5,7¢-(亚甲胺基)-二-8-羟基喹啉及其衍生物的密度泛函理论计算

在B3LYP/6-31G(d)水平上对5, 7¢-(亚甲胺基)-二-8-羟基喹啉及其5种衍生物进行了几何构型全优化, 探讨了喹啉不同位H被吸电子基团CN及羟基O被S原子取代对分子电离势(IP)、电子亲和势(EA) 、电荷转移、前线轨道能量和电子光谱等性质的影响. 用含时密度泛函理论(TD-DFT)计算了分子在气相及液相的吸收光谱, 计算结果与实验值基本符合. 取代基对5, 7¢-(亚甲胺基)-二-8-羟基喹啉锌分子的性质有较大影响. 电子亲和势计算表明, 该类化合物的电子亲和势较大, 都是较好的电子传输材料.     

高相对分子质量8-羟基喹啉锂聚合物的制备和性能

高分子电致发光显示器(PLED)是近几年来国际、国内的研究热点,取得了很大的进展,其中高分子化金属配合物是一类很有价值的功能材料。通过甲基丙烯酸甲酯(MMA)、苯乙烯(S)和含有8-羟基喹啉的单体共聚合成模板聚合物,再与氢氧化锂作用,实现了8-羟基喹啉锂配合物的高分子化,获得了一种能够溶解在普通的溶剂中的高相对分子质量的含喹啉锂配合物的发光聚合物,并利用元素分析、¹H-NMR、FTIR、UV、PL光谱、DSC、TGA、GPC等方法对其结构和性能作了表征。紫外吸收和光致发光(PL)光谱说明合成共聚物的发光来自于Liq基团,引入的可聚合的链段以及共聚物中的甲基丙烯酸甲酯或苯乙烯链段,并没有影响发光波长的改变。亲核溶剂改变8-羟基喹啉金属配合物分子结构,使共聚物光谱明显红移20nm左右。     

一种新型的橙红光发射材料聚8-羟基喹啉镓的合成与光谱特性

合成了高分子金属配合物聚8-羟基喹啉镓(Gaqq3)n.利用红外吸收光谱、X射线衍射谱(XRD)研究了配合物的分子结构、物相结构;利用热重(TG)分析研究了配合物的热稳定性;利用紫外吸收光谱、荧光激发和发射光谱研究了该配合物的光物理性能.结果表明:(Gaqq3)n的热分解温度为443.6℃,具有较高的热稳定性.(Gaqq3)n的紫外吸收带位于250～500 nm,存在较强的带尾吸收,表明禁带中存在带隙缺陷态.(Gaqq3).的荧光激发带位于380～456nm,荧光发射峰位于568nm,为橙红光发射.光学带隙2.49 eV.与Gaq3相比,荧光强度有所减弱,这是由于次甲基相连的两个喹啉环的扭曲导致了(Gaqq3)n的刚性和共平面性不好;由于分子共轭体系的增大,使(Gaqq3)n分子的π电子更加离域化,导致了荧光发射峰发生了红移.(Gaqq3)n有望在有机电致发光器件和有机光伏器件中得到应用.     

Crystal Structures, Interactions with Biomacromolecules and Anticancer Activities of Mn(II), Ni(II), Cu(II) Complexes of Demethylcantharate and 2-Aminopyridine

Three novel transition metal complexes (Hapy)(2)[M(DCA)(2)]·6H(2)O (M?=?Mn(II) (1), Ni(II) (2), Cu(II) (3); DCA?=?demethylcantharate, 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylate, C(8)H(8)O(5); Hapy?=?2-aminopyridine acid, C(5)H(7)N(2)) were synthesized and characterized by elemental analysis, infrared spectra, thermogravimetric analysis and X-ray diffraction. DNA binding properties of the complexes were investigated by electronic absorption spectra, fluorescence spectra and viscosity measurements. Results indicated the complexes could bind to DNA through partial intercalation mode with binding constants K ( b )/(L·mol(-1)) of 1.91?×?10(4) (1), 5.13?×?10(4) (2) and 1.12?×?10(5) (3) at 298?K. Meanwhile, the interactions of the complexes with BSA were also studied by fluorescence spectra. The results suggested that the complexes could quench the fluorescence of BSA through static quenching with the binding constants K ( A )/(L·mol(-1)) of 1.44?×?10(6) (1), 1.14?×?10(7) (2) and 2.98?×?10(4) (3). And the main contribution was tryptophan residues of BSA. The antiproliferative activity test revealed that complexes showed more intense inhibition ratios against human hepatoma cells lines and human gastric cancer cells lines in vitro. Copper(II) complex (3) possesses the strongest inhibition ratio against human hepatoma cells.     

Bipolar Alq3-based complexes: Effect of hole-transporting substituent on the properties of Alq3-center

Two bipolar Alq₃-based complexes, tris{5-[(carbazole-9'-yl)methyl]-8-hydroxyquinoline} aluminum (Al(CzHQ)₃) and tris{5-[(phenothiazine-9'-yl)methyl]-8-hydroxyquinoline} aluminum (Al(PHQ)₃), involving an Alq₃-center and three hole-transporting substituents (carbazole or phenothiazine), were prepared and characterized. Effects of hole-transporting substituent on the properties of Alq₃-center were investigated in detail. It is found that the two complexes have improved hole-transporting performance and appropriate thermal stability (the 5%-weight-loss temperatures T_5%>260 ^oC). Photoluminescence (PL) spectra indicate that both energy transfer and electron transfer can take place simultaneously in the PL process of these complexes. Both thermodynamics and dynamics of the electron transfer were studied and corresponding parameters were calculated. Energy transfer is favorable for the PL of Alq₃-center, while electron transfer is unfavorable for the PL of Alq₃-center. These results will be useful to explore novel OLEDs material with increased efficiency.     

8-羟基喹啉-山梨酸稀土配合物与鲱鱼精DNA相互作用的光谱研究

合成了以山梨酸(SA)和8-羟基喹啉(Hq)为配体的Sm(Ⅲ)、Eu(Ⅲ)为中心的三元稀土配合物,研究了配合物与DNA之间的作用机制。采用红外光谱、紫外-可见吸收光谱、差热热重、元素分析和摩尔电导等方法,确定了配合物的化学组成,采用光谱法探讨了配合物与鲱鱼精DNA的作用机制。结果表明:配合物的化学组成为Sm(Hq)(SA)2和Eu(Hq)(SA)2,其最大吸收峰在加入DNA后发生减色和红移,中性红(NR)使配合物-DNA体系的吸收发生减色,伴有等色点出现。配合物的加入导致NR-DNA体系的吸收峰强度和位置发生变化。计算求得Eu(Hq)(SA)2和Sm(Hq)(SA)2分别与DNA的结合位点数为5,在20℃下,Sm(Hq)(SA)2、Eu(Hq)(SA)2与DNA的结合常数分别是2.04×104L/mol和1.09×104L/mol。2种稀土配合物都能不同程度地猝灭NR-DNA体系的荧光,表明2种稀土配合物对DNA都有较强的嵌插作用且能自发进行,结合能力为Sm(Hq)(SA)2Eu(Hq)(SA)2。     

8—羟基喹啉金属螯合物的吸收光谱和发射光谱

测量了一系列８－羟基喹啉金属螯合物的吸收谱和发射谱，发现当喹啉螯合不同的金属阳离子，其各类光谱有不同程度的红移，本文经验地给出了８－羟基喹啉金属螯合物发射谱和吸收谱移动的规律并分析了金属离子影响光谱原因。     

The Infrared Spectra of the First Transition Series Metal(II) Bis(Aquo) Complexes Of 8-Hydroxyquinoline

Abstract

The infrared spectra (700–100 cm^?1) of the complexes [M(ox)₂(H₂O)₂] (ox = 8-hydroxyquinolinate anion, M = Mn, Fe, Co, Ni, Cu, Zn) are discussed. For the purposes of assignment of the metal ligand modes, deuterated 8-hydroxyquinoline-d ₇ was prepared by the Skraup synthesis and the spectra of the deuterated complexes were compared with those of the unlabelled species. Furthermore, [⁶⁴Zn(ox)₂(H₂O)₂] and [⁶⁸Zn(ox)₂(H₂O)₂] were prepared by reaction of ⁶⁴ZnSO₄ and ⁶⁸ZnSO₄ with 8-hydroxyquinoline and the effects of metal isotope labelling on the spectra were examined and compared with earlier isotopic data on the nickel and zinc complexes.     

Nanowires of metal (Cd,Cu) halide complexes with 8-hydroxyquinoline for photoelectrochemical and electrochemiluminescence sensing

Metal-hydroxyquinoline-halogen (MqX, M?=?Cd, Cu; q?=?8-hydroxyquinoline; X?=?Cl, Br, I) nanowires are synthesized via a sonochemical-assisted method. The elemental analysis (EA), inductively coupled plasma-optical emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS) support an M/q/X ratio of 1:1:1. The electron microscope images reveal a typical CdqX and CuqX nanowire diameter of 30–50 nm and a nanowire length of 400–600 nm. In addition, the synthesis of the MqX nanowires is only observed when there is an excess of halide ions (X/q molar ratio of 3 or greater). This halide deficiency results in the formation of micrometer-sized Mq₂ sheets. We demonstrated the conversion of the MqX nanowires to Mq₂ micro-sheets in an ultrasonic bath of 1 M 8-Hq ethanol solutions (50%, w/w) at 50 °C for 2 h, but not vice versa. The MqX nanowires exhibited excellent properties for photoluminescence, electrochemiluminescence (ECL), and photoelectrochemistry (PEC). The CdqBr and CdqI nanowires were coated onto a glass carbon and a fluorine-doped tin oxide glass electrode to develop the above ECL and PEC methods for the detection of H₂O₂ and Cu²⁺, respectively. In the range of 2 to 14 μM, the ECL intensity of the CdqBr nanowires was inversely proportional to the concentration of H₂O₂ with a detection limit of 0.26 μM. For Cu²⁺ sensing, the photocurrent of the CdqI nanowires exhibited a linear response to Cu²⁺ over the range of 2 to 16 μM of which a detection limit of 0.2 μM was observed.     

二正丁基锡三齿酰腙Schiff碱配合物的合成和红外光谱研究

合成了 4种三齿酰腙Schiff碱配体H2 L [H2 L1 :C6 H5C(O)NHN =CHC6 H4OH 2 ,H2 L2 :C6 H5C(O)NHN =CHC6 H3(OH) 2 2 ,4,H2 L3:NC5H4C(O)NHN =CHC6 H4OH 2 ,H2 L4:NC5H4C(O)NHN =CHC6 H3(OH) 2 2 ,4]和它们的二正丁基锡新型配合物 (n Bu) 2 SnL ,通过元素分析确定了这些配合物的组成 ,并对配合物在 4 0 0 0～ 40 0cm- 1范围内的主要红外光谱吸收峰进行了归属和讨论 ,推测出配合物可能的分子结构。     

光谱法研究七、八元瓜环对亚甲基蓝的分子识别

利用紫外-可见吸收光谱和荧光光谱法考察了七、八元瓜环(Q[7],Q[8])对客体亚甲基蓝染料(g)的分子识别作用.结果表明,Q[7]与g作用形成物质的量比为2:1的主客体配合物,Q[8]与g作用形成的是物质的量之比为1:2的主客体配合物.吸收光谱法测得的包结常数分别为KQ[7]-g=1.34×1012 L2·mol-2,KQ[8]-g=5.34×1012 L2·mol-2;荧光光谱法测得的KQ[7]-g=1.53×1012 L2·mol-2,KA[8]-g=6.11×1012 L2·mol-2,两种方法结果一致.随着Q[7或8]浓度的增加,瓜环对客体有明显的荧光增敏作用,而Q[8]对客体有明显的荧光猝灭作用.从Q[7]和Q[8]分别与客体作用体系的紫外-可见吸光度和荧光强度随pH值改变的变化规律可以看出,体系在pH在0.5～13范围内均能观察到主客体的相互作用,且作用比例不发生变化.     

The Infrared and 1H-NMR Spectra of 8-Hydroxyquinoline Adducts of 8-Hydroxyquinoline Complexes of Dioxouranium(VI), Thorium(IV) and Scandium(III)

The ¹H-nmr and infrared spectra of the complexes [M(ox)_n(Hox)] where M = UO₂ (n = 2), Th (n = 4) or Sc (n = 3) and Hox = 8-hydroxyquinoline are discussed. The nmr spectra of the adducts are uninformative with respect to the bonding and structure of these molecules since they dissociate in solution. The solid state ir spectra show that the adducted molecule of 8-hydroxyquinoline is bound to the metal through the phenolic oxygen, the proton forming an intramolecular hydrogen bond between the nitrogen atom of the adducted molecule and the oxygen atom of a neighbouring chelate ring. The mid-and far-ir spectra are reported for the first time and assignments for the δN-H, νM-O and νM-N modes have been made.     

La（Ⅲ）,Gd（Ⅲ）,Tb（Ⅲ）8—羟基喹啉固体配合物的光声光谱与 …

本文合成Ｌａ（Ⅲ）、Ｇｄ（Ⅲ）、Ｔｂ（Ⅲ）８－羟基喹啉固体配合物，通过对其光声光谱的分析，研究了８－羟基喹啉稀土配合物的荧光性质和驰豫过程。     

A terbium (III) complex with triphenylamine-functionalized ligand for organic electroluminescent device

A novel ligand, 4-diphenylamino-benzoic acid (HDPAB), and the corresponding Tb (III) complex, Tb (DPAB)₃ which can be dissolved easily in organic solvents were synthesized and characterized. Organic electroluminescent (EL) device with a structure of indium tin oxide (ITO)/poly(N-vinylcarbazole) (PVK): Tb (DPAB)₃ (50 wt%, 80 nm)/1,3,5-tris-(N-phenylbenzimidazol-2-yl)benzene (TPBI) (30 nm)/tri(8-hydroxyquinoline)aluminum (AlQ) (20 nm)/LiF (1 nm)/Al (150 nm) in which Tb (DPAB)₃ acted as an emitter were fabricated. The maximum luminance of 230 cd m⁻² at 20 V and the maximum efficiency of 0.62 cd A⁻¹ were obtained due to the introduction of hole-transporting group, representing the best result to date among Tb (III) carboxylate complexes based EL devices. These results indicate that modifications of rare earth complexes are a promising way to improve the properties of EL devices.     

Microwave assisted IMDAF# reaction: microwave irradiation applied with success to cycloaddition reaction of N-propargyl-N-p-tolyl-N-2-furfurylamines

The new tertiary furfurylamine with triple bond as a dienophylic part i.e. N-(5-methyl-2-furfuryl)-N-prop-2-ynyl-p-toluidine (1) was prepared and the intramolecular Diels-Alder reaction of the amine (1) was performed under microwave irradiation conditions and by heating a benzene solution of the amine under nitrogen. Comparing the results of the usual thermal and the MAOS reaction, we confirmed our expectations that MAOS could promote the outcome of IMDA reaction of the suitably N-substituted tertiary 2-furfuryl-amines. In the present example, N-p-tolyl-5-methyl-5,7a-dihydro-5,7a-epoxyisoindoline was obtained in much better yield and of higher purity.     

2-氯-5-三氟甲基苯胺水杨醛Schiff碱的结构及光谱性质研究

Schiff碱及其络合物的合成一直是研究的热点,其在药学、催化等领域有广泛的应用。实验以2-氯-5-三氟甲基苯胺、水杨醛为原料,合成2-氯-5-三氟甲基苯胺水杨醛Schiff碱,测定了Schiff碱的红外光谱和氢谱。利用密度泛函理论（DFT）B3LYP方法在6-311++G**基组上对合成的Schiff碱化合物进行了几何构型的优化和红外光谱的计算,得到了分子的优势构象、频率值及对应的红外强度,并比较了实验和理论计算的光谱数据,对分子的振动模式进行了全面的光谱归属,发现理论计算与实验测试结果吻合的较好。     

Synthesis, DNA-binding, Cytotoxicity, Photo Cleavage, Antimicrobial and Docking Studies of Ru(II) Polypyridyl Complexes

Three Ruthenium(II) polypyridine complexes, [Ru(phen)₂(mipc)]²⁺(1), [Ru(bpy)₂(mipc)]²⁺ (2) and [Ru(dmb)₂(mipc)]²⁺(3) [mipc?=?2-(6-methyl-3-(1H-imidazo[4, 5-f][1,10]-phenanthroline-2-yl)-4H-chromene-4-one, phen?=?1,10-phenanthroline,bpy?=?2, 2′bipyridine,dmb?=?4, 4′-dimethyl-2, 2′-bipyridine] have been synthesized and characterized by elemental analysis, IR, UV–Vis, ¹H& ¹³C NMR and mass spectra. The DNA-binding properties of the Ruthenium(II) complexes were investigated by spectrophotometric methods, viscosity measurements and light switch studies. These three complexes have been focused on photo activated cleavage studies with pBR-322 and antimicrobial studies. Experimental results indicate that the three complexes intercalate into DNA base pairs and follows the order of 1?>?2?>?3 respectively. Molecular docking studies also support the DNA interactions with complexes through hydrogen bonding and vander Waal’s interactions. Cytotoxicity studies with Hela cell lines has been revealing about anti tumor activity of these complexes.     

2-氯-5-三氟甲基苯胺水杨醛Schiff碱的结构及光谱性质研究

Schiff碱及其络合物的合成一直是研究的热点,其在药学、催化等领域有广泛的应用。实验以2-氯-5-三氟甲基苯胺、水杨醛为原料,合成2-氯-5-三氟甲基苯胺水杨醛Schiff碱,测定了Schiff碱的红外光谱和氢谱。利用密度泛函理论（DFT）B3LYP方法在6-311++G**基组上对合成的Schiff碱化合物进行了几何构型的优化和红外光谱的计算,得到了分子的优势构象、频率值及对应的红外强度,并比较了实验和理论计算的光谱数据,对分子的振动模式进行了全面的光谱归属,发现理论计算与实验测试结果吻合的较好。     

Tin oxide nanocubes, and tin-core/tin oxide-shell nanostructures, with and without a hollow interior

A number of nanoscale tin oxide structures including 2–5 nm tin oxide hollow nanoparticles, 3–5 nm tin oxide nanocubes, 80–120 nm tin-core/tin oxide-shell nanocubes, and hollow tin oxide nanocubes, have been prepared from phenanthroline (phen)-capped Sn nanoparticles. Transmission electron microscopy revealed the existence of a hollow interior in the tin-core/tin oxide-shell nanostructures. It is believed that the low melting Sn core was hollowed out by electron beam irradiation of the sample during microscopy. The 2–5 nm tin oxide hollow nanoparticles and 80–120 nm tin oxide hollow nanocubes had thin but stable shells capable of preserving the integrity of the large cavity within.