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首页> 外文期刊>Chemistry: A European journal >Vaulted trans-bis(salicylaldiminato)platinum(II) crystals: Heat-resistant, chromatically sensitive platforms for solid-state phosphorescence at ambient temperature
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Vaulted trans-bis(salicylaldiminato)platinum(II) crystals: Heat-resistant, chromatically sensitive platforms for solid-state phosphorescence at ambient temperature

机译：拱顶式反式双（水杨基铝二氨基）铂（II）晶体：耐热，对色敏感的平台，可在环境温度下进行固态磷光

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摘要

The synthesis, structure, and solid-state emission of vaulted trans-bis(salicylaldiminato)platinum(II) complexes are described. A series of polymethylene (1: n=8; 2: n=9; 3: n=10; 4: n=11; 5: n=12; 6: n=13) and polyoxyethylene (7: m=2; 8: m=3; 9: m=4) vaulted complexes (R=H (a), 3-MeO (b), 4-MeO (c), 5-MeO (d), 6-MeO (e), 4-CF_3O (f), 5-CF_3O (g)) was prepared by treating [PtCl_2(CH_3CN)_2] with the corresponding N,N′-bis(salicylidene)-1,ω-alkanediamines. The trans coordination, vaulted structures, and the crystal packing of 1-9 have been unequivocally established from X-ray diffraction studies. Unpredictable, structure-dependent phosphorescent emission has been observed for crystals of the complexes under UV excitation at ambient temperature, whereas these complexes are entirely nonemissive in the solution state under the same conditions. The long-linked complex crystals 4-6, 8, and 9 exhibit intense emission (Φ_(77K)=0.22-0.88) at 77 K, whereas short-linked complexes 1-3 and 7 are non- or slightly emissive at the same temperature (Φ_(77K)<0.01-0.18). At 298 K, some of the long-linked crystals, 4 a, 4 b, 5 c, 5 e, 6 c, 6 e, and 9 b, completely lose their high-emission properties with elevation of the temperature (Φ_(298K)<0.01-0.02), whereas the other long-linked crystals, 5 a, 6 a, 9 a, and 9 d, exhibit high heat resistance towards emission decay with increasing temperature (Φ_(298K)=0.21-0.38). Chromogenic control of solid-state emission over the range of 98 nm can be performed simply by introducing MeO groups at different positions on the aromatic rings. Orange, yellow-green, red, and yellow emissions are observed in the glass and crystalline state upon 3-, 4-, 5-, and 6-MeO substitution, respectively, whereas those with CF_3O substituents have orange emission, irrespective of the substitution position. DFT calculations (B3LYP/6-31G*, LanL2DZ) showed that such chromatic variation is ascribed to the position-specific influence of the substituents on the highest-occupied molecular orbital (HOMO) and lowest-unoccupied molecular orbital (LUMO) levels of the trans-bis(salicylaldiminato)platinum(II) platform. The solid-state emission and its heat resistance have been discussed on the basis of X-ray diffraction studies. The planarity of the trans-coordination sites is strongly correlated to the solid-state emission intensities of crystals 1-9 at lower temperatures. The specific heat-resistance properties shown exclusively by the 5 a, 6 a, 9 a, and 9 d crystals are due to their strong three-dimensional hydrogen-bonding interactions and/or Pt...Pt contacts, whereas heat-quenchable crystals 4 a, 4 b, 5 c, 5 e, 6 c, 6 e, and 9 b are poorly bound with limited interactions, such as non-, one-, or two-dimensional hydrogen-bonding networks. These results lead to the conclusion that Pt...Pt contacts are an important factor in the heat resistance of solid-state phosphorescence at ambient temperature, although the role of Pt...Pt contacts can be substituted by only higher-ordered hydrogen-bonding fixation. Tuning it in: Strong phosphorescent emission is observed for a variety of crystalline polymethylene- and polyoxyethylene-bridged trans-bis(salicylaldiminato) platinum(II) complexes (see figure). The heat resistance and color of the solid-state emission can be controlled by tuning the molecular array and electronic configuration of the vaulted complexes by altering linkers and substituents.
机译：描述了拱形反式双-（水杨基亚氨基）铂（II）配合物的合成，结构和固态发射。一系列的聚亚甲基（1：n = 8; 2：n = 9; 3：n = 10; 4：n = 11; 5：n = 12; 6：n = 13）和聚氧乙烯（7：m = 2; 8：m = 3; 9：m = 4）拱形复合物（R = H（a），3-MeO（b），4-MeO（c），5-MeO（d），6-MeO（e），通过用相应的N，N'-双（水杨基）-1，ω-链烷二胺处理[PtCl_2（CH_3CN）_2]，制备4-CF_3O（f），5-CF_3O（g））。通过X射线衍射研究已明确确定了1-9的反式配位，拱形结构和晶体堆积。在环境温度下，在紫外线激发下，观察到配合物的晶体发生了不可预测的，依赖于结构的磷光发射，而在相同条件下，这些配合物在溶液状态下完全不发光。长链复合物晶体4-6、8和9在77 K处显示出强发射（Φ_（77K）= 0.22-0.88），而短链复合物1-3和7在相同的条件下不发光或微发光。温度（Φ_（77K）<0.01-0.18）。在298 K时，某些长链晶体4a，4b，5c，5e，6c，6e和9b随着温度的升高而完全失去了高发射特性（Φ_（298K ）<0.01-0.02），而其他长链晶体5a，6a，9a和9d则表现出较高的耐热性，可抵抗随温度升高而产生的发射衰减（Φ_（298K）= 0.21-0.38）。只需在芳香环的不同位置引入MeO基团，即可在98 nm范围内对固态发射物进行发色控制。在分别被3-，4-，5-，6-MeO取代后，在玻璃和晶体状态下分别观察到橙色，黄绿色，红色和黄色发射，而具有CF_3O取代基的那些则与发射无关，而分别发生橙色位置。 DFT计算（B3LYP / 6-31G *，LanL2DZ）表明，这种色差归因于取代基的位置特异性影响，对取代基的最高占据分子轨道（HOMO）和最低未被占据分子轨道（LUMO）的水平反式（salicylaldiminato）铂（II）平台。在X射线衍射研究的基础上讨论了固态发射及其耐热性。反式配位位点的平面度与较低温度下晶体1-9的固态发射强度密切相关。 5a，6a，9a和9d晶体只显示出特定的耐热性能，这是由于它们具有很强的三维氢键相互作用和/或Pt ... Pt接触，而可热淬灭的晶体4a，4b，5c，5e，6c，6e和9b的结合有限，相互作用有限，例如非二维，一维或二维氢键网络。这些结果得出的结论是，尽管Pt ... Pt触点的作用只能由高阶氢原子取代，但在室温下Pt ... Pt触点是固态磷光耐热性的重要因素。键合固定。调优：观察到各种结晶的聚亚甲基和聚氧乙烯桥连的反式双（水杨基铝二氨基）铂（II）配合物的强磷光发射（见图）。固态发射的耐热性和颜色可以通过改变接头和取代基来调节拱形配合物的分子排列和电子构型，从而控制其稳定性。

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