冠醚化单和双Schiff碱的合成及其钴(II)配合物的氧加合性能

由苯并-15-冠-5经硝化、还原和缩合反应,制备了4'-(2-羟基苯亚甲基亚氨基)苯并-15-冠-5(L^1H)和4',5'-双(2-羟基苯亚甲基亚氨基)苯并-15-冠-5(L^4H~2)以及它们的取代衍生物L^2H和L^5H~2。在不同温度和不同轴配体存在下,测定了它们的钴(II)配合物的氧合常数和ΔHⅲ,ΔSⅲ,并与未冠醚化的类似物CoL~2^3和CoL^6比较,讨论了配体结构和轴配体碱性对配合物的氧分子加合性能的影响。     

冠醚化单和双Schiff碱的合成及其钴(II)配合物的氧加合性能

由苯并-15-冠-5经硝化、还原和缩合反应,制备了4'-(2-羟基苯亚甲基亚氨基)苯并-15-冠-5(L^1H)和4',5'-双(2-羟基苯亚甲基亚氨基)苯并-15-冠-5(L^4H~2)以及它们的取代衍生物L^2H和L^5H~2。在不同温度和不同轴配体存在下,测定了它们的钴(II)配合物的氧合常数和ΔHⅲ,ΔSⅲ,并与未冠醚化的类似物CoL~2^3和CoL^6比较,讨论了配体结构和轴配体碱性对配合物的氧分子加合性能的影响。     

稀土配合物的研究 I: 镧系元素与4-酰代-双吡唑啉酮及1,10-二氮杂菲的混配配合物的合成及表征

用镧系硝酸盐与1,6-双(1'-苯基-3'-甲基-5'-氧代吡唑-4'-基)-1,6-己二酮(1,H2L)和1,10-二氮杂菲(2, Phen)在乙醇-水溶液中, 于PH5-6时合成了12种新的固态配合物Ln2L3Phen2. 4H2O(Ln=Pr, Nd, Sm-Lu)。用元素分析、水份及配体分析、红外、紫外,质子核磁共振、荧光光谱和热分析鉴定了所有的配合物, 从而推测, 可能L是四啮配体,Phen是二啮配体。     

稀土配合物的研究 I: 镧系元素与4-酰代-双吡唑啉酮及1,10-二氮杂菲的混配配合物的合成及表征

用镧系硝酸盐与1,6-双(1'-苯基-3'-甲基-5'-氧代吡唑-4'-基)-1,6-己二酮(1,H2L)和1,10-二氮杂菲(2, Phen)在乙醇-水溶液中, 于PH5-6时合成了12种新的固态配合物Ln2L3Phen2. 4H2O(Ln=Pr, Nd, Sm-Lu)。用元素分析、水份及配体分析、红外、紫外,质子核磁共振、荧光光谱和热分析鉴定了所有的配合物, 从而推测, 可能L是四啮配体,Phen是二啮配体。     

含二苯并-18-冠-6席夫碱型液晶冠醚钾配合物的液晶行为

以顺(反)-4,4′-双[4-(4′-正烷氧基联苯基-4-羧基)苯亚氨基]二苯并-18-冠-6(Ⅰ和Ⅱ)为配体合成了2种系列席夫碱型液晶冠醚钾配合物,产率分别为85.5%～92.1%和88.7%～90.7%。配合物的结构通过元素分析、IR、UV-Vis和AAS等测试技术确证。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明,所有配合物均具有热致液晶性,且随分子末端烷氧基碳原子数增加,其熔点和清亮点呈规律性变化。近晶相温度范围渐增,向列相温度范围递减。与配体相比,配合物液晶态温度范围变宽。     

含X-型二维液晶基元和顺式-4,4′-双(4-羟基苯基偶氮)二苯并-18-冠-6冠醚环液晶共聚酯的合成与表征

以4,4'-(α,ω-辛二酰氧)二苯甲酰氯(M1)、2,5-双[4-'(对癸氧基苯基)苯甲酰氧基]对苯二酚(M2)和顺式-4,4'-双(4-羟基苯基偶氮)二苯并-18-冠-6(M3)为单体,通过溶液共缩聚反应,合成了一系列新的含X-型二维液晶基元和顺式-4,4'-双(4-羟基苯基偶氮)二苯并-18-冠-6冠醚环的主链犁液晶共聚酯.单体1(M1)由对羟基苯甲酸和辛二酰氯,通过酯化和取代反应制备,单体2(M2)由2,5-二羟基苯醌和对癸氧基苯基苯甲酰氯通过酯化和还原反应制备,单体3(M3)由顺式-二氨基二苯并-18-冠-6和苯酚通过重氮化和偶联反应制备.共聚酯的分子量小高,[η]在0.30～0.39之间.单体的化学结构通过 IR、UV、1H-NMR、MS 和元素分析等方法确证.共聚酯的外观为黄色粉状固体,除共聚酯 CP9 外,室温下不溶于 CHCl3 和 THF 溶剂.共聚酯的性质采用 GPC、[η]、DSC、TG、WAXD 和 POM 等方法进行了研究.发现所有的共聚酯加热到各自的熔融温度以上都能形成液晶态,在液晶态可以观察到近晶相和向列相的典型织构.共聚酯的熔融温度(Tm)和各向同性温度(T1)随共聚酯分子中顺式-4,4'-双(4-羟基苯基偶氮)二苯并-18-冠-6用量的改变呈规律性变化.WAXD 研究进一步证实了共聚酯的液晶性.     

含二苯并-18-冠-6席夫碱型液晶冠醚钾配合物的合成与表征

以顺(反)-4,4＇-双[4-(4＇-正烷氧基联苯基-4-羧基) 苯亚氨基] 二苯并-18-冠-6（I和II）为配体合成了2个系列席夫碱型液晶冠醚钾配合物,产率分别为85.5%~92.1%和88.7%~90.7%。配合物的结构通过元素分析、IR、UV-Vis和AAS等方法确证。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明,所有配合物均具有热致液晶性,且随分子末端烷氧基碳原子数增加,其熔点和清亮点呈规律性变化。近晶相温度范围渐增,向列相温度范围递减。与配体相比,配合物液晶态温度范围变宽     

铁系元素冠醚配合物的研究 Ⅹ.CoCl_2·Co(NO_3)_2与冠醚固态配合物的合成与性质

本文研究了COCl_2·6H_2O与二苯并-24-冠-8(L_c)。二苯并-30-冠_10(LD),4'-碘苯并-15-冠-5(L_E)和4'-溴苯并-15-冠-5(L_F);Co(NO_3)_2·6H_2O与苯并-15-冠-5(L_A)、L_E和L_F之间的反应,合成了7个尚未见报道的配合物,通过元素分析、摩尔电导、红外、紫外、差热-热重、X-射线粉末衍射等确定了它们的组成,比较分析了配体和配合物的有关性质。     

冠醚化双西佛碱钴(Ⅱ)配合物的合成、氧合和催化氧化性能 研究

合成和表征了三个新的冠醚化双西佛碱4',5'-双(2-羟基苯亚甲基亚氨基)苯并-12-冠-4(L^1H2),4',5'-双(5-氯-2-羟基苯亚甲基亚氨基)苯并-12-冠-4(L^1H2)和4',5'-双(5-溴-2-羟基苯亚甲基亚氨基)苯并-12-冠-4(L^3H2)以及它们的钴配合物。在吡啶溶液中和不同温度下,测定了配合物的饱和吸氧量,求出了它们的氧加合常数和热力学参数△H°,△S°,并以这些配合物为催化剂,活化分子氧氧化环已烯制备环已烯酮,通过与未冠醚化的类似物作比较,讨论了冠醚环的引入对配合物与氧分子加合性能以及催化氧化性能的影响。     

双二芳基乙烯配体构建的Ag (Ⅰ)配合物及多色光致变色性质

采用闭环态紫外最大吸收波长不同的2个二芳基乙烯:1,2-双(2'-甲基-5'-(4"-苯腈)-3'-噻吩)全氟环戊烯(L1)和顺-1,2-二氰基-1,2-双(2',4',5'-三甲基-3'-噻吩)乙烯(L2)为配体,以Ag(Ⅰ)为金属离子、具有强配位能力的CF_3COO~-为阴离子,合成了一个新的双组分光致变色Ag(Ⅰ)配合物1。通过红外光谱、核磁共振氢谱及质谱对其进行结构表征。以直接混合的双配体体系(L1+L2)为对照,用UV-Vis光谱法研究了配合物1在四氢呋喃(THF)溶液和聚甲基丙烯酸甲酯(PMMA)薄膜中的多色态光致变色性质。结果表明,银离子配位没有抑制而是调节了 2个配体的光致变色性质,经254、405 nm和大于550 nm波长光的不同组合照射,可选择性地使1中2个配体发生分步光异构化反应,成功实现了黄色、蓝色、红色和紫色4个色态的转变。     

Anchoring strength coefficient of a monomer and its dimer at a polymer-coated interface

The dialkoxyphenylbenzoate monomer '5005' (C₅H₁₁OC₆H₄COOC₆H₄OC₅H₁₁) and its dimer were aligned parallel to a buffed polyimide-coated glass substrate. A magnetically induced Freedericksz transition in both thick and thin cells was used in conjunction with a capacitance technique to determine the anchoring strength coefficient Was a function of temperature in the nematic phase. It was found that for both monomer and dimer, Wincreases with decreasing temperature. The anchoring coefficient for the dimer, however, was found to be an order of magnitude larger than for the monomer at comparable reduced temperatures. The splay elastic moduli were also determined for both species, and found to be of comparable magnitude, consistent with previous results.     

二噻吩并[2,3-b:2',3'-d]噻吩钯(Ⅱ)配合物引发AB型芴单体聚合

5-溴-2-三甲硅基-二噻吩并[2,3-b:2',3'-d]噻吩(bt-DTT-Br)与双(三环己基)膦钯(0)进行氧化加成反应,合成了相应的芳基钯(Ⅱ)配合物,X光晶体结构分析表明,配合物中心金属离子为平面四方构型,膦配体处于反式位置。该配合物在加热时可以引发AB型芴单体聚合,得到一个端基为bt-DTT的聚芴共轭聚合物。相似端基结构的聚芴可以由bt-DTT-Br与不同膦配体钯(0)配合物原位生成的芳基钯配合物引发AB型芴单体聚合制备。辅助配体为三(邻甲基苯基)膦或三叔丁基膦时,配合物引发的AB型芴单体聚合室温下即可进行,并给出单一且端基结构明确的聚芴。基质辅助激光解吸电离飞行时间质谱(MALDI-TOF)分析证实,聚合物的一个端基是来自芳基钯配合物中的bt-DTT,另一端基为Br/H原子或封端基团。凝胶渗透色谱(GPC)分析表明,聚合物相对分子质量随单体与催化剂的投料比增加呈线性增长,聚合反应遵循催化剂转移聚合机理。     

Living and enantiomer-selective polymerization of allene initiated by Ni complex containing chiral phosphine

In the polymerization of chiral allene by using chiral phosphine complex, the polymerization rate of L-1 is approximately 1.9 times that of D-1. This catalyst has enantiomer-selectivity for the polymerization of chiral allene derivative monomer.     

Luminescent Properties of Terbium（Ⅲ） and Europium（Ⅲ）Complexes with Six 4-Acetyl-bispyrazolones

The lowest triplet energy levels of the six ligands（T） were determined to be 22989 cm-1[1,3-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazolon-4＇）-1,3-propanedione,BPMPTD],23148 cm-1[1,4-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazolon-4＇）-1,4-butanedione,BPMPBD],23419 cm-1[1,5-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazolon-4＇）-1,5-pentane-dione,BPMPPD],23310 cm-1[1,6-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazolon-4＇）-1,6-hexanedione,BPMPHD],21978 cm-1[1,9-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazolon-4＇）-l,9-nonanedione,BPMPND] and 21930 cm-1[1,10-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazoion-4＇）-1,10-decanedione,BPMPDD],respectively.It was explained satisfactorily that the six ligands are more efficient for sensitizing the luminescence of Tb3＋ than that of Eu3＋ at room temperature,and the order of the luminescent intensities for the Tb3＋ complexes is explained by the relative energy gap between T and 5DJ of Tb3＋ or Eu3＋.As a conclusion,when 2700 cm-1＜△E（T-5D4）＜3000 cm-1,the luminescent intensity of the Tb3＋ complex is the strongest.This means that the lowest triplet energy level of the ligand is a chief factor to dominate RE3＋luminescence.     

含TEMPO配合物的合成、表征、谱学性质及光猝灭机理

A novel Pt(Ⅱ)-based metallointercalator terpyridine complex linked with a 2, 2, 6, 6-tetramethyl-1-piperidinyl N-oxide (TEMPO) derivative was prepared by a reaction between 4'-TEMPO-terpyridine (L) and a Pt(Ⅱ) salt. This complex presented unusual luminescence quenching owing to the effect of the stable nitroxide radical. The crystal structure of[Pt(terpy-TEMPO)Cl]Cl·H₂O·CH₃OH (terpy=2, 2':6', 2"-terpyridine) was elucidated by X-ray crystallography. Additionally, the effect of TEMPO on the photophysical properties of[Pt(terpy-TEMPO)Cl] Cl·H₂O·CH₃OH was investigated by UV-Vis, fluorescence emission, and electron paramagnetic resonance (EPR) spectroscopy. Data from the absorption and luminescence properties (298 K) of the[Pt(terpy-TEMPO)Cl]⁺ complex indicated the presence of two groups of typical bands:an intense band B with distinct vibronic structures (270-350 nm, ε>10⁴ dm³·mol^-1·cm^-1) and a less intense band A (370-450 nm, ε~10³ dm³·mol^-1·cm^-1). These two bands are generally assigned to ligand-to-ligand charge transfer (LLCT) and metal-to-ligand charge transfer (MLCT) excited states, respectively. Furthermore, efficient photoluminescent quenching behavior was observed in the emission spectra of this complex system. Quantum calculations of the molecular energy gaps and bands were performed by Gaussian 09 software. The calculated results verified that TEMPO greatly affects the energy gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital. Thus, the relationship between efficient photoquenching and molecular structure was theoretically interpreted. EPR results indicated that when TEMPO is attached to a macrocyclic terpyridine platinum complex, e.g., [Pt(terpy)Cl]⁺, the terpyridine platinum complex does not affect the hyperfine coupling constant (A value) and g factor (g values) but the rotation and relaxation times of the TEMPO radical.     

配合物[Eu(4-MOBA)3(terpy)(H2O)]2的合成、表征、热分解机理及性质

合成了一个新的配合物[Eu(4-MOBA)₃(terpy)(H₂O)]₂ (4-MOBA:4-甲氧基苯甲酸根, terpy:2, 2':6', 2"-三联吡啶)。采用傅里叶变换红外(FTIR)光谱、元素分析和X射线粉末衍射(XRD)技术对标题配合物进行了表征,用X射线单晶衍射仪测定了配合物的晶体结构,在配合物中每个Eu³⁺离子与一个三联吡啶分子、一个水分子和三个羧酸分子结合,配位数为9,羧酸基团的配位模式包含三种:双齿螯合,桥连双齿,单齿。根据热重-差示扫描量热/傅里叶变换红外(TG-DSC/FTIR)联用技术,研究了配合物的热分解机理。配合物的发射光谱显示出Eu³⁺离子的特征荧光发射,表明三联吡啶和4-甲氧基苯甲酸在该体系中可作为敏化集团。另外,文中还讨论了配合物对白色念珠菌和大肠杆菌的抑菌活性。     

6-取代氨基-2-烷硫基腺苷化合物的合成及抗血小板凝聚活性

以鸟苷(1)为原料, 经过糖环保护得到2',3',5'-三-O-乙酰基鸟嘌呤核苷(2), 化合物2与三氯氧磷反应得到2-氨基-6-氯-9-(2',3',5'-三-O-乙酰基-β-D-呋喃核糖基)嘌呤(3), 化合物3经重氮化后再与二烷基二硫醚反应得到2-烷硫基-6-氯-9-(2',3',5'-三-O-乙酰基-β-D-呋喃核糖基)嘌呤(4a~4d), 化合物4a~4d与胺进行亲核取代反应后, 脱去糖环保护得到12个新型的6-取代氨基-2-烷硫基腺苷化合物(5a~5l). 采用¹H NMR, ¹³C NMR, IR和高分辨质谱(HRMS)对目标化合物的结构进行了确证, 并对所有化合物进行了体外抗血小板聚集活性测试. 结果表明, 当测试浓度为10 μmol/L时, 化合物5a~5l仍具有一定的抗凝活性, 其中, 6-(3-苯基丙基)氨基-2-丙硫基腺苷(5d)活性最为显著, 抑制率可达90.2%.     

Ultrathin 2D Covalent Organic Framework Film Fabricated via Langmuir-Blodgett Method with a “Two-in-One” Type Monomer

In recent years, covalent organic frameworks(COFs) are evolving as a novel kind of porous materials for catalysis and molecular separation, gas adsorption, etc. Various functional building blocks have been explored to tune the pore channels, including the pore size and structures. In this article, a new terphenyl(TP) based COF(TP-COF) was developed via a “two-in-one” strategy by using a symmetric A₂B₂monomer, i.e., 4,4'-diamino-2',5'-diformyl-1,1':4',1'-terphenyl(DADFTP). The pore size of TP-COF was only 0.99 nm by shortening the arm length of the DADFTP monomer. Freestanding, continuous and ultrathin COF films could be facilely prepared at the air-liquid interface through the modified Langmuir-Blodgett(LB) method. TP-COF films exhibited high rejection of over 90% for dyes removal.     

Synthesis and characterisation of four- and eight-membered ring auralactam complexes

The reactions of the cyclo-aurated gold(III) dihalide complex [{C₆H₃(CH₂NMe₂)-2-(OMe)-5}AuCl₂] with N-cyanoacetylurethane [NCCH₂C(O)NHCO₂Et], 2-benzoylacetanilide [PhC(O)CH₂C(O)NHPh] and acetoacetanilide [MeC(O)CH₂C(O)NHPh], and [{C₆H₄(CH₂NMe₂)-2}AuCl₂] with acetoacetanilide in dichloromethane with excess silver(I) oxide gives the first examples of auralactam complexes, containing (O)---CHR′ four-membered rings. A single-crystal X-ray diffraction study on the complex [{C₆H₄(CH₂NMe₂)-2}A H(COMe)}] reveals similar structural features to related metallalactam complexes of platinum(II) and palladium(II). When a CDCl₃ solution of the complex [{C₆H₃(CH₂NMe₂)-2-(OMe)-5}A HCN}] is allowed to stand for 18 h, a novel dimerisation reaction occurs, giving the insoluble product [{C₆H₃(CH₂NMe₂)-2-(OMe)-5}Au{N(CO₂Et)C(O)CHCN}]₂·2CDCl₃, characterised by an X-ray structure determination. The dimer contains an eight-membered A

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ring.     

偶联噻吩引入对三苯胺成膜性提高及电致变色性能增强

合成了一种以三苯胺(TPA)为核、偶联噻吩为端基的有机小分子4,4'4?-三[4-(2-联噻吩基)苯基]胺(TBTPA), 并通过电化学聚合得到其相应的聚合物PTBTPA. 运用电化学工作站和紫外-可见光谱仪连用对该聚合物膜的光谱电化学性质进行了测试. 与先前已报道的三[4-(2-噻吩基)苯基]胺(TTPA)相比, TBTPA呈现出更好的电化学氧化还原活性. 在电化学聚合过程中, PTBTPA膜呈现出更好的成膜性能且在不同的电位下可以显示三种颜色(深橙色、橄榄绿、暗灰色). 此外, 光谱电化学测试结果表明, 与先前报道的PTTPA相比, PTBTPA具有更好的电致变色(EC)性能, 高的颜色对比度(44.7%), 更高的透射对比度(ΔT, 在720 及1100 nm处对比度分别为49%和52%)及较快的响应时间(在720 nm时为0.93 s, 在1100 nm 时为0.91 s), 同时, PTBTPA具有更高的着色效率(720 nm时为198 cm²·C^-1, 1100 nm时为285 cm²·C^-1). 从扫描电镜(SEM)照片得出PTBTPA薄膜呈现微球颗粒堆积形貌, 颗粒粒径为500 nm左右, 比PTTPA的粒径小. 良好的性能表明PTBTPA在电致变色器件上具有很大的应用前景.