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71.
72.
Summary. Parameters of the formalism [1–6] describing spin crossover in the solid state have been defined via molecular potentials in model systems of neutral and ionic complexes. In the first instance Lennard-Jones and electric dipole–dipole potentials have been used whereas in ionic systems Lennard-Jones and electric point-charge potentials have been used. Electric dipole–dipole interaction of neutral complexes brings about
a positive excess energy controlled by the difference of electric dipole moments of HS and LS molecules. Differences of the
order of Δμ = 1–2 D cause an abrupt spin crossover in systems with T1/2 = 100–150 K. Magnetic coupling contributes both to the excess energy and excess entropy, however the overall effect is equivalent
to a modest positive excess energy. Ionic systems in the absence of specific interactions are characterised by very small
excess energies corresponding to practically linear van’t Hoff plots. Detectable positive and negative excess energies in these systems may arise from interactions of ligands belonging
to neighbouring complexes. The HOMO–LUMO overlap in HS–LS pairs can bring about a nontrivial variation of the shape of transition
curves. Examples of regression analysis of experimental transition curves in terms of molecular potentials are given. 相似文献
73.
沉淀法合成纳米晶长余辉材料Y2O2S∶Eu3+,Ti 总被引:2,自引:0,他引:2
The long-lasting phosphorescent materials, yttrium oxysulfides doped by Eu and Ti, were systhesized by coprecipitation with their subsequent thermal decomposition in the presence of sulphur. The products were characterized by XRD, TEM, phosphorescent spectra, and thermoluminescence. The XRD results indicate that the lowest synthesis temperature is 700 ℃. From the TEM, the average diameter of particles was in the range of 60~120 nm, and augmented with the increase of temperature. The materials under UV excitation presented well afterglow from the transition of 5D0,1 → 7FJ of Eu3+, and the persistent time was about 2 h. The long-lasting afterglow mechanism was discussed, too. 相似文献
74.
Self‐Assembly of a Giant Tetrahedral 3 d–4 f Single‐Molecule Magnet within a Polyoxometalate System 下载免费PDF全文
Dr. Masooma Ibrahim Dr. Valeriu Mereacre Dr. Nicolas Leblanc Prof. Wolfgang Wernsdorfer Dr. Christopher E. Anson Prof. Annie K. Powell 《Angewandte Chemie (International ed. in English)》2015,54(51):15574-15578
A giant tetrahedral heterometallic polyoxometalate (POM) [Dy30Co8Ge12W108O408(OH)42(OH2)30]56?, which shows single‐molecule magnet (SMM) behavior, is described. This hybrid contains the largest number of 4f ions of any polyoxometalate (POM) reported to date and is the first to incorporate two different 3d–4f and 4f coordination cluster assemblies within same POM framework. 相似文献
75.
Methane as a Selectivity Booster in the Arc‐Discharge Synthesis of Endohedral Fullerenes: Selective Synthesis of the Single‐Molecule Magnet Dy2TiC@C80 and Its Congener Dy2TiC2@C80 下载免费PDF全文
Katrin Junghans Christin Schlesier Aram Kostanyan Nataliya A. Samoylova Qingming Deng Marco Rosenkranz Sandra Schiemenz Dr. Rasmus Westerström Prof. Dr. Thomas Greber Prof. Dr. Bernd Büchner Dr. Alexey A. Popov 《Angewandte Chemie (International ed. in English)》2015,54(45):13411-13415
The use of methane as a reactive gas dramatically increases the selectivity of the arc‐discharge synthesis of M‐Ti‐carbide clusterfullerenes (M=Y, Nd, Gd, Dy, Er, Lu). Optimization of the process parameters allows the synthesis of Dy2TiC@C80‐I and its facile isolation in a single chromatographic step. A new type of cluster with an endohedral acetylide unit, M2TiC2@C80, is discovered along with the second isomer of M2TiC@C80. Dy2TiC@C80‐(I,II) and Dy2TiC2@C80‐I are shown to be single‐molecule magnets (SMM), but the presence of the second carbon atom in the cluster Dy2TiC2@C80 leads to substantially poorer SMM properties. 相似文献
76.
Lanthanide Complexes with Multidentate Oxime Ligands as Single‐Molecule Magnets and Atmospheric Carbon Dioxide Fixation Systems 下载免费PDF全文
Dr. Małgorzata Hołyńska Dr. Rodolphe Clérac Mathieu Rouzières 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(38):13321-13329
The synthesis, structure, and magnetic properties of five lanthanide complexes with multidentate oxime ligands are described. Complexes 1 and 2 ( 1 : [La2(pop)2(acac)4(CH3OH)], 2 : [Dy2(pop)(acac)5]) are synthesized from the 2‐hydroxyimino‐N‐[1‐(2‐pyridyl)ethylidene]propanohydrazone (Hpop) ligand, while 3 , 4 , and 5 ( 3 : [Dy2(naphthsaoH)2(acac)4H(OH)]?0.85 CH3CN?1.58 H2O; 4 : [Tb2(naphthsaoH)2(acac)4H(OH)]?0.52 CH3CN?1.71 H2O; 5 : [La6(CO3)2(naphthsao)5 (naphthsaoH)0.5(acac)8(CO3)0.5(CH3OH)2.76H5.5(H2O)1.24]?2.39 CH3CN?0.12 H2O) contain 1‐(1‐hydroxynaphthalen‐2‐yl)‐ethanone oxime (naphthsaoH2). In 1 – 4 , dinuclear [Ln2] complexes crystallize, whereas hexanuclear LaIII complex 5 is formed after fixation of atmospheric carbon dioxide. DyIII‐based complexes 2 and 3 display single‐molecule‐magnet properties with energy barriers of 27 and 98 K, respectively. The presence of a broad and unsymmetrical relaxation mode observed in the ac susceptibility data for 3 suggest two different dynamics of the magnetization which might be a consequence of independent relaxation processes of the two different Dy3+ ions. 相似文献
77.
A spray‐based technique, originally developed for the production of semiconductor nanocrystals, is utilized for the preparation of high‐quality nanocrystalline thin films, as demonstrated with manganese sulfide. The films are formed by the use of pneumatic‐assisted thermospray or pneumatic nebulizers. Our simple, low‐cost, and low‐temperature process results in a dense and phase‐pure grain structure. The concepts and benefits of this technique are described and discussed. The film characteristics show dependence on the experimental parameters, in particular the rate of solvent vaporization. Three alternative film formation mechanisms are suggested for cases with varied experimental conditions. 相似文献
78.
79.
在三电极体系中,以硝酸锌水溶液作为电解液,采用阴极还原电沉积法成功实现了一维纳米结构ZnO阵列在TiO2纳米粒子/ITO导电玻璃薄膜基底上的沉积,并通过XRD、SEM、EDS和PL光谱等方法对样品进行了表征.重点研究了薄膜基底、电解液浓度、沉积时间、六次亚甲基四胺(HMT)的引入对ZnO沉积及其发光性质的影响.结果显示:与ITO玻璃基底相比,ZnO更易于在TiO2纳米粒子薄膜上实现电化学沉积.ZnO属于六方晶系的铅锌矿结构,并且沿着c-轴方向表现出明显的择优化生长,以形成垂直于基底的ZnO纳米棒阵列.延长沉积时间、增加电解液浓度和引入一定量的HMT等均对ZnO的生长有促进作用,进而使其纳米棒的结晶度和取向程度提高,进而解释了所得的薄膜分别约在375和520nm处表现出ZnO的强而窄的带边紫外光发射峰和弱而宽的表面态绿光发射带. 相似文献
80.
以硝酸铟作为前驱体,在蒸馏水和乙二胺的混合溶剂中制备出了InOOH纳米晶,详细地考察了反应溶剂及温度对终产物的影响。利用X射线粉末衍射(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)、扫描电子显微镜(SEM)和透射电镜(TEM)对样品的晶相结构、光吸收性质及其形貌进行了详细的表征。考察了样品在紫外光下及可见光下对液相中的染料罗丹明B(RhB)的光催化降解性能。发现InOOH在紫外光下可以彻底分解RhB,而在可见光下只能使RhB脱色。InOOH在紫外光和可见光下对RhB的分解遵循两种不同的反应机制。 相似文献