雙穩(wěn)態(tài)磁性配合物的設(shè)計合成和性能調(diào)控
發(fā)布時間：2018-07-17 04:15
【摘要】：隨著科技的發(fā)展,從分子水平上研究具有特殊磁性功能的材料已經(jīng)成為材料領(lǐng)域的研究熱點。具有雙穩(wěn)態(tài)的磁性材料是實現(xiàn)分子集合體作為新的光/熱開關(guān)以及信息存儲元件的理想分子體系,成為分子基磁性材料研究領(lǐng)域的一個熱點。目前,研究較為廣泛的磁性雙穩(wěn)態(tài)材料主要包括在低溫區(qū)具有緩慢磁弛豫的分子納米磁體(尤其是稀土單分子磁體)和在室溫附近具有自旋轉(zhuǎn)換行為的自旋交叉配合物。基于以上背景和研究思路,本論文旨在設(shè)計合成具有特殊結(jié)構(gòu)和性能的鑭系稀土單分子磁體和自旋交叉配合物,并深入研究了它們的磁構(gòu)關(guān)系及性能調(diào)控。研究成果如下:一、基于硫代杯[4]芳烴的五核稀土簇合物中的慢弛豫磁行為基于硫代杯[4]芳烴合成了六個五核簇狀配合物[Ln_5(μ_4-OH)(μ_3-OH)_4(L_1)(acac)_6](H_4L_1 = P-tert-butylthiacalix[4]arene;acac =acetylacetonate;Ln = Dy(1),Ho(2),Er(3))和[Ln_5(μ_5-OH)(μ_3-OH)_4(L_1)(L_2)_2(acac)_2(CH_3OH)_2](H_3L_2 = 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,26,27-trihydroxy-28-methoxy thiacalix[4]arene;Ln = Dy(4),Ho(5),Er(6))。每個配合物中的五個金屬中心通過配體上的氧原子形成四角錐構(gòu)型,不同之處是,在配合物1-3中,底面的四個LnⅢ離子通過一個μ4-OH橋聯(lián),而在4-6中,四邊形底面的氧原子則是采取μ5-的方式連接著五個LnⅢ離子。磁性測試表明,配合物1-6中的金屬離子之間存在弱的反鐵磁作用,其中,兩個含DyⅢ配合物的虛部交流磁化率具有明顯的溫度依賴行為。二、基于硫代杯[4]芳烴的Ni~(Ⅱ)-Ln~(Ⅲ)異雙核配合物中的慢弛豫磁行為利用硫代杯[4]芳烴配體(H_2L_3 = 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-dihydroxy-26,28-dimethoxy thiacalix[4]arene)和三齒席夫堿配體(H_3L_4 =1,1,1-tris[(salicylideneamino)methyl]ethane),采用分步合成的方法制備了一系列Ni~(Ⅱ)-Ln~(Ⅲ)異雙核配合物[(NiLNiⅡ-Ln_4)Ln(L_3)((CH_3OH)]·acetone(Ln = Gd(7),Tb(8),Dy(9))。配合物7-9是同構(gòu)的,NiⅡ和LnⅢ通過席夫堿配體的兩個酚羥基橋聯(lián)。NiⅡ離子處于{NiN3O3}的配位環(huán)境,六個配位原子全部來自配體L4;LnⅢ離子采取七配位{LnO7},被一個杯芳烴配體的四個氧原子緊緊包裹著。靜態(tài)磁學(xué)性質(zhì)表明這三個配合物中,NiⅡ與LnⅢ之間都存在鐵磁交換作用,擬合得到的耦合常數(shù)JNi-Gd = 0.80 cm-1。動態(tài)磁學(xué)性質(zhì)顯示,配合物9具有場誘導(dǎo)的單分子磁體行為。我們又利用抗磁性的YⅢ對配合物9進行摻雜,得到的摻雜樣品9'在零場下即表現(xiàn)出單分子磁體慢弛豫過程。三、溶劑得失調(diào)控的雙核酞菁類LnⅢ配合物基于大環(huán)酞菁配體合成了三例雙核稀土配合物[Ln_2(thd)_4Pc]·2C_6H_6(Hthd =2,2,6,6-tetramethylheptanedione;Pc = phthalocyanine;Ln = Sm(10),Tb(11),Dy(12))。當10-12中游離的苯分子丟失之后,可以得到配合物[Ln_2(thd)_4Pc](Ln= Sm(10'),Tb(11'),Dy(12')),溶劑誘導(dǎo)的結(jié)構(gòu)轉(zhuǎn)化是可逆的。實驗結(jié)果顯示,溶劑的丟失對配合物的結(jié)構(gòu)和磁性質(zhì)都產(chǎn)生了很大的影響。配合物12中只含有一種晶體學(xué)獨立的金屬中心,它表現(xiàn)出單弛豫過程,有效能壘為55.7 K。失去溶劑得到的12,含有兩種金屬中心,表現(xiàn)出雙弛豫過程,能壘分別為63.3 K和109.6 K。最重要的是,配合物的動態(tài)磁行為可以通過溶劑苯分子的吸附和脫附可逆地調(diào)控。四、溶劑交換調(diào)控的雙核酞菁類ErⅢ配合物我們利用Li_2Pc與[Er(thd)_3]·2H20制備了一例雙核ErⅢ配合物[Er_2(thd)_4Pc]·2C_6H_6(13),該配合物在空氣中穩(wěn)定。將其浸泡在二氯甲烷溶劑中,晶格中游離的苯分子可以完全被二氯甲烷置換,得到新的配合物[Er_2(thd)_4Pc]·2CH_2Cl_2(14)。磁性測試表明,配合物13和14中存在不同的耦合作用。動態(tài)磁學(xué)性質(zhì)分析結(jié)果顯示,13在600 Oe的外磁場下依然表現(xiàn)出快弛豫過程,估算的能壘Ea只有2.6 cm-1,而14則具有場誘導(dǎo)的單分子磁體慢弛豫行為,有效能壘為34.3 cm-1。從頭計算的結(jié)果表明13和14截然不同的磁行為與分子內(nèi)ErⅢ離子之間不同的耦合作用有關(guān),耦合作用的不同從根本上可歸因于晶體結(jié)構(gòu)的微小變化。對配合物13-re和14-re結(jié)構(gòu)和磁性的進一步測試表明,配合物的單分子磁體性質(zhì)可以通過溶劑交換可逆地調(diào)控。五、橋聯(lián)配體調(diào)控的雙核酞菁類DyⅢ配合物我們將配合物12'作為原料,與不同取代的水楊醛配體進一步反應(yīng),合成了兩例結(jié)構(gòu)新穎的雙核 DyⅢ配合物[Dy2(Pc)2(MeO-L5)2(H2O)]·2THF(15,MeO-HL5=3-Methoxysalicylaldehyde)和[Dy2(Pc)2(EtO-L5)2(H2O)]·2THF(16,EtO-HL5 =3-ethoxy-2-hydroxybenzaldehyde)。配合物15和16是結(jié)構(gòu)相似的混合型三層夾心型結(jié)構(gòu),上層和下層都是酞菁配體,中間層是兩個不同配位方式的RL5配體,兩個晶體學(xué)獨立的金屬中心Dy1和Dy2通過兩個RL5的酚羥基相連,每個DyⅢ離子都處于{DyN4O4}的配位環(huán)境。靜態(tài)磁學(xué)性質(zhì)表明這兩個配合物中,Dy1和Dy2之間存在不同強度的磁相互作用。動態(tài)磁學(xué)性質(zhì)的分析結(jié)果顯示,配合物15具有零場下的單分子磁體雙弛豫行為,而16在零場下卻表現(xiàn)出量子隧穿效應(yīng)導(dǎo)致的快弛豫行為。從頭計算的結(jié)果表明,15和16截然不同的磁行為與分子內(nèi)DyⅢ離子之間不同的耦合作用有關(guān),耦合作用的不同從根本可歸因于橋聯(lián)配體中不同尺寸的取代基對晶體結(jié)構(gòu)造成的變化。六、溶劑響應(yīng)的Fe~(Ⅱ)配合物及自旋態(tài)與熒光的耦合作用我 們 選 用[FeL_6(MeOH)_2](H_2L_6 = {diethyl(E,E)-2,2'-[1,2-phenylbis(iminomethylidyne)]bis[3-oxobutanoate]-(2-)-N,N'O3,O3'})作為反應(yīng)前驅(qū)體,與熒光配體 L7(1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)-ethene)自組裝,得到了配合物17·1.5CH2Cl2。17·1.5CH2Cl2具有四重穿插的二維網(wǎng)狀結(jié)構(gòu),溶劑分子處于穿插之后的小空腔內(nèi),并通過多種非經(jīng)典氫鍵作用與框架相連。對17和17·1.5CH2Cl2的變溫磁化率測試表明,溶劑分子對配合物的自旋交叉行為具有顯著影響。17的轉(zhuǎn)變溫度為205 K,而17·1.5CH2Cl2則表現(xiàn)出熱滯回現(xiàn)象,滯回溫度達到24 K。當溶劑為甲醇時,得到甲醇溶劑化的配合物17·3CH3OH,該配合物不僅表現(xiàn)出磁滯回現(xiàn)象,熱滯回溫度達到29 K,而且自旋轉(zhuǎn)變程度也大大增加。此外,17的自旋轉(zhuǎn)變溫度與它的熒光強度發(fā)生不尋常倒轉(zhuǎn)的溫度吻合。我們不僅通過溶劑交換的方法在二維聚合物體系中實現(xiàn)了自旋交叉行為的調(diào)控(熱滯回行為的開和關(guān)),而且成功地將熒光基團引入到自旋交叉體系中,并且兩種性質(zhì)之間存在協(xié)同效應(yīng)。
[Abstract]:With the development of science and technology, the study of materials with special magnetic functions at the molecular level has become a hot topic in the field of materials. Bistable magnetic materials are an ideal molecular system to realize molecular aggregation as a new optical / thermal switch and information storage element, and become a hot spot in the field of molecular based magnetic materials. At present, a wide range of magnetic bistable materials mainly include slow magnetic relaxor molecular nanomaterials (especially rare earth monomolecular magnets) and spin cross complexes with spin conversion behavior near room temperature in low temperature zones. Based on the above background and research ideas, the purpose of this paper is to design and synthesize special structures and properties. The lanthanide lanthanide monomolecular magnets and spin cross complexes have been studied, and their magnetic relations and properties are studied. The results are as follows: 1. The slow relaxation magnetic behavior of five nuclear rare earth clusters based on thiosulfate [4] aromatics is based on the synthesis of six five nuclear cluster complexes, [Ln_5 (mu _3-OH) _4 (L_1), based on thiosulfate [4] aromatics (L_1). (ACAC) _6] (H_4L_1 = P-tert-butylthiacalix[4]arene; ACAC =acetylacetonate; Ln = Dy (1), Ho (2), Er (3)) and [Ln_5 (micron). The metal center forms the four pyramid configuration through the oxygen atom on the ligand. The difference is that in the complex 1-3, the four Ln III ions at the bottom are bridged by a single 4-OH, and in 4-6, the oxygen atoms at the bottom of the quadrangle are connected to five Ln III ions by the way of 5-. The magnetic test shows that the metal ions in the complex 1-6 are between the metal ions. There is a weak antiferromagnetic effect, in which the imaginary ac susceptibility of two Dy III complexes has obvious temperature dependence. Two, the slow relaxation magnetic behavior in the Ni~ (II) -Ln~ (III) heteronuclear complexes based on thiosulfate [4] arene uses the thiosulfate [4] arene ligand (H_2L_3 = 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,27-dihydrox) Y-26,28-dimethoxy thiacalix[4]arene) and three tooth Schiff base ligand (H_3L_4 =1,1,1-tris[(salicylideneamino) methyl]ethane), a series of Ni~ (II) -Ln~ (II) -Ln~ (III) heteronuclear complexes [(NiLNi II -Ln_4) Ln (L_3)] (7), 8, 9) are prepared by step synthesis. The complex 7-9 is isomorphic The two hydroxyl bridged.Ni II ions of the Schiff base ligand are in the coordination environment of {NiN3O3}, and the six coordination atoms are all from the ligand L4; Ln III ions take seven coordination {LnO7} and are tightly wrapped by four oxygen atoms of a calixarene ligand. The static magnetic properties indicate that there are ferromagnetic fields between the three complexes, between Ni II and Ln III. The dynamic magnetic properties of the fitting coupling constant JNi-Gd = 0.80 cm-1. show that the complex 9 has the field induced single molecule magnet behavior. We also use the anti magnetic Y III to doping the complex 9, and the doped sample 9'shows the slow relaxation process of the single molecule magnets under zero field. Three, the double solvent gain and loss control Nuclear phthalocyanine Ln III complexes have synthesized three cases of [Ln_2 (Hthd =2,2,6,6-tetramethylheptanedione, Pc = phthalocyanine, Ln = Sm (10), Ln = Sm (10), Tb (11), 12) based on the macrocyclic phthalocyanine ligand. 2')), the structural transformation induced by solvent is reversible. The result of the experiment shows that the loss of the solvent has a great effect on the structure and magnetic properties of the complexes. The complex contains only one crystallographic independent metal center, which shows a single relaxation process, an effective barrier of 55.7 K. lost the solvent and two kinds of metal centers. The most important of the two relaxation processes, the energy barrier 63.3 K and the 109.6 K., is that the dynamic magnetic behavior of the complexes can be reversible by the adsorption and desorption of the solvent benzene molecules. Four, the binuclear phthalocyanine Er III complex controlled by the solvent exchange, we use Li_2Pc and [Er (THD) _3]. 2H20 to prepare a case of the dual nucleus Er III complex [Er_2 (THD). 4Pc]. 2C_6H_6 (13), the complex is stable in the air. It is soaked in the dichloromethane solvent. The free benzene molecules in the lattice can be completely replaced by dichloromethane, and the new complex [Er_2 (THD) _4Pc]. 2CH_2Cl_2 (14) is obtained. The magnetic test shows that there are different coupling effects in the complexes 13 and 14. The dynamic magnetic properties analysis results show that the complexes have different coupling effects. It is shown that 13 still shows a fast relaxation process under the external magnetic field of 600 Oe, the estimated energy barrier Ea is only 2.6 cm-1, and 14 has the field induced slow relaxation behavior of the single molecule magnet, and the effective energy barrier to 34.3 cm-1. ab initio shows that the 13 and 14 magnetic behaviors are related to the different coupling effects between the intramolecular Er III ions. The difference in use is fundamentally attributable to small changes in the crystal structure. Further tests on the structure and magnetism of the complexes 13-re and 14-re show that the properties of the single molecule magnets of the complexes can be reversible by solvent exchange. Five, the binuclear phthalocyanine Dy III complex regulated by the bridged ligand, we use the complex 12'as the raw material, and different Two Novel Binuclear Dy III complexes [Dy2 (Pc) 2 (MeO-L5) 2 (H2O)] 2THF (15, MeO-HL5=3-Methoxysalicylaldehyde) and [Dy2 (Pc) 2 (EtO-L5) 2 (H2O)] are synthesized by the substituted salicylaldehyde ligands. The complex 15 and 16 complexes are similar to the structure of three layer sandwich type junction. The upper and lower layers are phthalocyanine ligands, the middle layer is a RL5 ligand with two different coordination modes, two crystallographic independent metal centers Dy1 and Dy2 are connected by two RL5 phenolic hydroxyl groups, each Dy III ion is in the {DyN4O4} coordination environment. Static magnetic properties indicate that there are different strengths between Dy1 and Dy2 among the two complexes. Magnetic interaction. The analysis of the dynamic magnetic properties shows that the complex 15 has the double relaxation behavior of the single molecule magnets under zero field, while the 16 in the zero field shows the fast relaxation behavior caused by the quantum tunneling effect. The results of the ab initio show that the coupling effect between the 15 and 16 magnetic behavior and the intramolecular Dy III ions is different. The difference in coupling is fundamentally attributable to the changes in the crystal structure of the substituents of different sizes in the bridging ligands. Six, we choose [FeL_6 (MeOH) _2] (E, E) -2,2'-[1,2-phenylbis (iminomethylidyne)]bis[3-oxobutanoa by the coupling of the solvent response Fe~ (II) complex and the spin state with the fluorescence. Te]- (2-) -N, N'O3, O3'}), as a reaction precursor, is self assembled with the fluorescent ligand L7 (1,1,2,2-tetrakis (4- (pyridin-4-yl) phenyl) -ethene), and a two-dimensional mesh structure with four heavy interspersed ligand 17. Is obtained. The solvent molecules are in the small cavity after the insertion of the solvent, and through a variety of non classical hydrogen bonding interactions with the frame phase The variable temperature magnetic susceptibility test for 17 and 17 1.5CH2Cl2 shows that the solvent molecules have a significant effect on the spin cross behavior of the complex, and the transition temperature of.17 is 205 K, while 17. 1.5CH2Cl2 shows a thermal hysteresis, and the hysteresis temperature is 24 K.. When the solvent is methanol, the coordination compound of methanol is 17. 3CH3OH. The hysteresis of magnetic hysteresis is shown, the thermal hysteresis temperature reaches 29 K, and the spin transition degree is also greatly increased. In addition, the spin transition temperature of 17 is consistent with the unusual inversion temperature of its fluorescence intensity. We not only realize the regulation of the spin cross behavior in the two-dimensional polymer system by the method of solvent exchange (the thermal hysteresis behavior). The fluorescent group was successfully introduced into the spin crossover system, and synergistic effects between the two properties were achieved.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O641.4
[Abstract]:With the development of science and technology, the study of materials with special magnetic functions at the molecular level has become a hot topic in the field of materials. Bistable magnetic materials are an ideal molecular system to realize molecular aggregation as a new optical / thermal switch and information storage element, and become a hot spot in the field of molecular based magnetic materials. At present, a wide range of magnetic bistable materials mainly include slow magnetic relaxor molecular nanomaterials (especially rare earth monomolecular magnets) and spin cross complexes with spin conversion behavior near room temperature in low temperature zones. Based on the above background and research ideas, the purpose of this paper is to design and synthesize special structures and properties. The lanthanide lanthanide monomolecular magnets and spin cross complexes have been studied, and their magnetic relations and properties are studied. The results are as follows: 1. The slow relaxation magnetic behavior of five nuclear rare earth clusters based on thiosulfate [4] aromatics is based on the synthesis of six five nuclear cluster complexes, [Ln_5 (mu _3-OH) _4 (L_1), based on thiosulfate [4] aromatics (L_1). (ACAC) _6] (H_4L_1 = P-tert-butylthiacalix[4]arene; ACAC =acetylacetonate; Ln = Dy (1), Ho (2), Er (3)) and [Ln_5 (micron). The metal center forms the four pyramid configuration through the oxygen atom on the ligand. The difference is that in the complex 1-3, the four Ln III ions at the bottom are bridged by a single 4-OH, and in 4-6, the oxygen atoms at the bottom of the quadrangle are connected to five Ln III ions by the way of 5-. The magnetic test shows that the metal ions in the complex 1-6 are between the metal ions. There is a weak antiferromagnetic effect, in which the imaginary ac susceptibility of two Dy III complexes has obvious temperature dependence. Two, the slow relaxation magnetic behavior in the Ni~ (II) -Ln~ (III) heteronuclear complexes based on thiosulfate [4] arene uses the thiosulfate [4] arene ligand (H_2L_3 = 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,27-dihydrox) Y-26,28-dimethoxy thiacalix[4]arene) and three tooth Schiff base ligand (H_3L_4 =1,1,1-tris[(salicylideneamino) methyl]ethane), a series of Ni~ (II) -Ln~ (II) -Ln~ (III) heteronuclear complexes [(NiLNi II -Ln_4) Ln (L_3)] (7), 8, 9) are prepared by step synthesis. The complex 7-9 is isomorphic The two hydroxyl bridged.Ni II ions of the Schiff base ligand are in the coordination environment of {NiN3O3}, and the six coordination atoms are all from the ligand L4; Ln III ions take seven coordination {LnO7} and are tightly wrapped by four oxygen atoms of a calixarene ligand. The static magnetic properties indicate that there are ferromagnetic fields between the three complexes, between Ni II and Ln III. The dynamic magnetic properties of the fitting coupling constant JNi-Gd = 0.80 cm-1. show that the complex 9 has the field induced single molecule magnet behavior. We also use the anti magnetic Y III to doping the complex 9, and the doped sample 9'shows the slow relaxation process of the single molecule magnets under zero field. Three, the double solvent gain and loss control Nuclear phthalocyanine Ln III complexes have synthesized three cases of [Ln_2 (Hthd =2,2,6,6-tetramethylheptanedione, Pc = phthalocyanine, Ln = Sm (10), Ln = Sm (10), Tb (11), 12) based on the macrocyclic phthalocyanine ligand. 2')), the structural transformation induced by solvent is reversible. The result of the experiment shows that the loss of the solvent has a great effect on the structure and magnetic properties of the complexes. The complex contains only one crystallographic independent metal center, which shows a single relaxation process, an effective barrier of 55.7 K. lost the solvent and two kinds of metal centers. The most important of the two relaxation processes, the energy barrier 63.3 K and the 109.6 K., is that the dynamic magnetic behavior of the complexes can be reversible by the adsorption and desorption of the solvent benzene molecules. Four, the binuclear phthalocyanine Er III complex controlled by the solvent exchange, we use Li_2Pc and [Er (THD) _3]. 2H20 to prepare a case of the dual nucleus Er III complex [Er_2 (THD). 4Pc]. 2C_6H_6 (13), the complex is stable in the air. It is soaked in the dichloromethane solvent. The free benzene molecules in the lattice can be completely replaced by dichloromethane, and the new complex [Er_2 (THD) _4Pc]. 2CH_2Cl_2 (14) is obtained. The magnetic test shows that there are different coupling effects in the complexes 13 and 14. The dynamic magnetic properties analysis results show that the complexes have different coupling effects. It is shown that 13 still shows a fast relaxation process under the external magnetic field of 600 Oe, the estimated energy barrier Ea is only 2.6 cm-1, and 14 has the field induced slow relaxation behavior of the single molecule magnet, and the effective energy barrier to 34.3 cm-1. ab initio shows that the 13 and 14 magnetic behaviors are related to the different coupling effects between the intramolecular Er III ions. The difference in use is fundamentally attributable to small changes in the crystal structure. Further tests on the structure and magnetism of the complexes 13-re and 14-re show that the properties of the single molecule magnets of the complexes can be reversible by solvent exchange. Five, the binuclear phthalocyanine Dy III complex regulated by the bridged ligand, we use the complex 12'as the raw material, and different Two Novel Binuclear Dy III complexes [Dy2 (Pc) 2 (MeO-L5) 2 (H2O)] 2THF (15, MeO-HL5=3-Methoxysalicylaldehyde) and [Dy2 (Pc) 2 (EtO-L5) 2 (H2O)] are synthesized by the substituted salicylaldehyde ligands. The complex 15 and 16 complexes are similar to the structure of three layer sandwich type junction. The upper and lower layers are phthalocyanine ligands, the middle layer is a RL5 ligand with two different coordination modes, two crystallographic independent metal centers Dy1 and Dy2 are connected by two RL5 phenolic hydroxyl groups, each Dy III ion is in the {DyN4O4} coordination environment. Static magnetic properties indicate that there are different strengths between Dy1 and Dy2 among the two complexes. Magnetic interaction. The analysis of the dynamic magnetic properties shows that the complex 15 has the double relaxation behavior of the single molecule magnets under zero field, while the 16 in the zero field shows the fast relaxation behavior caused by the quantum tunneling effect. The results of the ab initio show that the coupling effect between the 15 and 16 magnetic behavior and the intramolecular Dy III ions is different. The difference in coupling is fundamentally attributable to the changes in the crystal structure of the substituents of different sizes in the bridging ligands. Six, we choose [FeL_6 (MeOH) _2] (E, E) -2,2'-[1,2-phenylbis (iminomethylidyne)]bis[3-oxobutanoa by the coupling of the solvent response Fe~ (II) complex and the spin state with the fluorescence. Te]- (2-) -N, N'O3, O3'}), as a reaction precursor, is self assembled with the fluorescent ligand L7 (1,1,2,2-tetrakis (4- (pyridin-4-yl) phenyl) -ethene), and a two-dimensional mesh structure with four heavy interspersed ligand 17. Is obtained. The solvent molecules are in the small cavity after the insertion of the solvent, and through a variety of non classical hydrogen bonding interactions with the frame phase The variable temperature magnetic susceptibility test for 17 and 17 1.5CH2Cl2 shows that the solvent molecules have a significant effect on the spin cross behavior of the complex, and the transition temperature of.17 is 205 K, while 17. 1.5CH2Cl2 shows a thermal hysteresis, and the hysteresis temperature is 24 K.. When the solvent is methanol, the coordination compound of methanol is 17. 3CH3OH. The hysteresis of magnetic hysteresis is shown, the thermal hysteresis temperature reaches 29 K, and the spin transition degree is also greatly increased. In addition, the spin transition temperature of 17 is consistent with the unusual inversion temperature of its fluorescence intensity. We not only realize the regulation of the spin cross behavior in the two-dimensional polymer system by the method of solvent exchange (the thermal hysteresis behavior). The fluorescent group was successfully introduced into the spin crossover system, and synergistic effects between the two properties were achieved.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O641.4
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