Synthesis,Crystal Structure and Photoluminescence of a Dinuclear Cuprous Complex with Thiocyanate Bridges
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摘要
A cuprous dinuclear copper complex [PPh_2PAr_2Cu(μ-SCN)_2CuPPh_2PAr_2](1,PPh_2PAr_2 =(1-bis(2-methylphenyl)-phosphine-2-diphenylphosphino)benzene) was synthesized from the reaction of Cu SCN and PPh_2PAr_2 in CH_3CN at room temperature. The compound was characterized by Elemental Analysis,NMR,UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic,space group P1 with a = 10.225(2),b = 11.360(2),c = 13.420(3) ?,α = 95.81(3),β = 93.45(3),γ = 113.78(3)°,V = 1410.4(5) ?~3,Z = 1,Mr = 1192.21,Dc = 1.404 g/cm~3,F(000) = 616,μ = 3.029 mm~(–1),GOOF = 1.052,the final R = 0.0359,and w R = 0.0964 for 4878 observed reflections with I > 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. The copper centers in the molecular structure are bridged by two thiocyanate anions and each Cu(I) is chelated further terminally by a PPh_2PAr_2 ligand. The [Cu(μ-SCN)_2Cu] cores have essential planar configurations. In the solid state,the complex exhibits blue photoluminescence with emission peaks λ_(max)= 478 nm(1),lifetimes 4.7 μs and quantum yields(ф = 0.43) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ~(1,3)MLCT excited states.
A cuprous dinuclear copper complex [PPh_2PAr_2Cu(μ-SCN)_2CuPPh_2PAr_2](1,PPh_2PAr_2 =(1-bis(2-methylphenyl)-phosphine-2-diphenylphosphino)benzene) was synthesized from the reaction of Cu SCN and PPh_2PAr_2 in CH_3CN at room temperature. The compound was characterized by Elemental Analysis,NMR,UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic,space group P1 with a = 10.225(2),b = 11.360(2),c = 13.420(3) ?,α = 95.81(3),β = 93.45(3),γ = 113.78(3)°,V = 1410.4(5) ?~3,Z = 1,Mr = 1192.21,Dc = 1.404 g/cm~3,F(000) = 616,μ = 3.029 mm~(–1),GOOF = 1.052,the final R = 0.0359,and w R = 0.0964 for 4878 observed reflections with I > 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. The copper centers in the molecular structure are bridged by two thiocyanate anions and each Cu(I) is chelated further terminally by a PPh_2PAr_2 ligand. The [Cu(μ-SCN)_2Cu] cores have essential planar configurations. In the solid state,the complex exhibits blue photoluminescence with emission peaks λ_(max)= 478 nm(1),lifetimes 4.7 μs and quantum yields(ф = 0.43) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ~(1,3)MLCT excited states.
A cuprous dinuclear copper complex [PPh_2PAr_2Cu(μ-SCN)_2CuPPh_2PAr_2](1,PPh_2PAr_2 =(1-bis(2-methylphenyl)-phosphine-2-diphenylphosphino)benzene) was synthesized from the reaction of Cu SCN and PPh_2PAr_2 in CH_3CN at room temperature. The compound was characterized by Elemental Analysis,NMR,UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic,space group P1 with a = 10.225(2),b = 11.360(2),c = 13.420(3) ?,α = 95.81(3),β = 93.45(3),γ = 113.78(3)°,V = 1410.4(5) ?~3,Z = 1,Mr = 1192.21,Dc = 1.404 g/cm~3,F(000) = 616,μ = 3.029 mm~(–1),GOOF = 1.052,the final R = 0.0359,and w R = 0.0964 for 4878 observed reflections with I > 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. The copper centers in the molecular structure are bridged by two thiocyanate anions and each Cu(I) is chelated further terminally by a PPh_2PAr_2 ligand. The [Cu(μ-SCN)_2Cu] cores have essential planar configurations. In the solid state,the complex exhibits blue photoluminescence with emission peaks λ_(max)= 478 nm(1),lifetimes 4.7 μs and quantum yields(ф = 0.43) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ~(1,3)MLCT excited states.
引文
(1)Tsuboyama,A.;Kuge,K.;Furugori,M.;Okada,S.;Hoshino,M.;Ueno,K.Photopysical properties of highly luminescent copper(I)halide complexes chelated with 1,2-bis(diphenylphosphino)benzene.Inorganic Chemistry 2007,46,1992–2001.
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(4)Volz,D.;Wallesch,M.;Grage,S.L.;Gottlicher,J.;Steininger,R.;Batchelor,D.;Vitova,T.;Ulrich,A.S.;Heske,C.;Weinhardt,L.;Baumann,T.;Brase,S.Labile or stable:can homoleptic and heteroleptic Pyr PHOS-copper complexes be processed from solution.Inorganic Chemistry 2014,53,7837–7847.
(5)Kang,L.;Chen,J.;Teng,T.;Chen,X.L.;Yu,R.;Lu,C.Z.Experimental and theoretical studies of highly emissive dinuclear Cu(I)halide complexes with delayed fluorescence.Dalton Trans 2015,44,11649–11659.
(6)Zink,D.M.;Volz,D.;Baumann,T.;Mydlak,M.;Flügge,H.;Friedrichs,J.;Nieger,M.;Br?se,S.Heteroleptic,dinuclear copper(I)complexes for application in organic light-emitting diodes.Chemistry of Materials 2013,25,4471–4486.
(7)Liu,Z.;Qiu,J.;Wei,F.;Wang,J.;Liu,X.;Helander,M.G.;Rodney,S.;Wang,Z.;Bian,Z.;Lu,Z.;Thompson,M.E.;Huang,C.Simple and high efficiency phosphorescence organic light-emitting diodes with codeposited copper(I)emitter.Chemistry of Materials 2014,26,2368–2373.
(8)Sheldrick,G.M.SHELXL-97,Program for Solution of Crystal Structures.Institute for Inorganic Chemistry,University of G?ttingen:G?ttingen,Germany 1997.
(9)Lee,C.T.;Yang,W.T.;Parr,R.G.Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density.Phys.Rev.B 1988,37,785–789.
(10)Becke,A.D.Density-functional thermochemistry.III.The role of exact exchange.J.Chem.Phys.1993,98,5648–5652.
(11)Bauernschmitt,R.;Ahlrichs,R.Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory.Chem.Phys.Lett.1996,256,454–464.
(12)Casida,M.E.;Jamorski,C.;Casida,K.C.;Salahub,D.R.Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory:characterization and correction of the time-dependent local density approximation ionization threshold.J.Chem.Phys.1998,108,4439–4449.
(13)Stratmann,R.E.;Scuseria,G.E.;Frisch,M.J.An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules.J.Chem.Phys.1998,109,8218–8224.
(14)Roy,L.E.;Hay,P.J.;Martin,R.L.Revised basis sets for the LANL effective core potentials.J.Chem.Theory Comput.2008,4,1029–1031.
(15)Frisch,M.J.;Trucks,G.W.;Schlegel,H.B.;Scuseria,G.E.;Robb,M.A.;Cheeseman,J.R.;Scalmani,G.;Barone,V.;Mennucci,B.;Petersson,G.A.;Nakatsuji,H.;Caricato,M.;Li,X.;Hratchian,H.P.;Izmaylov,A.F.;Bloino,J.;Zheng,G.;Sonnenberg,J.L.;Hada,M.;Ehara,M.;Toyota,K.;Fukuda,R.;Hasegawa,J.;Ishida,M.;Nakajima,T.;Honda,Y.;Kitao,O.;Nakai,H.;Vreven,T.;Montgomery,J.A.;Jr.;Peralta,J.E.;Ogliaro,F.;Bearpark,M.;Heyd,J.J.;Brothers,E.;Kudin,K.N.;Staroverov,V.N.;Kobayashi,R.;Normand,J.;Raghavachari,K.;Rendell,A.;Burant,J.C.;Iyengar,S.S.;Tomasi,J.;Cossi,M.;Rega,N.;Millam,J.M.;Klene,M.;Knox,J.E.;Cross,J.B.;Bakken,V.;Adamo,C.;Jaramillo,J.;Gomperts,R.;Stratmann,R.E.;Yazyev,O.;Austin,A.J.;Cammi,R.;Pomelli,C.;Ochterski,J.W.;Martin,R.L.;Morokuma,K.;Zakrzewski,V.G.;Voth,G.A.;Salvador,P.;Dannenberg,J.J.;Dapprich,S.;Daniels,A.D.;Farkas,?.;Foresman,J.B.;Ortiz,J.V.;Cioslowski,J.;Fox,D.J.Gaussian,Inc.,Wallingford CT.Gaussian 09,Revision D.01 2009.
(16)Czerwieniec,R.;Yu,J.;Yersin,H.Blue-light emission of Cu(I)complexes and singlet harvesting.Inorganic Chemistry 2011,50,8293–8031.
(17)Feng,H.T.;Xiong,J.B.;Zheng,Y.S.;Pan,B.;Zhang,C.;Wang,L.;Xie,Y.Multicolor emissions by the synergism of intra/intermolecular slippedπ-πstackings of tetraphenylethylene-Di BODIPY conjugate.Chemistry of Materials 2015,27,7812–7819.
(18)Deaton,J.C.;Switalski,S.C.;Kondakov,D.Y.;Young,R.H.;Pawlik,T.D.;Giesen,D.J.;Harkins,S.B.;Miller,A.J.M.;Mickenberg,S.F.;Peters,J.C.E-Type delayed fluorescence of a phosphine-supported Cu2(μ-NAr2)2 diamond core:harvesting singlet and triplet excitons in OLEDs//.Journal of the American Chemical Society 2010,132,9499–9508.
(19)Linfoot,C.L.;Leitl,M.J.;Richardson,P.;Rausch,A.F.;Chepelin,O.;White,F.J.;Yersin,H.;Robertson,N.Thermally activated delayed fluorescence(TADF)and enhancing photoluminescence quantum yields of[Cu I(diimine)(diphosphine)]+complexes-photophysical,structural,and computational studies.Inorganic Chemistry 2014,53,10854–10861.
(20)Yersin,H.;Rausch,A.F.;Czerwieniec,R.;Hofbeck,T.;Fischer,T.The triplet state of organo-transition metal compounds.Triplet harvesting and singlet harvesting for efficient OLEDs.Coordination Chemistry Reviews 2011,255,2622–2652.
(2)Zink,D.M.;Baumann,T.;Friedrichs,J.;Nieger,M.;Brase,S.Copper(I)complexes based on five-membered P^N heterocycles:structural diversity linked to exciting luminescence properties.Inorganic Chemistry 2013,52,13509–13520.
(3)Zink,D.M.;Bachle,M.;Baumann,T.;Nieger,M.;Kuhn,M.;Wang,C.;Klopper,W.;Monkowius,U.;Hofbeck,T.;Yersin,H.;Brase,S.Synthesis,structure,and characterization of dinuclear copper(I)halide complexes with P^N ligands featuring exciting photoluminescence properties.Inorganic Chemistry 2013,52,2292–2305.
(4)Volz,D.;Wallesch,M.;Grage,S.L.;Gottlicher,J.;Steininger,R.;Batchelor,D.;Vitova,T.;Ulrich,A.S.;Heske,C.;Weinhardt,L.;Baumann,T.;Brase,S.Labile or stable:can homoleptic and heteroleptic Pyr PHOS-copper complexes be processed from solution.Inorganic Chemistry 2014,53,7837–7847.
(5)Kang,L.;Chen,J.;Teng,T.;Chen,X.L.;Yu,R.;Lu,C.Z.Experimental and theoretical studies of highly emissive dinuclear Cu(I)halide complexes with delayed fluorescence.Dalton Trans 2015,44,11649–11659.
(6)Zink,D.M.;Volz,D.;Baumann,T.;Mydlak,M.;Flügge,H.;Friedrichs,J.;Nieger,M.;Br?se,S.Heteroleptic,dinuclear copper(I)complexes for application in organic light-emitting diodes.Chemistry of Materials 2013,25,4471–4486.
(7)Liu,Z.;Qiu,J.;Wei,F.;Wang,J.;Liu,X.;Helander,M.G.;Rodney,S.;Wang,Z.;Bian,Z.;Lu,Z.;Thompson,M.E.;Huang,C.Simple and high efficiency phosphorescence organic light-emitting diodes with codeposited copper(I)emitter.Chemistry of Materials 2014,26,2368–2373.
(8)Sheldrick,G.M.SHELXL-97,Program for Solution of Crystal Structures.Institute for Inorganic Chemistry,University of G?ttingen:G?ttingen,Germany 1997.
(9)Lee,C.T.;Yang,W.T.;Parr,R.G.Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density.Phys.Rev.B 1988,37,785–789.
(10)Becke,A.D.Density-functional thermochemistry.III.The role of exact exchange.J.Chem.Phys.1993,98,5648–5652.
(11)Bauernschmitt,R.;Ahlrichs,R.Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory.Chem.Phys.Lett.1996,256,454–464.
(12)Casida,M.E.;Jamorski,C.;Casida,K.C.;Salahub,D.R.Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory:characterization and correction of the time-dependent local density approximation ionization threshold.J.Chem.Phys.1998,108,4439–4449.
(13)Stratmann,R.E.;Scuseria,G.E.;Frisch,M.J.An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules.J.Chem.Phys.1998,109,8218–8224.
(14)Roy,L.E.;Hay,P.J.;Martin,R.L.Revised basis sets for the LANL effective core potentials.J.Chem.Theory Comput.2008,4,1029–1031.
(15)Frisch,M.J.;Trucks,G.W.;Schlegel,H.B.;Scuseria,G.E.;Robb,M.A.;Cheeseman,J.R.;Scalmani,G.;Barone,V.;Mennucci,B.;Petersson,G.A.;Nakatsuji,H.;Caricato,M.;Li,X.;Hratchian,H.P.;Izmaylov,A.F.;Bloino,J.;Zheng,G.;Sonnenberg,J.L.;Hada,M.;Ehara,M.;Toyota,K.;Fukuda,R.;Hasegawa,J.;Ishida,M.;Nakajima,T.;Honda,Y.;Kitao,O.;Nakai,H.;Vreven,T.;Montgomery,J.A.;Jr.;Peralta,J.E.;Ogliaro,F.;Bearpark,M.;Heyd,J.J.;Brothers,E.;Kudin,K.N.;Staroverov,V.N.;Kobayashi,R.;Normand,J.;Raghavachari,K.;Rendell,A.;Burant,J.C.;Iyengar,S.S.;Tomasi,J.;Cossi,M.;Rega,N.;Millam,J.M.;Klene,M.;Knox,J.E.;Cross,J.B.;Bakken,V.;Adamo,C.;Jaramillo,J.;Gomperts,R.;Stratmann,R.E.;Yazyev,O.;Austin,A.J.;Cammi,R.;Pomelli,C.;Ochterski,J.W.;Martin,R.L.;Morokuma,K.;Zakrzewski,V.G.;Voth,G.A.;Salvador,P.;Dannenberg,J.J.;Dapprich,S.;Daniels,A.D.;Farkas,?.;Foresman,J.B.;Ortiz,J.V.;Cioslowski,J.;Fox,D.J.Gaussian,Inc.,Wallingford CT.Gaussian 09,Revision D.01 2009.
(16)Czerwieniec,R.;Yu,J.;Yersin,H.Blue-light emission of Cu(I)complexes and singlet harvesting.Inorganic Chemistry 2011,50,8293–8031.
(17)Feng,H.T.;Xiong,J.B.;Zheng,Y.S.;Pan,B.;Zhang,C.;Wang,L.;Xie,Y.Multicolor emissions by the synergism of intra/intermolecular slippedπ-πstackings of tetraphenylethylene-Di BODIPY conjugate.Chemistry of Materials 2015,27,7812–7819.
(18)Deaton,J.C.;Switalski,S.C.;Kondakov,D.Y.;Young,R.H.;Pawlik,T.D.;Giesen,D.J.;Harkins,S.B.;Miller,A.J.M.;Mickenberg,S.F.;Peters,J.C.E-Type delayed fluorescence of a phosphine-supported Cu2(μ-NAr2)2 diamond core:harvesting singlet and triplet excitons in OLEDs//.Journal of the American Chemical Society 2010,132,9499–9508.
(19)Linfoot,C.L.;Leitl,M.J.;Richardson,P.;Rausch,A.F.;Chepelin,O.;White,F.J.;Yersin,H.;Robertson,N.Thermally activated delayed fluorescence(TADF)and enhancing photoluminescence quantum yields of[Cu I(diimine)(diphosphine)]+complexes-photophysical,structural,and computational studies.Inorganic Chemistry 2014,53,10854–10861.
(20)Yersin,H.;Rausch,A.F.;Czerwieniec,R.;Hofbeck,T.;Fischer,T.The triplet state of organo-transition metal compounds.Triplet harvesting and singlet harvesting for efficient OLEDs.Coordination Chemistry Reviews 2011,255,2622–2652.