水杨醛亚胺二氟化硼络合物的合成及压致荧光变色性质研究

发布时间：2018-04-11 17:59

  本文选题：水杨醛亚胺 + 压致荧光变色　； 参考：《吉林大学》2017年硕士论文

【摘要】：压致荧光变色材料是一类能对力刺激产生荧光响应的智能材料。利用其它途径如热处理,溶剂熏蒸荧光又能恢复到原始状态,因此是一种可循环使用的材料。作为检测用途的材料,通常其发射光谱相比吸收光谱所受干扰更少,同时灵敏度更高。因而压致荧光变色材料在力传感、荧光开关、无墨书写、保密存储、商标防伪等方面具有广泛应用。二氟化硼络合物类材料因诸多光学和结构方面的优点如,荧光量子产率高、结构易于修饰等而引起人们广泛兴趣。水杨醛单元是重要的化工中间体也是重要的配体单元,在医药、生物和材料领域被广泛使用。因此,本论文从设计合成新型咔唑和三苯胺修饰的水杨醛亚胺二氟化硼络合物出发,考察分子结构与材料发光之间的关系,并研究了该材料的压致荧光变色性质。取得了如下创新性研究结果:(1)设计并合成了新型咔唑功能化的水杨醛亚胺二氟化硼络合物。这种D-π-A型化合物具有ICT发射,发光可以被水杨醛上取代基调节。对该类化合物的光物理性质的研究表明,八个化合物固体能够在紫外光下发出强烈荧光,并表现出可逆的压致荧光变色行为。例如,研磨TCH的原始样品,可以使其荧光发射峰从488nm红移至571nm。值得注意的是,83nm这样大的发射位移在非金属有机化合物中很少有报道。研磨过的TCH样品经过二氯甲烷熏蒸或者在200℃加热2分钟,荧光能从橙色恢复到蓝绿色。外界刺激使材料从晶体到无定形态的转变是实现压致荧光变色的根本原因。因此通过调节D-p-A型化合物的ICT性质来设计具有高性能的压致荧光变色材料是一种可行的策略。(2)设计并合成了新型三苯胺功能化的水杨醛亚胺二氟化硼络合物。结果发现四个目标化合物表现出压致荧光变色性质,并且取代基可以调节其发光。化合物固体TH,TB,TT和TO能够在紫外光下发出强烈荧光并表现出可逆的压致荧光变色行为。TH的原始样品发出中心为551nm的黄色荧光,经过研磨,发光颜色变为中心为600nm橙红色荧光。TB的原始样品发出中心为545nm的黄色荧光,经过研磨,发光颜色变为中心为610nm橙红色荧光。研磨过的样品经过二氯甲烷熏蒸或在150°C加热1分钟,固态材料的荧光能恢复到初始状态,这说明压致荧光变色过程能够可逆进行。研磨处理使固体的吸收红移,研磨可能导致分子平面化。XRD和DSC表征表明材料从晶体到无定形态的转变是产生压致荧光变色现象的本质原因。三苯胺结构基元扭曲的非平面空间结构和D-π-A电子结构是实现压致荧光变色性质的重要条件。
[Abstract]:Pressure-induced fluorescence discoloration material is a kind of intelligent material which can produce fluorescence response to force stimulation.Solvent fumigation can return to its original state by other means such as heat treatment, so it is a recyclable material.Materials used for detection are usually less interfered and more sensitive in their emission spectra than in absorption spectra.Therefore, pressure-induced fluorescent discoloration materials are widely used in force sensing, fluorescent switch, ink free writing, secret storage, trademark anti-counterfeiting and so on.Boron difluoride complex materials have attracted much attention due to their optical and structural advantages such as high fluorescence quantum yield and easy modification of structures.Salicylic aldehyde units are important chemical intermediates and important ligand units, which are widely used in medicine, biology and materials.Therefore, based on the design and synthesis of novel carbazole and trianiline modified boron difluoride complexes, the relationship between molecular structure and luminescence of the materials was investigated, and the pressure-induced fluorescence discoloration properties of the materials were studied.A novel carbazole-functionalized boron difluoride complex was designed and synthesized.The D- 蟺 -A compound has ICT emission, and its luminescence can be regulated by the substituents on salicylaldehyde.The photophysical properties of these compounds show that eight solid compounds can emit strong fluorescence under ultraviolet light and exhibit reversible pressure-induced fluorescence discoloration behavior.For example, by grinding the original sample of TCH, the fluorescence emission peak can be shifted from 488nm red to 571 nm.It is worth noting that a large emission shift of 83 nm is rarely reported in nonmetallic organic compounds.The ground TCH sample was fumigated by dichloromethane or heated at 200 鈩，

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