Luminescence of Novel Neodymium Sulfonylaminate Complexes in Organic Media

Luminescence of Nd(III) in an organic solvent having C-H bonds was achieved for the first time by complexing Nd(III) with long-chain perfluoroalkylated ligands such as bis(perfluorooctylsulfonyl)aminate (pos). The complex [Nd(pos)(3)] gave an emission quantum yield of 3.0+/-0.5 % in undeuterated acetone. The bulky pos ligands suppress the excitation of C-H vibrations, energy migration at diffusional collision, and the coordination of acetone molecules (see picture) to the Nd(III) center, which otherwise quench the luminescence.     

Designing Simple Tridentate Ligands for Highly Luminescent Europium Complexes

A series of tridentate benzimidazole‐substituted pyridine‐2‐carboxylic acids have been prepared with a halogen, methyl or alkoxy group in the 6‐position of the benzimidazole ring, which additionally contains a solubilising N‐alkyl chain. The ligands form neutral homoleptic nine‐coordinate lanthanum, europium and terbium complexes as established from X‐ray crystallographic analysis of eight structures. The coordination polyhedron around the lanthanide ion is close to a tricapped trigonal prism with ligands arranged in an up–up–down fashion. The coordinated ligands serve as light‐harvesting chromophores in the complexes with absorption maxima in the range 321–341 nm (ε=(4.9–6.0)×10⁴ M ^?1 cm^?1) and triplet‐state energies between 21 300 and 18 800 cm^?1; the largest redshifts occur for bromine and electron‐donor alkoxy substituents. The ligands efficiently sensitise europium luminescence with overall quantum yields ( ) and observed lifetimes (τ_obs) reaching 71 % and 3.00 ms, respectively, in the solid state and 52 % and 2.81 ms, respectively, in CH₂Cl₂ at room temperature. The radiative lifetimes of the Eu(⁵D₀) level amount to τ_rad=3.6–4.6 ms and the sensitisation efficiency η_sens= (τ_rad/τ_obs) is close to unity for most of the complexes in the solid state and equal to approximately 80 % in solution. The photophysical parameters of the complexes correlate with the triplet energy of the ligands, which in turn is determined by the nature of the benzimidazole substituent. Facile modification of the ligands makes them promising for the development of brightly emissive europium‐containing materials.     

Thermal Decomposition of Neodymium Amide Complexes

The decomposition of NdCl₃ L(L = N,N-dimethylformamide [DMF] or N,N-dimethyacetamide [DMA]) compounds has been investigated by thermogravimetric and differential thermal analysis (TGA and DTA) coupled with Fourier transform infrared (FTIR) spectroscopy. When heated in air, the NdCl₃L compounds decompose by a mechanism involving oxidation of the amide ligand to CO₂ and HCl. Some free armide is also released in the thermal decomposition in air. However, when heated under nitrogen, clean release of DMA or DMF is observed. In both cases, the amide is released two steps. From 30 to 40% of the amide is initially released with little or no associated enthalpy as measured by DTA. As the temperature is increased, the remaining 60 to 70% of the amide is released via an endothermic process. The enthalpy for this release is 53.1 - 3.8 kJ/mole for DMF and 40.9 - 1.1 kJ/mole for DMA, suggesting that DMF binds more strongly to Nd(III) than does DMA. Steric effects caused by the additional methyl group in DMA might be responsible for the weaker binding of this amide compared to DMF.     

聚合负载三氯化钕配合物的合成及其催化活性——含硫醇和亚砜基团的配合物

合成了含—CH     

Collisional Deactivation of K(7s2S) and K(5d2D) by No

Radiative lifetimes and total deactivation cross sections of K(7²S) and K(5²D) by collision with NO are studied. The K atomic vapor in either the 7²S or the 5²D state was prepared by two- photon absorption using a dye laser. The decay signal of the time-resolved fluorescence from the 7²S – 4²P_1/2 or 5²D – 4²P_3/2 transition was then monitored. Based on a Stern-Volmer analysis, the radiative lifetimes are 155 ±8 ns and 561 ± 18 ns for the K(7²S) and K(5²D) states, respectively. The total deactivation cross sections are 88 ±1Ų and 70 ±2Ų for the K(7²S)-NO and K(5₂D)-NO collisions, respectively. In the absence of NO collisions the radiative lifetimes obtained in this work show excellent agreement with those previously reported. The quenching cross sections for NO have been measured for the first time, and have values in a reasonable range, when compared with Na-N₂ collisions.     

HOD分子在(~C)1B1态的光解动力学:产物OH/OD的分支比以及OD键解离能

Photodissociation of jet-cooled HOD via the ? state around 124 nm has been studied using the H(D)-atom Rydberg tagging time-of-flight technique. Rotational state resolved action spectrum and the product translational energy distribution spectra have been recorded for both D+OH and H+OD dissociation channels. Product channel OH/OD branching ratios for the individual ?- X rotational transition have been determined. A comparison is also given with the B- X and ?- X transitions. In addition, the dissociation energy of the OD bond in HOD has been determined accurately to be 41751.3±5 cm^-1.     

Ab initio Study of the Potential Energy Surface and Product Branching Ratios for Reaction of O（^1D） with C2H5CI

The potential energy surface of O（^1D）＋C2H5Cl reaction was studied using QCISD（T）/6- 311＋＋G（d,p）//MP2/6-31G（d,p） method. The calculations reveal an insertion-elimination mechanism. The insertion reaction of O（^1D） and C2H5Cl produces two energy-rich intermediates, IM1 and IM2, which subsequently decompose into various products. The calculations of the branching ratios of various products formed through the two intermediates were carried out using RRKM （Rice-Ramsperger-Kassel-Marcus） theory at the collision energies of 0, 20.9, 41.8, 62.7, 83.6, 104.5, and 125.4 kJ/mol. HCl is the main decomposition product for IM1; CH2OH is the main decomposition product for IM2. Since IM1 is more stable than IM2, HCl is probably the main product of the O（^1D）＋C2H5Cl reaction.     

Mode Specificity Dynamics of Prototypical Multi-Channel H+CH3OH Reaction on Globally Accurate Potential Energy Surface

The H+CH\begin{document}$ _3 $\end{document}OH reaction, which plays an important role in combustion and the interstellar medium, presents a prototypical system with multiple channels. In this work, mode specific dynamics of different product channels is investigated theoretically on a recently developed reliable potential energy surface based on a large number of data points calculated at the level of UCCSD(T)-F12a/AVTZ. It has been demonstrated that vibrational excitations of the O\begin{document}$ - $\end{document}H stretching motion, the torsional motion, the C\begin{document}$ - $\end{document}H stretching vibrations, show different influences on the four product channels, H\begin{document}$ _2 $\end{document}+CH\begin{document}$ _3 $\end{document}O, H\begin{document}$ _2 $\end{document}+CH\begin{document}$ _2 $\end{document}OH, H\begin{document}$ _2 $\end{document}O+CH\begin{document}$ _3 $\end{document}, and H+CH\begin{document}$ _3 $\end{document}OH. This work is helpful for understanding the mode-specific dynamics and controlling the competition for complicated reactions with multiple product channels.     

Correlation of Broad Absorption Band with Small Singlet-Triplet Energy Gap in Organic Photovoltaics

Organic photovoltaics (OPV) are one of the most effective ways to harvest renewable solar energy, with the power conversion efficiency (PCE) of the devices soaring above 19 % when processed with halogenated solvents. The superior photocurrent of OPV over other emerging photovoltaics offers more opportunities to further improve the efficiency. Tailoring the absorption band of photoactive materials is an effective way to further enhance OPV photocurrent. However, the field has mostly been focusing on improving the near-infrared region photo-response, with the absorption shoulders in short-wavelength region (SWR) usually being neglected. Herein, by developing a series of non-fullerene acceptors (NFAs) with varied side-group conjugations, we observe an enhanced SWR absorption band with increased side-group conjugation length. The underpinning factors of how molecular structures and geometries improve SWR absorption are clearly elucidated through theoretical modelling and crystallography. Moreover, a clear relationship between the enhanced SWR absorption and reduced singlet-triplet energy gap is established, both of which are favorable for the OPV performance and can be tailored by rational structure design of NFAs. Finally, the rationally designed NFA, BO-TTBr, affords a decent PCE of 18.5 % when processed with a non-halogenated green solvent.     

Modeling of Eu3+ Energy Levels in Complexes with 1,10-Phenanthroline Derivatives

The experimental electronic spectra of the Eu³⁺ ion in three groups of the Eu complexes (-diketonates, acetates, and nitrates) with the 1,10-phenanthroline derivatives were used to calculate the crystal field parameters for the model of the nearest environment of this ion with the C ₂ point group symmetry. It was shown that these parameters can be used for estimating the coordination number of the metal cation and establishing the structural peculiarities.     

氯化钕配合物在4—乙烯吡啶聚合反应中的催化作用

氯化钕配合物是双烯烃聚合催化剂组分之一 ,与烷基铝所构成的二元体系对丁二烯聚合具有较佳活性 [1,2 ] ,但用氯化钕配合物催化极性单体的聚合反应尚未见报导 .极性单体的聚合是人们感兴趣的课题 ,例如 Benito等 [3 ]用过渡金属化合物 (VCl3-Al Et3)体系催化聚合 4-乙烯吡啶 (4VPy)极性单体 .但是它的催化活性较低 ,催化效率为 3.1×1 0 -4 kg· mol-1· h-1.我们研究了将含少量的氯化钕配合物催化剂用于该聚合反应 ,催化活性得到很大提高 ,催化效率达到 50 .71 Kg· mol-1· h-1.表明氯化钕配合物催化体系不仅对双烯烃而且对极性单体聚…     

Lack of Linear Free Energy Relationships in the p-Toluenesulfonic Acid Mediated Chromium(VI) Oxidation of Organic Sulfides

Summary.  The oxidation of methylphenyl sulfide by imidazolium dichromate in acetonitrile mediated by p-toluenesulfonic acid is first order in IDC and TsOH and zero order in MeSPh in the concentration range studied. The IDC oxidation of 14 para-, meta-, and ortho-substituted phenylmethylsulfides at 20–45°C conforms to the isokinetic relationship but not to any of the linear free energy relationships; the isokinetic temperature lies within the experimental temperature range. Received April 18, 2000. Accepted (revised) July 12, 2000     

芳烃金属配合物在有机合成中的应用

本文讨论了芳烃金属配合物中的芳香部份在与金属配合后性质上的变化,以及这些变化后的性质在有机合成中的应用。     

单糖和硼酸形成络合物的讨论

本文用平均络合平衡常数的测定及~(13)C NMR两种方法对一些单糖、糖苷和硼酸生成的络合物进行了研究。研究结果表明醛戊糖、醛己糖虽在溶液中主要以吡喃环存在,但当它们与硼酸络合时即由吡喃转变成呋喃。     

环糊精包合有机磷酸作为缓蚀剂的理论研究

采用分子模拟对三种有机磷酸(5-单磷酸腺苷(A)、羟基乙叉二磷酸(B)、2-磷酸基-1, 2, 4-三羧酸丁烷(C))及其与阳离子改性的β-环糊精(HPTEA-β-CD)形成的包合物作为缓蚀剂进行了理论研究,并通过失重法进行了实验验证.量子化学的计算结果表明,三种有机磷酸分子的反应活性主要集中在N、O、P等原子上,其中C分子的反应活性更强.同时采用分子动力学模拟HPTEA-β-CD包合A、B、C分子作为缓蚀剂在Fe(001)表面上的平衡吸附,结果表明C-HPTEA-β-CD的缓蚀效率最强.通过失重法分析,三种缓蚀剂对q²35碳钢均有良好的缓蚀性,其中C-HPTEA-β-CD的缓蚀效率最高,达到了91.50%,实验结果与理论计算的分析一致.     

水杨酰二甲双胍钕的模板法合成及其降血糖作用

在无水乙醇中组合水杨酸甲酯、HDMBG及三氯化钕, 通过“模板反应”成功地合成了水杨酰二甲双胍合钕配合物, 表征了其化学组成和结构. 通过糖尿病小鼠模型观察了它们的降血糖作用, 通过ESR谱测定了其对人工脂质体膜超氧自由基的清除率. 实验表明, 配合物的降血糖作用和对超氧自由基的清除率均高于盐酸二甲双胍(HDMBG•HCl), 提示药物的降血糖作用与其抗氧化作用或对细胞脂膜的保护作用有关.     

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.     

取代自由酞菁及二层和三层三明治型配合物的红外光谱

钕配合物;取代自由酞菁及二层和三层三明治型配合物的红外光谱