Gold(III) Macrocyclic Complexes in Aqueous Solution

Synthesis of 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraenatogold(III) perchlorate is described. The behavior of complex cations of gold(III) with macrocyclic ligands—N,N"-bis(2-aminoethyl)-2,4-pentanediiminatogold(III) (A²⁺) and 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraenatogold(III) (B⁺)—is studied in aqueous solutions. The formation of A²⁺and B⁺complexes and the protonation of a B⁺complex are investigated, and the solubility products are determined for perchlorate salts of A²⁺and B⁺cations. The six-membered -diiminate rings of the complex cation B⁺are suggested to be nonequivalent in aqueous solutions: one of them either undergoes intramolecular rearrangement or becomes entirely open.     

Biological Properties of Antimony(III) Fluoride Complexes

Result of a study of how antimony trifluoride and fluoride complexes MSb₂F₇ (M = K, Rb, Cs, Tl, NH₄), MSbF₄ (M = Na, K, Rb, Cs, NH₄), and M₂SbF₅ (M = Na, K, Rb, Cs, Tl, NH₄) affect the growth of associations of marine bacteria and vital activity of marine alga Ulva Fenestrata are presented. The possible ways of using Sb(III) fluoride compounds are discussed.     

Thermochemistry of Solution of Fe(III) and Mn(III) Complexes with Natural Porphyrins

The enthalpies of solution of Fe(III), Mn(III) complexes with porphyrins of the chlorophyllgroup (chlorophyll ligand, pheophorbid, chlorin e ₆) and protoporphyrin in various organic solvents at298.15 K were determined calorimetrically. The influence of the structural features of porphyrin molecules and nature of the solvent on the enthalpy characteristics of porphyrin-solvent interaction was discussed.     

Redox Properties of Rhodium(III) Oxo-Bridged Carboxylate Complexes

Chemical and electrochemical oxidation of rhodium (III) oxo-bridged carboxylate complexes was studied. The chemical [with O₃ and Ce(IV) salts] or electrochemical (at potentials of 1.00-1.20 V) oxidations of the binuclear complexes [Rh₂(-O)(-O₂CCH₃)₂(H₂O)₆]^{2 +} and [Rh₂(-O)(-O₂CCF₃)₂(H₂O)₆]^{2 +} leads to the superoxo complexes [Rh₂(-O)(O₂-)(-O₂CCH₃)₂(H₂O)₅]⁺ and [Rh₂(-O)(O₂ ^-)(-O₂CCF₃)₂(H₂O)₅]⁺ with terminal coordination of O₂-. The trinuclear acetate [Rh₃(₃-O)(-O₂CCH₃)₆(H₂O)₃]⁺, unlike its trifluoroacetate analog [Rh3(₃-O)(-O₂CCF₃)₆(H₂O)₃]⁺, is oxidized only electrochemically at a potential of 1.38 V. The oxidation of [Rh₃(₃-O)(-O₂CCH₃)₆(H₂O)₃]⁺ is reversible and involves formation of an unstable superoxo group O₂ ^- between two Rh₃III(₃-O) cores.     

新型酰胺功能化铱[III]配合物的光电性能

设计并制备三种具不同官能团的铱[III]邻菲啰啉配合物: [Ir(ppy)₂phen-Br]Cl, [Ir(ppy)₂phen-COOH]Cl, [Ir(ppy)₂phen-Si]Cl,以及对比参照物[Ir(ppy)₂phen-NH₂]Cl.其中, ppy为2-苯基吡啶, phen-Br为2-溴-2甲基-N-(1, 10-菲啰啉-5-基)丙酰胺, phen-COOH为4-[(1, 10-菲啰啉-5-基)氨基]-4-酰基丁烯酸, phen-Si为5-[N, N-二-3-(三乙氧硅)基]酰亚胺-1, 10-菲啰啉, phen-NH₂为5-氨基-邻菲啰啉,并采用核磁共振(NMR)、质谱(MS)、紫外-可见(UV-Vis)吸收光谱、荧光(PL)光谱法和循环伏安法(CV)等对上述配合物进行了分析和表征.光物理性能研究结果表明:这些配合物在蓝-紫色可见光区域有较强吸收,可发射出明亮的黄色到橙红色荧光,量子效率达到12%以上.相比较于参照物[Ir(ppy)₂phen-NH₂]Cl (5.78 μs),三种新型配合物在量子效率未明显降低甚至提高的前提下,荧光寿命有了显著的提高(9.18-12.00 μs).其中, [Ir(ppy)₂phen-Br]Cl (1)不但有最高的荧光量子产率(32%)和最长的荧光寿命(12.00 μs),而且也具有最好的氧传感性能, I₀/I (无氧与纯氧条件下的荧光强度比值)可达到10.91.这使得[Ir(ppy)₂phen-Br]Cl有望成为接枝型,较高性能的光学氧传感器的候选氧敏指示剂.除此之外,还通过含时密度泛函理论(TD-DFT)计算对配合物光电性能进行补充说明,理论计算表明:这些配合物是以铱为中心的近似八面体结构,理论计算结果与实际实验数据相一致.     

Luminescence Spectral Properties of Europium(III) and Terbium(III) Complexes with Cinnamic Acid

Europium and terbium mixed-ligand complexes with cinnamic acid of composition Ln(Cin)₃· nD · xH₂O, where Ln = Eu³⁺or Tb³⁺, Cin is a cinnamate ion (C₆H₅CH=CHCOO^–), D = 1,10-phenantroline, 2,2"-dipyridyl, benzotriazole (n= 2, x= 0), triphenylphosphine oxide (n= 1, x= 2), or H₂O (n= 0 or 1, x= 0), were synthesized. The compounds were characterized by elemental analysis, IR and luminescence spectroscopy. The Stark structure of the ⁵ D ₀–⁷ F _j(j= 0, 1, 2) electronic transitions in the low-temperature luminescence spectra of europium complexes was analyzed. IR study has revealed a bidentate coordination of the cinnamate ion in the compounds.     

Preparation and Optical Properties of Au(III) Phenylpyridynate Complexes

Russian Journal of General Chemistry -     

铕(III)三元配合物荧光性质的研究

According to fluorescent spectra of a series of Eu(III) ternary complexes in the three solvents EtOH, DMF and CH3CN, the fluorescence is stronger in the solvent CH3CN than in the solvents EtOH and DMF, and fluorescent intensity is contrary to the affinity of three solvents with rare earth ions. Center ions emit fluorescence mainly by an intramolecular energy transfer from the broad absorbing β-diketonate TTA, BTA or BA to the chelated rare earth ions.     

Synthesis and Spectral Properties of Terbium(III) and Gadolinium(III) Complexes with Hydroxybenzoic Acids

Russian Journal of General Chemistry - Coordination compounds of terbium(III) and gadolinium(III) with some hydroxybenzoic acids were electrochemically synthesized. Structure and spectral...     

19F NMR Study of Antimony(III) Fluoride Complexes in Solution

The state of SbF₃, Sb₃O₂F₅, MSb₃F₁₀, MSb₂F₇, M₃Sb₄F₁₅, MSbF₄, and M₂SbF₃, as well as HF and MF (M = Na, K, Rb, Cs, NH₄, and Tl), in a 0.25 M aqueous solution at room temperature was studied by ¹⁹F NMR. It is found that chemical shifts of the ¹⁹F NMR signals (relative to CFCl₃) for the compounds under investigation vary in the 73.3–157.5 ppm range. For the Sb(III) fluoride complexes, chemical shifts in the ¹⁹F NMR spectra vary in the 73.3–85.5 ppm range (relative to CFCl₃). Although the crystals of Sb(III) fluoride complexes contain different polyhedra that are joined in different ways, the NMR spectra of all compounds under study show one narrow signal. The spectra of aqueous solutions of Sb(III) fluoride complexes do not contain signals of free fluoride ions and oxofluoride Sb₃O₂F₅.     

双环金属铱(Ⅲ)异腈配合物的二阶非线性光学性质

采用密度泛函理论(DFT)方法对双环金属Ir(III)异腈配合物的非线性光学(NLO)性质进行计算研究。用B3PW91(UB3PW91)(金属原子采用LANL2DZ基组,非金属原子采用6-31G*基组)方法对配合物进行几何结构优化。在优化构型基础上,采用B3PW91(UB3PW91)和B3LYP(UB3LYP)方法计算了配合物的第一超极化率(βtot),并用CAM-B3LYP(UCAM-B3LYP)(金属原子采用LANL2DZ基组,非金属原子采用6-31G**基组)方法模拟配合物的吸收光谱。结果表明,主配体的取代基(R1)和副配体的取代基(R2)对第一超极化率值贡献不大。配合物发生氧化还原反应,电荷转移方式增多,电荷转移程度增大,使βtot值显著增加,其中1a+([(C∧N)2Ir(CNR)2]+(R=CH3))发生氧化反应和还原反应的βtot值分别增大了75倍和144倍。因此,这类双环金属铱(III)异腈配合物的氧化还原反应可以有效地调节其二阶NLO性质。     

稀土配合物的发光特性及其能量传递研究

利用激光诱导荧光技术研究了稀土铕等金属配合物的发光特性及其能量传递动力学过程．得到了这些稀土配合物中中心离子Eu（3 ）的激发光谱，配体的三线态发时光谱和单线态发射光谱；在实验上观察到由于中心离子Eu（3 ）的5D2←7F0马跃迁吸收造成的配体发射光谱中的凹陷行为     

Binuclear Homoleptic Manganese(III,III) and Manganese(IV,III) Complexes with Deprotonated D-Mannose from Aqueous Solution

Just a “reducing” sugar —namely, D -mannose—is a starting material in the synthesis of a mixed-valence complex of manganese in the oxidation states +III and +IV . Ba₂[Mn^IIIMn^IV(β-D -ManfH₋₅)₂]Cl⋅14 H₂O (Manf=mannofuranose; the structure of the anion is shown on the right) is prepared in aqueous solution by oxidation of an analogous Mn₂^III complex with oxygen. In neutral solutions the Mn^IIIMn^IV binuclear complex is formed by disproportionation of the Mn₂^III precursor.     

Acid–Basic Properties of Al(III), Ga(III), and In(III) Complexes with Octaphenyltetraazaporphine

Al(III), Ga(III), and In(III) complexes with octaphenyltetraazaporphine and halide axial ligands of the composition [(X)MTAP] (X = F, Cl, Br) and In(III) complexes with bidentate ligands of the composition [(Y)InTAP] (Y = nitrite (NO₂) and 2,3-naphthodiolate (NpO₂)) were synthesized. The acid–basic properties of the complexes were studied in the proton-donor media and the concentration stability constants of the acidic forms obtained at the first protonation stage were determined. The effect of the nature of a metal and extra ligand on the basic properties of meso-nitrogen atom in macrocyclic ligand was discussed.     

三价金配合物抗肿瘤活性研究*

三价金配合物具有潜在的抗肿瘤活性,是目前金属药物领域的研究热点。本文按配位原子的不同总结了稳定三价金配合物的结构特征,按其生物活性的构效关系、生物靶点和作用机制综述了三价金配合物抗肿瘤活性研究的最新成果：配体的结构特点以及离去基团对三价金配合物的体外细胞毒性影响较大;介绍了用于检测三价金配合物与可能的生物靶分子之间的相互作用的多种物理和生物学方法,重点关注了相互作用的模式,如嵌入/静电吸引/共价结合等,并解释了三价金配合物抗肿瘤活性的原因。最后提出了一些研究新思路,以期有助于设计得到靶标明确的具有良好药理活性的抗肿瘤药物。     

单核Mn(III)-Shiff碱配合物的晶体结构与性质

报导了两个Schiff碱配体的单核Mn（Ⅲ）配合物（[Mn（Ⅲ）（L1）（H2O）］4CIO。·ZH。O（1）和［Mn（ffi）（LZ）厂Ic。·ZH。O（2》的合成、晶体结构及性反X一衍射晶体结构分析证实：配合物1的晶体属于正交晶系，Pna21空间群．其晶胞参数为α＝10．932（7）A，b＝22．393（5）A，c＝8．960（3）A，V=2193（1）A3，Z＝4．2的晶体属于正交晶系，P212121空间群，α＝17．345（3）A，b＝17．905（2）A，c=7．789（1）A，V＝2418．9（6）A3，Z=4．电化学研究结果显示：配合2是稳定的电化学产物，而1在电场作用下容易歧化．由此说明配位环境是影响化合物稳定性的重要因素．     

Luminescent Properties of Phosphonate Ester-Supported Neodymium(III) Nitrate and Chloride Complexes

This study examines the synthesis of two geminal bisphosphonate ester-supported Ln³⁺ complexes [Ln(L3)₂(NO₃)₃] (Ln = Nd³⁺ (5), La³⁺ (6)) and optical properties of the neodymium(III) complex. These results are compared to known mono-phosphonate ester-based Nd³⁺ complexes [Nd(L1/L2)₃X₃]_n (X = NO₃⁻, n = 1; Cl⁻, n = 2) (1–4). The optical properties of Nd³⁺ compounds are determined by micro-photoluminescence (µ-PL) spectroscopy which reveals three characteristic metal-centered emission bands in the NIR region related to transitions from ⁴F_3/2 excited state. Additionally, two emission bands from ⁴F_5/2, ²H_9/2 → ⁴I_J (J = 11/2, 13/2) transitions were observed. PL spectroscopy of equimolar complex solutions in dry dichloromethane (DCM) revealed remarkably higher emission intensity of the mono-phosphonate ester-based complexes in comparison to their bisphosphonate ester congener. The temperature-dependent PL measurements enable assignment of the emission lines of the ⁴F_3/2 → ⁴I_9/2 transition. Furthermore, low-temperature polarization-dependent measurements of the transitions from R₁ and R₂ Stark sublevel of ⁴F_3/2 state to the ⁴I_9/2 state for crystals of [Nd(L3)₂(NO₃)₃] (5) are discussed.     

含联吡啶，Eu(III)或Gd(III)的手性高分子配合物的合成及荧光性质研究

手性高分子P–1由(R)-5,5′-二溴-6,6′-二(4-三氟甲基苯基)-2,2′-二正辛氧基-1,1′-联萘(R–M–1)和5,5′-二乙烯基-2,2′-联吡啶(M–2)通过Pd催化的Heck偶合反应合成得到,高分子配合物P-2和P-3由高分子P-1与Eu(TTA)3·2H2O和Gd(TTA)3·2H2O (TTA– = 2-噻吩甲酰三氟丙酮)反应生成。手性高分子P-1能发射强的蓝色荧光,这是由于手性重复单元(R)-6,6′-二(4-三氟甲基苯基)-2,2′-二正辛氧基-1,1′-联萘和单元2,2′-联吡啶通过亚乙烯基桥连形成共轭高分子结构造成的。在不同的激发波长激发下,含Eu(III)的高分子配合物P–2不仅显示高分子荧光,还可显示Eu(III) (5D0→7F2)特征荧光。含Gd(III)的高分子配合物P–3仅发射高分子荧光。基于高分子及含RE(III)的高分子配合物的荧光性质研究发现,共轭高分子并没有把能量转移到Eu(III)或Gd(III) 配合物部分,只发射它自身的荧光,含Eu(III)的高分子配合物P–2发射Eu(III) (5D0→7F2)特征荧光能量主要来源于配阴离子TTA–。     

Vanadium(III) Complexes with Picolinic Acid and Dipicolinic Acid in Aqueous Solution

The complex species formed in aqueous solution (25 ^∘C, I = 3.0 mol-dm⁻³ KCl ionic medium) between V³⁺ cation and the ligands: picolinic acid (Hpic, HL) and dipicolinic acid (H₂dipic, H₂L), have been studied potentiometrically and by spectrophotometric measurements. The application of the least-squares computer program LETAGROP to the experimental emf (H) data, taking into account the hydrolytic species of V³⁺ ion, indicates that under the employed experimental conditions, the formation of the complexes [VL]²⁺, [V(OH)L]⁺, [VL₂]⁺, [VL₃], [V₂OL₄] with picolinic acid and the complexes [VL]⁺, [V(OH)L], [V(OH)₂L]⁻, [V(HL)(L)], and [VL₂]⁻ with dipicolinic acid were observed. The stability constants of the complexes formed were determined by potentiometric measurements, and spectrophotometric measurements were done in order to perform a qualitative characterization of the complexes formed in aqueous solution.