• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Molecular quadratic non-linear optical properties of dipolar trans-tetraammineruthenium (II) complexes with pyridinium and thiocyanate ligands
【24h】

Molecular quadratic non-linear optical properties of dipolar trans-tetraammineruthenium (II) complexes with pyridinium and thiocyanate ligands

机译：具有吡啶鎓和硫氰酸酯配体的偶极反式四氨合钌（II）配合物的分子二次非线性光学性质

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Seven new complex salts trans-[Ru~(II)(NCS)(NH_3)_4(L~A)][PF_6]_2 (L~A = N-methyl-4,4'-bipyridinium (MeQ~+) 1, N-methyl-2,7-diazapyrenium (Medap~+) 2, N-methyl-4-[trans-2-(4-pyridyl) ethyl] pyridinium (Mebpe~+) 3, N-phenyl0-4,4'-bipyridinium (PhQ~+) 4, N-phenyl-4-[trans-2-(4-pyridyl) ethyl] pyridinium (Phbpe~+) 5, N-(4-acetylphenyl)-4,4'-bipyridinium (4-AcPhQ~+) 6, or N-(2-pyrimidyl)-4,4'-bipyridinium (2-PymQ~+) 7] have been prepared. The electronic absorption spectra of 1-7 display intense, visible metal-to-lignd charge-transfer (MLCT) bands, the energies (E_(max)) of which decrease in the order 2>1>3>4>6>5>7, as the electron-acceptinb ability of L~A increases. The E_(max) values generally correlate with cyclic voltammetric and ~1H NMR data. Comparisons of the MLCT absorption and electrochemical data for 1-7 show that a trans-{Ru~(II)(NCS)(NH_3)_4}~+ centra is a stronger electron donor than analogous groups containing only neutral ligands. Molecular first hyperpolarizabilities beta have been measured by using the hyper-Rayleigh scattering technique with acetonitrile solutions and a 1064 nm laser, and static first hyperpolarizabilities beta_0 [H] were obtained by application of the two-model. Stark (electroabsorption) spectroscopic studies in butyronitrile glasses at 77 K have afforded dipole moment changes DELTAmu_(12) for the MLCT transitions which have been used to calcualte beta_0[S] values according to the two-state equation beta_0 = 3DELTAmu_(12)~2/(E_(max))~2 (mu_(12) = transition dipole moment). Both the beta_0[H] and beta_0[S] data confirm that the increased electron donor ability of a trans-{Ru~(II)(NCS)(NH_3)_4}~+ centre affords enhanced beta_0 values, when compared with related complexes containing the neutral trans ligands NH_3, 4-(dimethylamino) pyridine, N-methylimidazole (mim) or pyridine. However, the magnitude of the observed beta_0 increase with respect to the analogous mim complexes varies over a range of ca. 25-120%, depending upon L~A.
机译：七个新的复杂盐反式-[Ru〜（II）（NCS）（NH_3）_4（L〜A）] [PF_6] _2（L〜A = N-甲基-4,4'-联吡啶（MeQ〜+）1 ，N-甲基-2,7-二氮杂py（Medap〜+）2，N-甲基-4- [反式-2-（4-吡啶基）乙基]吡啶鎓（Mebpe〜+）3，N-苯基0-4,4 '-联吡啶鎓（PhQ〜+）4，N-苯基-4- [反式-2-（4-吡啶基）乙基]吡啶鎓（Phbpe〜+）5，N-（4-乙酰苯基）-4,4'-联吡啶鎓制备了（4-AcPhQ〜+）6或N-（2-嘧啶基）-4,4'-联吡啶鎓（2-PymQ〜+）7]，1-7的电子吸收光谱显示出强烈的可见金属到电荷的电荷转移（MLCT）谱带，其能量（E_（max））以2> 1> 3> 4> 6> 5> 5> 7的顺序降低，作为L〜A的电子接受能力E_（max）值通常与循环伏安法和〜1H NMR数据相关。1-7的MLCT吸收和电化学数据的比较表明，反式-{Ru〜（II）（NCS）（NH_3）_4} 〜+中心比仅含中性配体的类似基团更强的电子供体。使用乙腈溶液和1064 nm激光，使用超瑞利散射技术进行测量，通过应用两个模型获得了静态第一超极化率beta_0 [H]。在77 K的丁腈玻璃中进行的斯塔克（电吸收）光谱研究为MLCT跃迁提供了偶极矩变化DELTAmu_（12），该值已用于根据二态方程beta_0 = 3DELTAmu_（12）计算出beta_0 [S]值。 2 /（E_（max））〜2（mu_（12）=过渡偶极矩）。 beta_0 [H]和beta_0 [S]数据均证实，与相关配合物相比，反式{Ru〜（II）（NCS）（NH_3）_4}〜+中心电子供体能力的提高提供了更高的beta_0值。含有中性反式配体NH_3、4-（二甲基氨基）吡啶，N-甲基咪唑（mim）或吡啶。但是，相对于类似的mim复合物，观察到的beta_0的增加幅度在ca范围内变化。 25-120％，取决于L〜A。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号