本文選題：光敏配位化合物 + 熒光-光色材料��； 參考：《華南理工大學(xué)》2016年碩士論文

【摘要】：化合物對光、熱和機械壓力等外界刺激產(chǎn)生相應(yīng)的熒光變化的特性,可用于設(shè)計與制備熒光分子開關(guān)、傳感器、顯示器和光儲存設(shè)備等器件所需的熒光調(diào)制材料。近來,探討分子的修飾、分子結(jié)構(gòu)的設(shè)計、分子間相互作用以及不同外界刺激對物質(zhì)熒光調(diào)控方面的研究,倍受國內(nèi)外研究者的關(guān)注。本文以大環(huán)多配位點熒光配體PYTPY作為吸收光能的觸角和發(fā)射熒光的主要基團,通過配體和金屬的配位來實現(xiàn)化合物結(jié)構(gòu)的調(diào)控,制備了系列具有不同結(jié)構(gòu)的配位基熒光分子材料,并對其開展結(jié)構(gòu)、熱穩(wěn)定性、熒光與光色、紅外與紫外等光譜的表征。所取得的具體研究結(jié)果如下:1.通過配體基團的設(shè)計,調(diào)控其配合物的結(jié)構(gòu)、與熒光等物化特性。已設(shè)計和制備三種大環(huán)熒光配體,其中PYTPY(4'-(4-吡啶基)-2,2':6',2''-三聯(lián)吡啶)配體的端基為缺電子的吡啶環(huán),可在配位化合物中作為電子受體;DMATPY(4′-(4-N,N′-二甲氨基苯基)-2,2′:6′,2″-三聯(lián)吡啶)的端基為富電子的二甲氨基,是很好的熒光探針材料;CPTPY(4′-(4-羧基苯基)-2,2′:6′,2″-三聯(lián)吡啶)的端基為羧基,含有N,O兩種配位原子,可用于與不同金屬配位構(gòu)建多結(jié)構(gòu)配位分子體系。2.以PYTPY為電子受體,利用水熱法中DMF分解產(chǎn)生的甲酸為電子給體,與鎘離子配合構(gòu)建了一例熒光調(diào)制型D-A光色配位化合物Cd(NO_3)(HCOO)(H_2O)(PYTPY)(1)。該分子的密堆積結(jié)構(gòu)導(dǎo)致其可構(gòu)成固體光激激基締合物。在光照的條件下,化合物1展示出有趣的熒光調(diào)制和光色變化現(xiàn)象,為一例有趣的配位基光敏分子體系。3.以PYTPY為電子受體,Cl離子為電子給體,與鎘原子配合構(gòu)建了一例熒光D-A配位化合物CdCl_2(PYTPY)(2)�；衔�2的晶體結(jié)構(gòu)中給受體分子間的距離較遠,固態(tài)無光激激基締合物特性。將其溶于溶液中,隨著給受體間的分子間距離縮小,其可展現(xiàn)出同上例光激激基締合物類似的現(xiàn)象。以PYTPY為配體,在其端基吡啶氮參與配位的條件下,構(gòu)建一例雙核鎘氯簇層狀超分子結(jié)構(gòu)Cd_3Cl_6(PYTPY)_2(3),該化合物的熒光在外力的作用下可發(fā)生由弱到強的變化,展示出有趣的碾磨機械調(diào)制熒光現(xiàn)象。4.以DMATPY和CPTPY為熒光配體合成的小分子CdCl_2(DMATPY)(4)和Zn(CPTPY)_2(5)。由于其配體的富電子性,以其構(gòu)建的配位化合物與需探測的金屬離子之間可發(fā)生較強的相互作用。此類配體與金屬離子間的拉電效應(yīng)致的熒光遷移特性可用于探測不同離子的存在與濃度。
[Abstract]:The properties of the compounds to the external stimuli, such as light, heat and mechanical pressure, can be used to design and fabricate fluorescent modulating materials for devices such as fluorescent molecular switches, sensors, displays and optical storage devices. Recently, researches on molecular modification, molecular structure design, intermolecular interaction and the regulation of substance fluorescence by different external stimuli have attracted much attention from researchers at home and abroad. In this paper, the macrocyclic multi-coordination point fluorescence ligand PYTPY is used as the main group for absorption of light energy and emission fluorescence, and the structure of the compound is regulated by the coordination of ligand and metal. A series of coordination group fluorescent molecular materials with different structures were prepared and characterized by their structure, thermal stability, fluorescence and light color, IR and UV spectra. The specific results obtained are as follows: 1. 1. Through the design of ligand group, the structure of its complex and its physicochemical properties such as fluorescence were regulated. Three macrocyclic fluorescent ligands have been designed and prepared, in which the end group of PYTPYC4O4-PYTPYO4-PYTPYO4-PYTPYO4- 4- pyridyl ~ (2 +) (2: 6) is an electron-deficient pyridine ring, and the end group of the ligands is electron-deficient pyridine ring. In the coordination compound, the terminal group of the electron acceptor, DMATPYO4 (4) -N (N) -dimethylaminophenyl (2) (2 "), is electron-rich dimethylamino (DMTA), which can be used as an electron acceptor in the coordination compound, and can be used as an electron acceptor. It is a very good fluorescent probe material, CPTPYO4, 4-carboxyl-phenyl-2-tripyridine), the terminal group of which is carboxyl group and contains two kinds of coordination atoms. It can be used to coordinate with different metals to construct multi-structure coordination molecule system. Using PYTPY as electron acceptor and formic acid decomposed from DMF in hydrothermal process as electron donor, a fluorescent modulated D-A photochromic coordination compound CDNO _ 3 was constructed by using CD ~ (2 +) ~ (2 +) as an electron donor. The dense stacking structure of the molecule leads to the formation of a solid photoexcited group association complex. Under light condition, compound 1 exhibits interesting fluorescence modulation and photochromatic variation, which is an interesting ligand Guang Min system. 3. Using PYTPY as electron acceptor Cl ion as electron donor, a fluorescent D-A coordination compound CdCl2PYTPYPYYPU was constructed with cadmium atom. The distance between the acceptor molecules in the crystal structure of compound 2 is relatively long, and the characteristics of the solid-state light-free excimer association complex. When it is dissolved in the solution, the similar phenomenon of photoluminescent association complex can be shown as the distance between the donors decreases. Using PYTPY as ligand, a binuclear cadmium chloride cluster with layered supermolecular structure CD _ 3Cl _ 6 / PYTPY _ 2 was constructed under the condition that its terminal pyridine nitrogen participated in the coordination. The fluorescence of this compound can change from weak to strong under the action of external force. Show interesting milling machine modulation fluorescence phenomenon. 4. DMATPY and CPTPY were used as fluorescent ligands. Due to its electron-rich ligands, there is a strong interaction between the coordination compounds and the metal ions to be detected. The fluorescence migration characteristics of the ligand and metal ions can be used to detect the existence and concentration of different ions.
【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O641.4

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