发光环甲基化铬（III）络合物

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-04-17 DOI:10.1021/acs.organomet.4c00075

Laura Stein, Christoph Förster, Katja Heinze

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引用次数: 0

摘要

通过单晶 X 射线结构分析、循环伏安法和吸收/发射光谱法，对二甲胺（X = NMe2，face-1）和二苯基膦（X = PPh2，face-2）供体的三(环甲基化)铬(III)配合物 fac-Cr(C∧X)3 进行了全面表征。这两种络合物在固态或冷冻溶液中都能在近红外光谱区发光。膦烷配合物 fac-2 具有半衰期，并在流体溶液中与悬挂的 PPh2 给体形成弱发射性的五配位配合物。在 DFT 和 CASSCF/NEVPT2 理论水平上进行的量子化学计算对光谱测定有帮助。Fac-1 和 Fac-2 与环甲基化吡啶络合物 Fac-Cr(PY)3（PY- = 去质子化的 2-苯基吡啶）相辅相成，从而建立了芳基、吡啶、膦烷和胺供体的新紫外系列。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Luminescent Cyclometalated Chromium(III) Complexes

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Luminescent Cyclometalated Chromium(III) Complexes

Tris(cyclometalated) chromium(III) complexes fac-Cr(C^∧X)₃ with dimethylamine (X = NMe₂, fac-1) and diphenylphosphane (X = PPh₂, fac-2) donors were fully characterized by single crystal X-ray structure analyses, cyclic voltammetry, and absorption/emission spectroscopy. Both complexes are luminescent in the near-infrared spectral region in the solid state or in frozen solution. The phosphane complex fac-2 is hemilabile and forms a weakly emissive, five-coordinate complex with a dangling PPh₂ donor in fluid solution. Spectroscopic assignments are aided by quantum chemical calculations at the DFT and CASSCF/NEVPT2 levels of theory. fac-1 and fac-2 complement the cyclometalated pyridine complex fac-Cr(ppy)₃ (ppy^– = deprotonated 2-phenylpyridine) and allow establishment of a nephelauxetic series of aryl, pyridine, phosphane, and amine donors.

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.