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When Donors Turn into Acceptors: Ground and Excited State Properties of FeII Complexes with Amine-Substituted Tridentate Bis-imidazole-2-ylidene Pyridine Ligands.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-06-12 , DOI: 10.1021/acs.inorgchem.0c00393 Yannik Vukadinovic 1 , Lukas Burkhardt 1 , Ayla Päpcke 2 , Anabel Miletic 1 , Lorena Fritsch 1 , Björn Altenburger 2 , Roland Schoch 1 , Adam Neuba 1 , Stefan Lochbrunner 2 , Matthias Bauer 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-06-12 , DOI: 10.1021/acs.inorgchem.0c00393 Yannik Vukadinovic 1 , Lukas Burkhardt 1 , Ayla Päpcke 2 , Anabel Miletic 1 , Lorena Fritsch 1 , Björn Altenburger 2 , Roland Schoch 1 , Adam Neuba 1 , Stefan Lochbrunner 2 , Matthias Bauer 1
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In search of new ligand motifs for photoactive iron(II) complexes with long-lived MLCT states, a series of six complexes with tridentate amine-functionalized bis-n-heterocyclic carbene (NHC)-pyridine ligands is presented. In the homoleptic complexes imidazole-, methylimidazole-, or benzimidazole-2-ylidene, NHC donors are employed in combination with pyridine, functionalized in the 4-position by dimethylamine or dibenzylamine. The effects of these different functionalities on the electronic structure of the complexes are examined through detailed ground state characterization by NMR, single crystal X-ray diffraction, as well as electrochemical and spectroscopic methods. The net influence of these different functionalities on orbital–orbital and electrostatic ligand–iron interactions is investigated thoroughly by density functional theory, and changes in the excited state behavior and lifetimes are finally examined by ultrafast optical spectroscopy. Great deviations of the initially expected effects by substitution in 4-position on the photochemical properties are observed, together with a significantly increased π-acceptor interaction strength in the benzimidazole-2-ylidene functionalized complexes.
中文翻译：
当供体变成受体时：FeII配合物被胺取代的三齿双-咪唑-2-亚吡啶吡啶配体的基态和激发态性质。
为了寻找具有长寿命MLCT状态的光敏铁（II）配合物的新配体基序，一系列由六齿胺官能化的bis- n组成的六种配合物提出了-杂环卡宾（NHC）-吡啶配体。在咪唑-，甲基咪唑-或苯并咪唑-2-亚基的均配络合物中，将NHC供体与吡啶结合使用，并通过二甲胺或二苄胺在4-位官能化。通过NMR，单晶X射线衍射以及电化学和光谱学方法对基态进行详细表征，从而研究了这些不同官能团对配合物电子结构的影响。通过密度泛函理论深入研究了这些不同功能对轨道-轨道和静电配体-铁相互作用的净影响，最后通过超快光谱研究了激发态行为和寿命的变化。
更新日期：2020-07-06
中文翻译：
当供体变成受体时：FeII配合物被胺取代的三齿双-咪唑-2-亚吡啶吡啶配体的基态和激发态性质。
为了寻找具有长寿命MLCT状态的光敏铁（II）配合物的新配体基序，一系列由六齿胺官能化的bis- n组成的六种配合物提出了-杂环卡宾（NHC）-吡啶配体。在咪唑-，甲基咪唑-或苯并咪唑-2-亚基的均配络合物中，将NHC供体与吡啶结合使用，并通过二甲胺或二苄胺在4-位官能化。通过NMR，单晶X射线衍射以及电化学和光谱学方法对基态进行详细表征，从而研究了这些不同官能团对配合物电子结构的影响。通过密度泛函理论深入研究了这些不同功能对轨道-轨道和静电配体-铁相互作用的净影响，最后通过超快光谱研究了激发态行为和寿命的变化。
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