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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Luminescence color alteration induced by trapped solvent molecules in crystals of tetrahedral gold(I) complexes: near-unity luminescence mixed with thermally activated delayed fluorescence and phosphorescence
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Luminescence color alteration induced by trapped solvent molecules in crystals of tetrahedral gold(I) complexes: near-unity luminescence mixed with thermally activated delayed fluorescence and phosphorescence

机译：在四面体金（I）复合物的晶体中被捕获的溶剂分子引起的发光颜色改变：与热活化的延迟荧光和磷光混合的近乎统一发光

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The tetrahedral gold(I) complex [Au(L-tBu)(2)]Cl 1Cl [L-tBu = 1,2-bis[bis(4-tert-butylphenyl) phosphino] benzene], having eight tert-butyl (tBu) groups, was synthesized and characterized. Emission color alteration caused by solvent molecules captured in the crystal lattice of 1Cl was investigated. The recrystallization of 1Cl in mixed solvents of tetrahydrofuran, THF, and various alkanes afforded two single crystals: 1Cl center dot THF (1BG), presenting intense blue-green luminescence with an emission peak wavelength, lambda(max), = 507 nm and 1Cl center dot THF center dot 0.5n-hexane center dot H2O (1OR), exhibiting weak orange luminescence with lambda(max) = 625 nm. The emission quantum yields, phi(PL), of the two complexes were 0.95 and 0.06, respectively. X-ray structural analysis revealed that all the solvent molecules captured in the crystal were located inside the spaces surrounded by the tBu groups of the 1(+) cation. Further, an n-hexane molecule in 1OR was found to be sandwiched between two 1(+) cations via CH/pi interactions. The structure of 1Cl in 1OR could be distorted by the n-hexane molecule incorporated in the crystal, leading to the red-shift of the emission peak wavelength and the low quantum efficiency of 1OR over that of 1BG. On the other hand, [Au(L)(2)]Cl [L = 1,2-bis (diphenylphosphino) benzene], having no peripheral tBu groups, was unable to incorporate the solvent molecules in the crystal by recrystallization from the mixed solvents, and thus, the crystal solely yielded intense blue light emission. The results revealed that the tBu groups of the peripheral phenyl units are essential for the luminescence color alteration caused by the incorporation of organic solvent molecules into the crystal lattice. Finally, studies on the emission spectra and quantum yields in the temperature range 77-293 K revealed that luminescence from both 1BG and 1OR was composed of phosphorescence and thermally activated delayed fluorescence.
机译：四面体金（I）复合物[Au（L-TBU）（2）] Cl 1Cl [L-TBU = 1,2-双[双（4-叔丁基苯基）磷基]苯]，具有八叔丁基（ TBU）组被合成和表征。研究了在1CL晶格中捕获的溶剂分子引起的发射颜色改变。在四氢呋喃，THF和各种烷烃的混合溶剂中重结晶1CL，得到两个单晶：1CL中心点THF（1BG），具有发射峰值波长，λ（最大），= 507nm和1cl呈现强烈的蓝绿色发光中心点THF中心点0.5N-己烷中心点H2O（1OR），含有λ（MAX）= 625nm的弱橙色发光。两种配合物的发射量子产率，PHI（PL）分别为0.95和0.06。 X射线结构分析显示，在晶体中捕获的所有溶剂分子位于由1（+）阳离子的TBU基团包围的空间内。此外，发现101中的正己烷分子被发现通过CH / Pi相互作用夹在两种1（+）掩留之间。 1OR中的1Cl的结构可以被掺入晶体中的正己烷分子扭曲，导致发射峰值波长的红色偏移和10℃的低量子效率。另一方面，没有没有外周TBU基团的[AU（1）（2）] Cl [L = 1,2-双（二苯基膦基）苯，不能通过从混合中重结晶通过晶体中的溶剂分子掺入晶体中的溶剂分子溶剂，因此，晶体仅产生强烈的蓝色发光。结果表明，外周苯基单元的TBU基团对于由掺入晶格中的有机溶剂分子引起的发光颜色改变是必不可少的。最后，对温度范围77-293k的发射光谱和量子产率的研究表明，来自1bg和1010的发光由磷光和热活化的延迟荧光组成。

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