Kaufhold Simon, Rosemann Nils W, Chábera Pavel, Lindh Linnea, Bolaño Losada Iria, Uhlig Jens, Pascher Torbjörn, Strand Daniel, Wärnmark Kenneth, Yartsev Arkady, Persson Petter
Center for Analysis and Synthesis (CAS), Department of Chemistry, Lund University, Box 124, SE-22100 Lund, Sweden.
Division of Chemical Physics, Department of Chemistry, Lund University, Box 124, SE-22100 Lund, Sweden.
J Am Chem Soc. 2021 Jan 27;143(3):1307-1312. doi: 10.1021/jacs.0c12151. Epub 2021 Jan 15.
The photofunctionality of the cobalt-hexacarbene complex [Co(III)(PhB(MeIm))] (PhB(MeIm) = tris(3-methylimidazolin-2-ylidene)(phenyl)borate) has been investigated by time-resolved optical spectroscopy. The complex displays a weak (Φ ∼ 10) but remarkably long-lived (τ ∼ 1 μs) orange photoluminescence at 690 nm in solution at room temperature following excitation with wavelengths shorter than 350 nm. The strongly red-shifted emission is assigned from the spectroscopic evidence and quantum chemical calculations as a rare case of luminescence from a metal-centered state in a 3d complex. Singlet oxygen quenching supports the assignment of the emitting state as a triplet metal-centered state and underlines its capability of driving excitation energy transfer processes.
通过时间分辨光谱对钴-六卡宾配合物[Co(III)(PhB(MeIm))]（PhB(MeIm) = 三(3-甲基咪唑啉-2-亚基)(苯基)硼酸酯）的光功能进行了研究。在室温下的溶液中，用波长小于350 nm的光激发后，该配合物在690 nm处显示出微弱（Φ ∼ 10）但寿命极长（τ ∼ 1 μs）的橙色光致发光。从光谱证据和量子化学计算来看，这种强烈红移的发射被归因于3d配合物中金属中心态发光的罕见情况。单线态氧猝灭支持将发射态归为三重态金属中心态，并突出了其驱动激发能量转移过程的能力。
