Excited-State Reactivity of [Mn(im)(CO)3 (phen)]+ : A Structural Exploration,Journal of Computational Chemistry

当前位置： X-MOL 学术 › J. Comput. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Excited-State Reactivity of [Mn(im)(CO)3 (phen)]+ : A Structural Exploration
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2018-09-12 , DOI: 10.1002/jcc.25535
Maria Fumanal ₁ , Yu Harabuchi ₂ , Etienne Gindensperger ₁ , Satoshi Maeda _{2,

3} , Chantal Daniel ₁

Affiliation

The electronic excited state reactivity of [Mn(im)(CO)3(phen)]+ (phen = 1,10‐phenanthroline; im = imidazole) ranging between 420 and 330 nm have been analyzed by means of relativistic spin–orbit time‐dependent density functional theory and wavefunction approaches (state‐average‐complete‐active‐space self‐consistent‐field/multistate CAS second‐order perturbation theory). Minimum energy conical intersection (MECI) structures and connecting pathways were explored using the artificial force induced reaction (AFIR) method. MECIs between the first and second singlet excited states (S1/S2‐MECIs) were searched by the single‐component AFIR (SC‐AFIR) algorithm combined with the gradient projection type optimizer. The structural, electronic, and excited states properties of [Mn(im)(CO)3(phen)]+ are compared to those of the Re(I) analogue [Re(im)(CO)3(phen)]+. The high density of excited states and the presence of low‐lying metal‐centered states that characterize the Mn complex add complexity to the photophysics and open various dissociative channels for both the CO and imidazole ligands. © 2018 Wiley Periodicals, Inc.

中文翻译：

[Mn(im)(CO)3 (phen)]+ 的激发态反应性：结构探索

[Mn(im)(CO)3(phen)]+（phen = 1,10-菲咯啉；im = 咪唑）在 420 到 330 nm 之间的电子激发态反应性已通过相对论自旋轨道时间进行了分析依赖密度泛函理论和波函数方法（状态平均完全活动空间自洽场/多态 CAS 二阶微扰理论）。使用人工力诱导反应 (AFIR) 方法探索了最小能量圆锥相交 (MECI) 结构和连接路径。通过结合梯度投影类型优化器的单分量 AFIR (SC-AFIR) 算法搜索第一和第二单重激发态 (S1/S2-MECI) 之间的 MECI。将 [Mn(im)(CO)3(phen)]+ 的结构、电子和激发态特性与 Re(I) 类似物 [Re(im)(CO)3(phen)]+ 的特性进行比较。Mn 络合物的高激发态密度和低金属中心态的存在增加了光物理的复杂性，并为 CO 和咪唑配体打开了各种解离通道。© 2018 Wiley Periodicals, Inc.

更新日期：2018-09-12

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文本刊介绍/投稿指南11