Near-infrared emission from bis-Pt(II) complexes of doubly N-confused calix[6]phyrins(1.1.1.1.1.1).
Near-infrared emission from bis-Pt(II) complexes of doubly N-confused calix[6]phyrins(1.1.1.1.1.1).
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DOI：
10.1002/anie.200801713
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发表时间：
2008-07
影响因子：
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通讯作者：
Dong-Hoon Won;Motoki Toganoh;Y. Terada;S. Fukatsu;H. Uno;H. Furuta
中科院分区：
文献类型：
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作者：
Dong-Hoon Won;Motoki Toganoh;Y. Terada;S. Fukatsu;H. Uno;H. Furuta
铂(II)卟啉显示出强烈的室温磷光，与其他类型的磷光有机化合物相比寿命大大缩短，[1-3]这打破了荧光-磷光的区别，使它们在基于磷光猝灭的氧气传感[2]和发光器件(LED)等应用中非常有用。[3]然而，对于潜在的生物系统，发光的PtII络合物应该被设计成覆盖整个可见光和近红外范围(即650-1100 nm)。[4]最近，我们报道了双N-混淆己烷(1.1)。1.1.1.1)(N2C-Hex)，它们能够在由六个氮和两个碳原子(NNNC，NNNC)组成的矩形配位环境中与两个金属离子形成配合物。[5]然而，由于合成原因尚不清楚，并且容易被氧化，只有一种类型的二氧代取代己烷(N2CO-Hex)具有NNNO，NNNO核的双金属配合物(N2CO-Hex)；由于自由配体的发射光谱在近红外(&gT；1050 nm)观察到。为了获得与完整的NNNC或NNCC核的配位，这有望使发射带接近或在感兴趣的光谱窗口内，我们研究了非共轭N-混乱的六氢呋喃的合成及其PtII金属化。大环包含两个金属配位腔，由氮原子和碳原子组成，类似于一个共轭原子。在这里，我们报道了含有NNNC、NNNC或NNNN、NNCC核的双N-混杂杯[6]卟啉及其双-PtII配合物的合成，它们在1000 nm附近发光。这些是第一个令人困惑的
Platinum (II) porphyrins display intense room-temperature phosphorescence with significantly shorter lifetimes than other types of phosphorescent organic compounds,[1–3] which defies the fluorescence–phosphorescence distinction and makes them useful for such applications as oxygen sensing based on phosphorescence quenching [2] and light-emitting devices (LEDs).[3] For potential use in biological systems, however, the light-emitting PtII complexes should be designed to cover the full visible and near-infrared range (ie, 650–1100 nm).[4]Recently, we reported doubly N-confused hexaphyrin (1.1. 1.1. 1.1)(N2C-Hex) that are capable of forming complexes with two metal ions in their rectangular coordination environment consisting of six nitrogen and two carbon atoms (NNNC, NNNC).[5] However, because of the synthetic reason yet unclear and of susceptibility to oxidation, only one type of bis-metal complex of dioxo-substituted hexaphyrin (N2CO-Hex) bearing an NNNO, NNNO core has been characterized; the emission bands due to the free ligand are observed in the near-infrared (IR) region (> 1050 nm). In an attempt to attain coordination with intact NNNC or NNCC cores, which is expected to bring the emission band close to or within the spectral window of interest, we examined the synthesis of nonconjugated N-confused hexaphyrins and their PtII metalation. The macrocycles contain two metal coordination cavities consisting of nitrogen and carbon atoms similar to a conjugated one. Herein, we report the synthesis of doubly N-confused calix [6] phyrins bearing NNNC, NNNC or NNNN, NNCC cores and their bis-PtII complexes, which exhibit phosphorescence around 1000nm. These are the first confused