Deuterated Molecular Ruby with Record Luminescence Quantum Yield.
Deuterated Molecular Ruby with Record Luminescence Quantum Yield.
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DOI：
10.1002/anie.201711350
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发表时间：
2018-01
影响因子：
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通讯作者：
Cui Wang;Sven Otto;Matthias Dorn;Elisabeth Kreidt;Jakob Lebon;L. Sršan;Patrick Di Martino‐Fumo;M. Gerhards;U. Resch‐Genger;Michael Seitz;K. Heinze
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文献类型：
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作者：
Cui Wang;Sven Otto;Matthias Dorn;Elisabeth Kreidt;Jakob Lebon;L. Sršan;Patrick Di Martino‐Fumo;M. Gerhards;U. Resch‐Genger;Michael Seitz;K. Heinze
最近报道的发光铬（III）配合物13+（[Cr（ddpd）2 ]3+ ; ddpd=N，N ′-二甲基-N，N ′-联吡啶-2-基-吡啶-2，6-二胺）在环境条件下（Φ= 11%）在水中在775 nm处显示出异常强的近IR发射，具有微秒寿命，因为13+中的配体设计有效地消除了非辐射衰变途径，例如光取代，后星系间交叉和三角扭曲。在不存在能量受体（例如分子氧）的情况下，剩余的衰变途径是能量转移到高能溶剂和配体振荡器，即OH和CH伸缩振动。溶剂和ddpd配体的选择性氘化探测了这些振荡器在激发态失活中的效率。在第一和第二配位层中解决这些能量转移途径，在室温下溶液中具有地球丰富金属离子的金属络合物的量子产率和2.3毫秒的寿命达到创纪录的30%。
The recently reported luminescent chromium(III) complex 13+ ([Cr(ddpd)2 ]3+ ; ddpd=N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) shows exceptionally strong near-IR emission at 775 nm in water under ambient conditions (Φ=11 %) with a microsecond lifetime as the ligand design in 13+ effectively eliminates non-radiative decay pathways, such as photosubstitution, back-intersystem crossing, and trigonal twists. In the absence of energy acceptors, such as dioxygen, the remaining decay pathways are energy transfer to high energy solvent and ligand oscillators, namely OH and CH stretching vibrations. Selective deuteration of the solvents and the ddpd ligands probes the efficiency of these oscillators in the excited state deactivation. Addressing these energy-transfer pathways in the first and second coordination sphere furnishes a record 30 % quantum yield and a 2.3 millisecond lifetime for a metal complex with an earth-abundant metal ion in solution at room temperature.