联吡啶Ru~(Ⅱ/Ⅲ)配合物二阶非线性光学性质的理论研究
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摘要
采用密度泛函理论(DFT)方法对联吡啶Ru~(Ⅱ/Ⅲ)配合物的几何结构、氧化还原性质、UV-Vis光谱及二阶非线性光学(NLO)性质进行计算.研究结果表明,醌基的引入能够有效增大第一超极化率(β_(tot))值,但醌基在氮苯基上位置的改变对β_(tot)值影响不大.分子轨道和自旋密度分布分析结果表明,金属Ru~Ⅱ和副配体均能成为氧化中心,并且氧化中心位置不同,会导致配合物氧化态的电荷转移形式产生差别,进而改变氧化态的β_(tot)值.氧化态配合物1b和2b的β_(tot)值减小,而配合物3b和4b的β_(tot)值显著增大,超瑞利散射方法计算的第一超极化率(β_(HRS))值也符合此规律.含时密度泛函理论(TD-DFT)结果表明,配合物本征态主要是金属到配体的电荷转移(MLCT/ML'CT),而氧化态则是配体到金属的电荷转移(LMCT/L'MCT),给、受体发生明显改变.因此,通过改变副配体的种类及氧化还原反应,可有效调节这类联吡啶Ru~(Ⅱ/Ⅲ)配合物的二阶NLO响应.
The geometry structures,redox properties,UV-Vis electronic absorption spectra and second-order nonlinear optical( NLO) properties of Ru~(Ⅱ/Ⅲ)-bipyridyl complexes were investigated by density functional theory( DFT). The results present that the introduction of anthraquinone ligands can effectively increase the first hyperpolarizabilities( β_(tot)) values,but the position of anthraquinone ligands on the nitrogen phenyl group has little effect on the β_(tot) values. The analysis of molecular orbital and spin density distributions illustrates that both of the metal Ru~Ⅱand ancillary ligands can serve as the oxidation center of eigenstates. The difference in the oxidation center has a influence on the charge transfer mode,thus affect the βtotvalues of oxidized forms.The β_(tot) values of oxidation states complexes 1b and 2b were decreased whereas the β_(tot) values of the complexes 3b and 4b enhance dremarkably. The first hyperpolarizabilities( β_(HRS)) calculated by the Hyper-Rayleigh Scattering method also comply with this phenomenon. Time-dependent density functional( TD-DFT) results indicate that the eigenstates are mainly performed metal-to-ligand charge transfer( MLCT/ML' CT) mode,while the oxidation states complexes are ligand-to-metal charge transfer( LMCT/L'MCT). This is resulting from the inverse changes in donors and acceptors. Therefore,for such Ru~(Ⅱ/Ⅲ)-bipyridyl complexes,second-order NLO properties can be effectively regulated by the change of ancillary ligands and redox reactions.
The geometry structures,redox properties,UV-Vis electronic absorption spectra and second-order nonlinear optical( NLO) properties of Ru~(Ⅱ/Ⅲ)-bipyridyl complexes were investigated by density functional theory( DFT). The results present that the introduction of anthraquinone ligands can effectively increase the first hyperpolarizabilities( β_(tot)) values,but the position of anthraquinone ligands on the nitrogen phenyl group has little effect on the β_(tot) values. The analysis of molecular orbital and spin density distributions illustrates that both of the metal Ru~Ⅱand ancillary ligands can serve as the oxidation center of eigenstates. The difference in the oxidation center has a influence on the charge transfer mode,thus affect the βtotvalues of oxidized forms.The β_(tot) values of oxidation states complexes 1b and 2b were decreased whereas the β_(tot) values of the complexes 3b and 4b enhance dremarkably. The first hyperpolarizabilities( β_(HRS)) calculated by the Hyper-Rayleigh Scattering method also comply with this phenomenon. Time-dependent density functional( TD-DFT) results indicate that the eigenstates are mainly performed metal-to-ligand charge transfer( MLCT/ML' CT) mode,while the oxidation states complexes are ligand-to-metal charge transfer( LMCT/L'MCT). This is resulting from the inverse changes in donors and acceptors. Therefore,for such Ru~(Ⅱ/Ⅲ)-bipyridyl complexes,second-order NLO properties can be effectively regulated by the change of ancillary ligands and redox reactions.
引文
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[3]Kim H.M.,Cho B.R.,J.Mater.Chem.,2009,19,7402-7409
[4]Asselberghs I.,Clays K.,Persoons A.,Ward M.D.,Mc Cleverty J.,J.Mater.Chem.,2004,14,2831-2839
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[19]Whittemore T.J.,White T.A.,Turro C.,J.Am.Chem.Soc.,2018,140,229-234
[20]Becke A.D.,J.Chem.Phys.,1993,98,5648-5652
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[24]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.,Keith T.,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 O.,Foresman J.B.,Ortiz J.V.,Cioslowski J.,Fox D.J.,Gaussian 09,Revision D.01,Gaussian Inc.,Wallingford CT,2013
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