Synthesis,Crystal Structure and Photoluminescence of a TADF Cuprous Complex
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摘要
A cuprous mononuclear copper complex [Cu(adpypz)CH3CNPPh3]BF4·CH2Cl2(1, adpypz = 9,9-dimethyl-10-(6-(3-phenyl-1H-pyrazol-1-yl)pyridin-2-yl)-9,10-dihydroacridine) was synthesized and characterized by Elemental Analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic, space group P1 with a = 11.3388(4), b = 13.4569(4), c = 16.2561(6) ?, α = 97.154(3), β = 92.187(3), γ = 114.119(4)°, V = 2235.38(13) ?3, Z = 2, Mr = 967.12, Dc = 1.437 g/cm~3, F(000) = 996, μ = 2.62 mm~(–1), GOOF = 1.031, the final R = 0.0417, and w R = 0.1024 for 8043 observed reflections with I > 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. In the solid state, the complex exhibits bluish-green photoluminescence with emission peaks λmax = 492 nm(1), lifetimes 235 μs and quantum yields(ф = 0.279) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence(TADF) at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ILCT excited states.
A cuprous mononuclear copper complex [Cu(adpypz)CH3CNPPh3]BF4·CH2Cl2(1, adpypz = 9,9-dimethyl-10-(6-(3-phenyl-1H-pyrazol-1-yl)pyridin-2-yl)-9,10-dihydroacridine) was synthesized and characterized by Elemental Analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic, space group P1 with a = 11.3388(4), b = 13.4569(4), c = 16.2561(6) ?, α = 97.154(3), β = 92.187(3), γ = 114.119(4)°, V = 2235.38(13) ?3, Z = 2, Mr = 967.12, Dc = 1.437 g/cm~3, F(000) = 996, μ = 2.62 mm~(–1), GOOF = 1.031, the final R = 0.0417, and w R = 0.1024 for 8043 observed reflections with I > 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. In the solid state, the complex exhibits bluish-green photoluminescence with emission peaks λmax = 492 nm(1), lifetimes 235 μs and quantum yields(ф = 0.279) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence(TADF) at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ILCT excited states.
A cuprous mononuclear copper complex [Cu(adpypz)CH3CNPPh3]BF4·CH2Cl2(1, adpypz = 9,9-dimethyl-10-(6-(3-phenyl-1H-pyrazol-1-yl)pyridin-2-yl)-9,10-dihydroacridine) was synthesized and characterized by Elemental Analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic, space group P1 with a = 11.3388(4), b = 13.4569(4), c = 16.2561(6) ?, α = 97.154(3), β = 92.187(3), γ = 114.119(4)°, V = 2235.38(13) ?3, Z = 2, Mr = 967.12, Dc = 1.437 g/cm~3, F(000) = 996, μ = 2.62 mm~(–1), GOOF = 1.031, the final R = 0.0417, and w R = 0.1024 for 8043 observed reflections with I > 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. In the solid state, the complex exhibits bluish-green photoluminescence with emission peaks λmax = 492 nm(1), lifetimes 235 μs and quantum yields(ф = 0.279) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence(TADF) at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ILCT excited states.
引文
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(16)Czerwieniec,R.;Yu,J.;Yersin,H.Blue-light emission of Cu(I)complexes and singlet harvesting.Inorg.Chem.2011,50,8293–8301.
(17)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 II.J.Am.Chem.Soc.2010,132,9499–9508.
(18)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.Inorg.Chem.2014,53,10854–10861.
(19)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.Coordin.Chem.Rev.2011,255,2622–2652.
(2)Volz,D.;Chen,Y.;Wallesch,M.;Liu,R.;Flechon,C.;Zink,D.M.;Friedrichs,J.;Flugge,H.;Steininger,R.;Gottlicher,J.Bridging the efficiency gap:fully bridged dinuclear Cu(I)-complexes for singlet harvesting in high-efficiency OLEDs.Adv.Mater.2015,27,2538–2543.
(3)Hofbeck,T.;Monkowius,U.;Yersin,H.Highly efficient luminescence of Cu(I)compounds-TADF combined with short-lived phosphorescence.J.Am.Chem.Soc.2014,137,399–404.
(4)Czerwieniec,R.;Yu,J.;Yersin,H.Blue-light emission of Cu(I)complexes and singlet harvesting.Inorg.Chem.2011,50,8293–8301.
(5)Yersin,H.;Leitl,M.J.;Czerwieniec,R.TADF for singlet harvesting:next generation OLED materials based on brightly green and blue emitting Cu(I)and Ag(I)compounds.2014,9183,91830N-91830N-11.
(6)Chen,X.L.;Yu,R.;Zhang,Q.K.;Zhou,L.J.;Wu,C.Y.;Zhang,Q.;Lu,C.Z.Rational design of strongly blue-emitting cuprous complexes with thermally activated delayed fluorescence and application in solution-processed OLEDs.Chem.Mater.2013,25,3910–3920.
(7)Chen,X.L.;Lin,C.S.;Wu,X.Y.;Yu,R.M.;Teng,T.;Zhang,Q.K.;Zhang,Q.;Yang,W.B.;Lu,C.Z.Highly efficient cuprous complexes with thermally activated delayed fluorescence and simplified solution process OLEDs using the ligand as host.J.Mater.Chem.C 2015,3,1187–1195.
(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.1993,98,5648–5653.
(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.Inorg.Chem.2011,50,8293–8301.
(17)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 II.J.Am.Chem.Soc.2010,132,9499–9508.
(18)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.Inorg.Chem.2014,53,10854–10861.
(19)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.Coordin.Chem.Rev.2011,255,2622–2652.