Nonlinear optical and two-photon absorption properties of octupolar tris(bipyridyl)metal complexes
Nonlinear optical and two-photon absorption properties of octupolar tris(bipyridyl)metal complexes
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DOI：
10.1021/jp0735381
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发表时间：
2007-09-20
影响因子：
2.9
通讯作者：
Humphrey, Mark G.
中科院分区：
文献类型：
--
作者：
Feuvrie, Christophe;Maury, Olivier;Humphrey, Mark G.
报道了以4，4‘-双[(二丁氨基)苯乙烯基]-2，2’-联吡啶为配体的D-3[(Fe(II)，Ru(II)，Ni(II)，Cu(II)，Zn(II)]八极金属配合物的线性(吸收和发射)和非线性光学(NLO)性质。锌(II)、镍(II)和铜(II)络合物在可见光区(波长(ILCT)=474-476 nm)有相似的吸收光谱，归属于排列内和电荷转移(ILCT)带。金属中心的性质对二次和三次非线性光学性质有很大影响。在波长为1.91微米处的谐光散射研究表明，这些生色团在(211-340)×10(-30)esu范围内表现出较大的第一超极化率β(1.91)，用Ni(II)或Cu(II)取代金属离子可使静态β(0)系数减小1.5-1.6倍。在765和965 nm处的Z扫描测量显示了相对较大的双光子吸收截面[650<；sigma(2)<；2200Gm]，表明β和sigma(2)值都可以通过简单的金属离子修饰来调节。
The linear (absorption and emission) and nonlinear optical (NLO) properties of a series of D-3 [(Fe(II), Ru(II), Ni(II), Cu(II), Zn(II)] octupolar metal complexes featuring the 4,4 '-bis[(dibutylamino)styryl]-2,2 '-bipyridine ligand are reported. Zinc(II), nickel(II), and copper(II) complexes exhibit similar absorption spectra in the visible region (lambda(ILCT) = 474-476 nm) which are assigned to intraligand charge-transfer (ILCT) bands. The quadratic and cubic NLO properties are strongly influenced by the nature of the metallic center. Harmonic light scattering studies at lambda = 1.91 mu m reveal that these chromophores display large first hyperpolarizabilities beta(1.91) in the range of (211-340) x 10(-30) esu; replacing the Zn(II) metal ion by Ni(II) or Cu(II) results in a decrease of the static beta(0) coefficient by a factor of 1.5-1.6. Z-scan measurements at 765 and 965 nm reveal relatively large two-photon absorption cross-sections [650 < sigma(2) < 2200 GM], showing that both beta and sigma(2) values can be tuned by simple modification of the metal ion.