Electronic Structure Studies and Photophysics of Luminescent Th(IV) Anilido and Imido Complexes
Electronic Structure Studies and Photophysics of Luminescent Th(IV) Anilido and Imido Complexes
复制标题
DOI：
10.1021/acs.inorgchem.3c00375
复制
发表时间：
2023-04-05
影响因子：
4.6
通讯作者：
Schelter，Eric J.
中科院分区：
文献类型：
--
作者：
Lapsheva，Ekaterina;Yang，Qiaomu;Schelter，Eric J.
一系列钍苯胺化合物[ThNHArR(TriNOx)] (R =para-OCH3(1-ArOMe),para-H (1-ArH),para-Cl (1-ArCl),para-CF3(1-Ar4-CF3), TriNOx3−=三(2-叔丁基羟基氨基)苄胺)及其相应的酰亚胺化合物[Li(DME)][Th=NArR(TriNOx)] (2-ArR) 以及烷基同系物 [ThNHAd(TriNOx)] (1-Ad) 和 [Li(DME)][Th=NAd(TriNOx)] (2-Ad) 已被制备。引入芳基酰亚氨基部分上的对位取代基是为了系统地改变其给电子和吸电子能力，这些变化在ArR部分的ipso-C原子的13C{1H}NMR化学位移的测量中是明显的。四种新的钍亚氨基化合物以及先前报道的[Li(THF)2][Th=NAr3,5-CF3(TriNOx)] (2-Ar3,5-CF3)和[Li(THF)(Et2O)][Ce=NAr3,5-CF3(TriNOx)](3-Ar3,5-CF3)的室温溶液态发光已被描述。在这些配合物中，2-Ar3,5-CF3表现出最强烈的发光特征，激发波长为398 nm，发射波长为453 nm。发光测量与时间依赖性密度泛函理论 (TD-DFT) 研究一起，帮助揭示了配体内 n → π* 跃迁，该跃迁被指定为亮蓝色发光的起源；3-Ar3,5-CF3 与其前配体相比，激发能有 1.2 eV 红移。其他衍生物（2-ArRand3-Ar3,5-CF3）的弱发光归因于源自配体间跃迁（2-ArR）或配体到金属电荷转移带（3-Ar3,5-CF3）的低激发态的非辐射衰变。总体而言，结果扩大了钍亚氨基有机金属化合物的范围，并证明钍(IV)配合物可以支持强配体发光。结果还证明了应用 Th(IV) 中心来调节相关亚氨基部分的 n → π* 发光能量和强度的效用。
A series of thorium anilide compounds [ThNHArR(TriNOx)] (R =para-OCH3(1-ArOMe),para-H (1-ArH),para-Cl (1-ArCl),para-CF3(1-Ar4-CF3), TriNOx3−=tris(2-tert-butylhydroxylaminato)benzylamine), and their corresponding imido compounds [Li(DME)][Th═NArR(TriNOx)] (2-ArR) as well as the alkyl congeners [ThNHAd(TriNOx)] (1-Ad) and [Li(DME)][Th═NAd(TriNOx)] (2-Ad), have been prepared. Thepara-substituents on the arylimido moiety were introduced for systematic variation of their electron-donating and withdrawing abilities, changes that were evident in measurements of the13C{1H} NMR chemical shifts of theipso-C atom of the ArRmoiety. Room temperature, solution-state luminescence of the four new thorium imido compounds, along with the previously reported [Li(THF)2][Th═NAr3,5-CF3(TriNOx)] (2-Ar3,5-CF3) and [Li(THF)(Et2O)][Ce═NAr3,5-CF3(TriNOx)] (3-Ar3,5-CF3) have been described. Among these complexes,2-Ar3,5-CF3demonstrated the most intense luminescence feature with excitation at 398 nm and emission at 453 nm. The luminescence measurements, together with a time-dependent density functional theory (TD-DFT) study, helped uncover an intra-ligand n → π* transition that was assigned as the origin of the bright blue luminescence;3-Ar3,5-CF3has an 1.2 eV redshift in excitation energy compared with its proligand. The weak luminescence of other derivatives (2-ArRand3-Ar3,5-CF3) was attributed to non-radiative decay from low-lying excited states originating from inter-ligand transitions (2-ArR) or ligand-to-metal charge transfer bands (3-Ar3,5-CF3). Overall, the results expand the range of the thorium imido organometallic compounds and demonstrate that thorium(IV) complexes can support strong ligand luminescence. The results also demonstrate the utility of applying a Th(IV) center for tuning the n → π* luminescence energy and intensity of an associated imido moiety.