-diiodoperfluorobenzene FIB)gives isomorphous cocrystals of(1-3)·2(FBrB)and 1·2(FIB),correspondingly,whose structures were studied by single-crystal X-ray diffractometry.The crystal structures demonstrate similar intermolecular contact types:short arene MS_(4)…π-hole stacking contacts,X…S halogen bonds,C-H…X(X=Br,I)bonds and C-H…F hydrogen bonds.In these structures,the{d_(z^(2))-M^(Ⅱ)S_(4)}moiety functions as an integrated five-center acceptor(that includes a metal d_(z^(2))-orbital,even for a poorly d_(z^(2))-nucleophilic Ni^(Ⅱ) center)toward theπ-hole of an X-substituted perfluoroarene.This interaction provides stacking of inorganic and organic units furnishing the reverse sandwich structures.Density functional theory(DFT)calculations,in combination with quantum theory of atoms-in-molecules(QTAIM)and noncovalent interaction plot(NCIplot)analyses,supported the structure-defining role of the{MS_(4)}…π-hole contacts.The nucleophilicity of the{MS_(4)}cores toward electron deficient π-holes was verified from the molecular electrostatic potential surface(MEP)and electron density/electrostatic potential(ED/ESP)profiles,and atoms-in-molecules(AIM)charge analysis.The relatively strong{MS_(4)}…π-hole contact strength(interaction energies for an{MS_(4)}…π-hole 1:1 adduct range from^(-1)2.1 to^(-1)3.5 kcal mol^(-1))is probably due to the large overlap between the electron deficient π-cloud and the integrated{MS_(4)}nucleophilic core.The 1:1 adduct based on 3 demonstrates the largest strength(13.5 kcal mol^(-1))in the series and this strength agrees well with the higher d_(z^(2))-nucleophilicity of the Pt^(Ⅱ) center revealed by the MEP analysis(-33.6 kcal mol^(-1)).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
Co-crystallization of dithiocarbamate complexes[M^(Ⅱ)(S_(2)CNEt_(2))_(2)](M=Cu 1,Ni 2,Pd 3,Pt 4)and 1,3,5-triiodotrifluorobenzene(FIB)gives an isomorphic series of(1-4)·2FIB co-crystals exhibiting quadruple Cu/N...Co-crystallization of dithiocarbamate complexes[M^(Ⅱ)(S_(2)CNEt_(2))_(2)](M=Cu 1,Ni 2,Pd 3,Pt 4)and 1,3,5-triiodotrifluorobenzene(FIB)gives an isomorphic series of(1-4)·2FIB co-crystals exhibiting quadruple Cu/Ni/Pd/Pt isostructural exchange.In the structures of(1-4)·2FIB,the halogen-bonded C-I…M(Ni,Pd,Pt)and semicoordination M…I-C(Cu)metal-involving contacts were identified by X-ray diffractometry and their nature was verified theoretically.The directionality of the I_(σ-hole)…d_(z)^(2)M^(Ⅱ) and M^(Ⅱ)…I_(electron belt)interactions depends on the identity of a metal center:on going from a rather electrophilic Cu^(Ⅱ) to substantially more nucleophilic Ni^(Ⅱ),Pd^(Ⅱ),and Pt^(Ⅱ) centers,we observed the electron belt-to-σ-hole switch of a noncovalently bound iodine(I)of FIB and,correspondingly,its shift from semicoordination to halogen bonding.The negative values of the electrostatic potentials(given in parentheses)were estimated for all metal centers and they decrease in the order Cu^(Ⅱ)(-8.8)>Ni^(Ⅱ)(-24.5)>Pd^(Ⅱ)(-28.6)>Pt^(Ⅱ)(-33.3 kcal mol^(-1)).Despite the negative potentials at all M^(Ⅱ)s,the semicoordinative contact Cu…I was established by the recognition of the LP(I)→LP*(Cu)charge transfer using natural bond orbital(NBO)analysis and the comparison of electron density(ED)and electrostatic potential(ESP)minima positions along the I…Cu bond paths.In the case of the rather nucleophilic(although positively charged)Pd^(Ⅱ) and Pt^(Ⅱ) centers,the contacts C-I…d_(z)^(2)[Pd]and C-I…d_(z)^(2)[Pt]can be attributed to the unconventional metal-involving halogen bonding;these contacts are among the strongest(4.30 and 5.42 kcal mol^(-1),correspondingly)between any metal center and iodine(Ⅰ)-based σ-hole donors.展开更多
Crystallization of[CuI(CNXyl)_(3)](1)with I_(2)(exhibiting strong halogen bond donor properties),at different molar ratios between the reactants,resulted in a series of(XylNC)Cu^(Ⅰ) crystal polyiodides formed along w...Crystallization of[CuI(CNXyl)_(3)](1)with I_(2)(exhibiting strong halogen bond donor properties),at different molar ratios between the reactants,resulted in a series of(XylNC)Cu^(Ⅰ) crystal polyiodides formed along with gradual accumulation of iodine,namely[Cu(I_(3))(CNXyl)_(3)](two crystalline polymorphs 2^(Ⅰ) and 2^(Ⅱ)),[Cu(I_(3))(CNXyl)_(3)]·1/2I_(2)(2·1/2 I_(2))and[Cu(CNXyl)_(3)](I_(5))(3);all these compounds were studied by X-ray diffractometry.Molecular electrostatic potential(MEP)surface plots were also calculated using density functional theory(DFT)for isolated molecules of 2 and I_(2),showing electrophilic and nucleophilic sites.Halogen bonding in 2·1/2 I_(2) was additionally elucidated for both crystal and cluster models,including combined quantum theory of atoms-in-molecules(QTAIM)and one-electron potential(OEP)projections.For model clusters,DFT energetic analysis,quantum theory of atoms-in-molecules,combined with the noncovalent interaction index plot(QTAIM/NCIplot),natural bond orbital(NBO)donor–acceptor charge transfer analysis,and Wiberg bond index(WBI)analysis were used.In the structure of 2·1/2I_(2),the presence of an I_(2)…I_(3)_(−)halogen bonded linkage gives a key toward the understanding of the precise mechanism for the generation of I_(5)^(−)(and then I_(8)^(2−))ligands from I_(2) and metal-coordinated I_(3)_(−).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funded by the Russian Science Foundation(project 19-13-00013)Measurements were performed at the Center for Magnetic Resonance,Center for X-ray Diffraction Studies,Center for Chemical Analysis and Materials Research,and Chemistry Educational Center(all belonging to Saint Petersburg State University).A.F.thanks the MICIU/AEI of Spain(project PID2020-115637GB-I00,FEDER funds)for financial support of these theoretical studies.
文摘In the structures of the isostructural cocrystals[Cu^(I)_(3)(CNXyl)_(3)]·CHX_(3)(X=Br,I),two adjacent Cu^(I)-bound isocyanide groups,whose carbon lone pairs are blocked by ligation,exhibit nucleophilic properties induced by aπ-donating d10[Cu^(I)]center and function as an integrated two-center halogen bond acceptor forming bifurcatedμ_(2)-X⋯(C,C)halogen bonds.
基金supported by the Russian Foundation for Basic Research(project 20-03-00073,synthetic and crystal engineering studies)the Russian Science Foundation(project 21-73-00059,ELF,ED/ESP,AIM analyses)the MICIU/AEI from Spain for financial support of his computational studies(project number PID2020-115637GB-I00,FEDER funds,MEP,QTAIM and NCIplot analyses).
文摘Cocrystallization of the dithiocarbamate complexes[M(S_(2)CNEt_(2))_(2)](M=Ni 1,Pd 2,Pt 3)and X-substituted perfluoroarenes(X=I,Br;1,2-dibromoperfluorobenzene FBrB and 1,2-diiodoperfluorobenzene FIB)gives isomorphous cocrystals of(1-3)·2(FBrB)and 1·2(FIB),correspondingly,whose structures were studied by single-crystal X-ray diffractometry.The crystal structures demonstrate similar intermolecular contact types:short arene MS_(4)…π-hole stacking contacts,X…S halogen bonds,C-H…X(X=Br,I)bonds and C-H…F hydrogen bonds.In these structures,the{d_(z^(2))-M^(Ⅱ)S_(4)}moiety functions as an integrated five-center acceptor(that includes a metal d_(z^(2))-orbital,even for a poorly d_(z^(2))-nucleophilic Ni^(Ⅱ) center)toward theπ-hole of an X-substituted perfluoroarene.This interaction provides stacking of inorganic and organic units furnishing the reverse sandwich structures.Density functional theory(DFT)calculations,in combination with quantum theory of atoms-in-molecules(QTAIM)and noncovalent interaction plot(NCIplot)analyses,supported the structure-defining role of the{MS_(4)}…π-hole contacts.The nucleophilicity of the{MS_(4)}cores toward electron deficient π-holes was verified from the molecular electrostatic potential surface(MEP)and electron density/electrostatic potential(ED/ESP)profiles,and atoms-in-molecules(AIM)charge analysis.The relatively strong{MS_(4)}…π-hole contact strength(interaction energies for an{MS_(4)}…π-hole 1:1 adduct range from^(-1)2.1 to^(-1)3.5 kcal mol^(-1))is probably due to the large overlap between the electron deficient π-cloud and the integrated{MS_(4)}nucleophilic core.The 1:1 adduct based on 3 demonstrates the largest strength(13.5 kcal mol^(-1))in the series and this strength agrees well with the higher d_(z^(2))-nucleophilicity of the Pt^(Ⅱ) center revealed by the MEP analysis(-33.6 kcal mol^(-1)).
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supported by the Russian Foundation for Basic Research(20-03-00073)Saint Petersburg State University for a postdoctoral fellowship.
文摘Co-crystallization of dithiocarbamate complexes[M^(Ⅱ)(S_(2)CNEt_(2))_(2)](M=Cu 1,Ni 2,Pd 3,Pt 4)and 1,3,5-triiodotrifluorobenzene(FIB)gives an isomorphic series of(1-4)·2FIB co-crystals exhibiting quadruple Cu/Ni/Pd/Pt isostructural exchange.In the structures of(1-4)·2FIB,the halogen-bonded C-I…M(Ni,Pd,Pt)and semicoordination M…I-C(Cu)metal-involving contacts were identified by X-ray diffractometry and their nature was verified theoretically.The directionality of the I_(σ-hole)…d_(z)^(2)M^(Ⅱ) and M^(Ⅱ)…I_(electron belt)interactions depends on the identity of a metal center:on going from a rather electrophilic Cu^(Ⅱ) to substantially more nucleophilic Ni^(Ⅱ),Pd^(Ⅱ),and Pt^(Ⅱ) centers,we observed the electron belt-to-σ-hole switch of a noncovalently bound iodine(I)of FIB and,correspondingly,its shift from semicoordination to halogen bonding.The negative values of the electrostatic potentials(given in parentheses)were estimated for all metal centers and they decrease in the order Cu^(Ⅱ)(-8.8)>Ni^(Ⅱ)(-24.5)>Pd^(Ⅱ)(-28.6)>Pt^(Ⅱ)(-33.3 kcal mol^(-1)).Despite the negative potentials at all M^(Ⅱ)s,the semicoordinative contact Cu…I was established by the recognition of the LP(I)→LP*(Cu)charge transfer using natural bond orbital(NBO)analysis and the comparison of electron density(ED)and electrostatic potential(ESP)minima positions along the I…Cu bond paths.In the case of the rather nucleophilic(although positively charged)Pd^(Ⅱ) and Pt^(Ⅱ) centers,the contacts C-I…d_(z)^(2)[Pd]and C-I…d_(z)^(2)[Pt]can be attributed to the unconventional metal-involving halogen bonding;these contacts are among the strongest(4.30 and 5.42 kcal mol^(-1),correspondingly)between any metal center and iodine(Ⅰ)-based σ-hole donors.
基金supported by the Russian Science Foundation projects 22-13-00078(experimental part and XRD analysis)22-73-00021(theoretical calculations under periodic conditions and for cluster mode)The QTAIM/NCIPlot calculations were funded by the MICIU/AEI of Spain(project PID2020-115637GB-I00 FEDER funds)。
文摘Crystallization of[CuI(CNXyl)_(3)](1)with I_(2)(exhibiting strong halogen bond donor properties),at different molar ratios between the reactants,resulted in a series of(XylNC)Cu^(Ⅰ) crystal polyiodides formed along with gradual accumulation of iodine,namely[Cu(I_(3))(CNXyl)_(3)](two crystalline polymorphs 2^(Ⅰ) and 2^(Ⅱ)),[Cu(I_(3))(CNXyl)_(3)]·1/2I_(2)(2·1/2 I_(2))and[Cu(CNXyl)_(3)](I_(5))(3);all these compounds were studied by X-ray diffractometry.Molecular electrostatic potential(MEP)surface plots were also calculated using density functional theory(DFT)for isolated molecules of 2 and I_(2),showing electrophilic and nucleophilic sites.Halogen bonding in 2·1/2 I_(2) was additionally elucidated for both crystal and cluster models,including combined quantum theory of atoms-in-molecules(QTAIM)and one-electron potential(OEP)projections.For model clusters,DFT energetic analysis,quantum theory of atoms-in-molecules,combined with the noncovalent interaction index plot(QTAIM/NCIplot),natural bond orbital(NBO)donor–acceptor charge transfer analysis,and Wiberg bond index(WBI)analysis were used.In the structure of 2·1/2I_(2),the presence of an I_(2)…I_(3)_(−)halogen bonded linkage gives a key toward the understanding of the precise mechanism for the generation of I_(5)^(−)(and then I_(8)^(2−))ligands from I_(2) and metal-coordinated I_(3)_(−).
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.
