Amino-anthraquinone chromophores functionalised with 3-picolyl units: structures, luminescence, DFT and their coordination chemistry with cationic Re(I) di-imine complexes.
Amino-anthraquinone chromophores functionalised with 3-picolyl units: structures, luminescence, DFT and their coordination chemistry with cationic Re(I) di-imine complexes.
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DOI：
10.1039/c0dt01383h
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发表时间：
2011-03
影响因子：
4
通讯作者：
J. Jones;B. Kariuki;Benjamin D. Ward;Simon J. A. Pope
中科院分区：
文献类型：
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作者：
J. Jones;B. Kariuki;Benjamin D. Ward;Simon J. A. Pope
以3-吡啶甲基氨基蒽醌（AQ）为基础，通过一锅还原胺化法合成了四个新的配体，得到了所需的配体L1-L4（L1，1-（3-吡啶甲酰基氨基）蒽-9，10-二酮; L2，1-羟基-4-（3-吡啶甲酰基氨基）蒽-9，10-二酮; L3，1，4-双（3-吡啶甲酰基氨基）蒽-9，10-二酮; L4，1，5-双（3-吡啶甲酰基氨基）蒽-9，10-二酮）。每种配体在溶液中通过（1）H和（13）C{（1）H} NMR表征，其中三个实施例给出单晶X射线衍射数据。结构证实了所提出的配方，也揭示了醌和仲胺单元之间存在分子内氢键。的配体的电子特性进行了研究，使用相结合的实验/理论方法，揭示在每种情况下，在可见光区的吸收构成显着的电荷转移（CT）字符，从N-（胺）-醌转换，是溶剂敏感的。密度泛函理论（DFT）计算还表明，在AQ核心的氨基取代的位置影响的最低能量特征的波长，通过调制的HOMO，而不是LUMO能量。通过与fac-[Re（CO）（3）（di-imine）（MeCN）]（BF（4））的反应，探讨了配体的配位化学，其中di-imine = 1，10-菲咯啉（phen）和2，9-二甲基-1，10-菲咯啉（dmp）。结合结构和光谱的研究证实，配体协调Re（i）完全通过吡啶基单元，但在L3的情况下，只有monopolysaccharides配合物被分离。复合物的光学性质主要由叠加在（1）MLCT特征上的以AQ为中心（>425 nm）的吸收以及基于二亚胺的配体内（<350 nm）跃迁所控制。复合物的发光性质通常显示双发射，这取决于敏化波长，短寿命AQ荧光叠加在长寿命（3）MLCT磷光上。
The syntheses of four new ligands based upon 3-picolyl functionalised amino anthraquinone (AQ) chromophores are described via a one-pot reductive amination procedure giving the desired ligands L1-L4 (L1, 1-(3-picolylamino)anthracene-9,10-dione; L2, 1-hydroxy-4-(3-picolylamino)anthracene-9,10-dione; L3, 1,4-bis(3-picolylamino)anthracene-9,10-dione; L4, 1,5-bis(3-picolylamino)anthracene-9,10-dione). Each ligand was characterised in solution via(1)H and (13)C{(1)H} NMR, with three examples giving single crystal X-ray diffraction data. The structures confirmed the proposed formulations and also revealed the presence of intramolecular H-bonding between the quinone and secondary amine units. The electronic characteristics of the ligands were investigated using a combined experimental/theoretical approach, revealing that in each case absorption in the visible region constitutes significant charge transfer (CT) character, originating from N-(amine)-to-quinone transitions, and is solvent sensitive. Density functional theory (DFT) calculations also suggest that the position of amino-substitution at the AQ core influences the wavelength of the lowest energy feature, by modulation of the HOMO, rather than the LUMO energy. The coordination chemistry of the ligands was probed through reaction with fac-[Re(CO)(3)(di-imine)(MeCN)](BF(4)) where di-imine = 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmp). Combined structural and spectroscopic studies confirmed that the ligands coordinate to Re(i) exclusively via the pyridyl units, however in the case of L3 only monometallic complexes were isolated. The optical properties of the complexes are dominated by AQ-centred (>425 nm) absorptions superimposed upon (1)MLCT features, as well as diimine-based intra-ligand (<350 nm) transitions. The luminescence properties of the complexes generally display dual emission, which was dependent upon the wavelength of sensitisation, with short-lived AQ fluorescence superimposed upon long-lived (3)MLCT phosphorescence.