High-spin iron(III) complexes: structural,spectroscopic, and photochemical studies

Reaction of FeCl₃ with one equivalent of acac (acac = pentane-2,4-dionate) and KTp^Me2 (Tp^Me2 = hydrotris(3,5-dimethyl-pyrazol-1-yl)borate) yielded Tp^Me2Fe(acac)Cl (3), which upon reaction with methanolic solution of sodium azide resulted in the formation of a six coordinate compound Tp^Me2Fe(acac)N₃ (4) with a single azide. When the reaction of FeCl₃ and KTp^Me2 was performed with two equivalents of sodium azide and one equivalent of 3,5-dimethylpyrazole (Pz^Me2H), a six coordinate cis azide compound [Tp^Me2Fe(Pz^Me2H)(N₃)₂] (5) was obtained. These compounds were characterized by spectroscopic methods and single crystal X-ray crystallography. Electrochemical studies of 5 show that it can be irreversibly reduced at relatively lower potential than 4. The photolysis of 5 was performed at 77 K at different wavelengths (480, 419, and 330 nm) showing that 5 was photoreduced to a high-spin Fe(II) species instead of photooxidized to Fe(V).     

Synthesis,structure and properties of aquabis(2,4′-bipyridine)di(propionato-O)copper(II)

The title complex has been synthesized and characterized by elemental and thermal analysis, IR and electronic spectroscopy, conductivity studies and X-ray crystallography. In the crystal, the complex has two-fold symmetry and the copper atom adopts square pyramidal coordination. Bond valences for Cu were computed. Cu–O_(propionate) bonds are slightly stronger than the Cu–N bonds, and the Cu–O_(water) bond is distinctly weaker. Molecules are linked by O–H···O hydrogen bonds to form infinite hydrogen-bonded chains along the y axis.     

Triphenyltin chloride complexes containing bidentate organodiimines as effective antitumor agents

Three triphenyltin chloride complexes, [(Ph₃SnCl)₂?·?(bpy)_1.5] (1), [(Ph₃SnCl)₂.tbpe] (2), and [(Ph₃SnCl)₂?·?bpe] (3), were synthesized by reaction of triphenyltin chloride with 4,4′-bipyridine (bpy), trans-1,2-bis(4-pyridyl)ethylene (tbpe), and 1,2-bis(4-pyridyl)ethane (bpe) in water/acetonitrile. Both 2 and 3 are binuclear; each consists of two Ph₃SnCl molecules bridged by the bidentate ligand. Complex 1 consists of two crystallographically independent and chemically different coordination complexes, mononuclear and binuclear in equal proportion. The structures of these complexes were investigated by single-crystal X-ray analysis, elemental analyses, NMR spectroscopy as well as electronic absorption and emission spectroscopy. The three complexes exhibit in vitro antitumor activity against human breast cancer cell line, MCF7.     

A moving mesh algorithm for aero‐thermo‐mechanical modelling in turbomachinery

This paper describes the development of a mesh deformation method used for aero‐thermo‐mechanical coupling of turbo‐engine components. The method is based on the nonlinear solution of an elastic medium analogy, solved using finite element discretisation and modified to let the boundary nodes be free to slide over the deflected surfaces. This sliding technique relies on a B‐spline reconstruction of the moving boundary and increases the robustness of the method in situations where the boundary deflection field presents significant gradients or large relative motion between two distinct boundaries. The performance of the method is illustrated with the application to an interstage cavity of a turbine assembly, subjected to the deformations computed by a coupled thermo‐mechanical analysis of the engine component. Copyright © 2011 John Wiley & Sons, Ltd.     

Br2分子里德堡态的高分辨转动谱研究

用窄线宽（０．０８ｃｍ＾－＾１）脉冲可调谐紫外激光和（２＋１）多光子电离方法测量了Ｂｒ２的里德堡（Ｒｙｄｂｅｒｇ）态光谱,在７００００－７１５００ｃｍ＾－＾１范围内,获得了溴分子［П３／２］４ｄ振动系列,测量（ｖ＇,ｖ”）＝（１,０）,（２,０）的高分辨振转谱,得到其转动常数Ｂ’７９－８１分别为０．０８８３２和０．０８８０５ｃｍ＾－＾１,并提出此系列的角动量量子数Ω应为１。     

A passive solar heater-refrigerator

Summary In this paper we study the nonequilibrium thermodynamic steady-state behaviour of a model system representing a core surrounded by an envelope in which the envelope interacts with the solar radiation and with an external bath having a given temperature profile. The heat flow between core and envelope can be controlled by varying the thermal conductivity of their interface. We show that this system acts as a passive heat pump raising the core average temperature with respect to the average equilibrium value corresponding to a fixed value of the interface conductivity, at the same time flattening its oscillation in time. By changing the time dependence of the conductivity the systemvice versa acts as a refrigerator. We show how the limits of this performance depend on the passive parameters such as surfaces, conductivities, heat capacities. The periodicity considered in this study is the daily cycle.

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Riassunto In questo lavoro si studia lo stato stazionario di non equilibrio termodinamico per un sistema che rappresenta modellisticamente un corpo circondato da un involucro; questo interagisce con la radiazione solare e con un bagno termico esterno caratterizzato da una temperatura che dipende dal tempo in modo prefissato. Il flusso di calore fra l'interno e l'involucro è controllato variando la conducibilità termica dell'interfaccia. Noi mostriamo che questo sistema funziona come una pompa di calore passiva, cioè innalza la temperatura media dell'interno rispetto a quella che si avrebbe nel caso di conducibilità fissa e, allo stesso tempo, riduce le oscillazioni di codesta temperatura. Semplicemente cambiando la dipendenza oraria del controllo, il sistema funziona come un frigorifero. Si mostra in che modo tale effetto dipenda dai parametri passivi che sono le superfici, i calori specifici, la conducibilità. Consideriamo in questo studio il ciclo giornaliero.

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Резюме В этой работе мы исследуем неравновесное термодинамическое стационарное поведение модельной системы, представляющей ядро, окруженное оболочкой, которая взаимодействует с солнечным излучением и с внешним термостатом, имейщим заданный профиль температур. Поток тепла между ядром и оболочкой можно контролировать посредством изменения теплопровдности их границы раздела. Мы покзываем, что эта система действует, как пассивный тепловой насос, поднимающий среднюю температуру ядра относительно средней равновесной величины, соответствующей фиксировчнной величине теплопроводности границе раздела, и в то же время сглаживающий осцилляции температуры во времени. Изменяя временную зависимость теплопроводности, описанная система может действовать как холодильник. Мы показываем, как указанный эффект зависит от таких пассивных параметров, как поверхности, проводимости, теплоемкости. Периодичность рассмотренной системы представляет суточный цикл.

     

Maximum irreversible availability for continuous systems

Summary In this paper we generalize the study of the irreversible availability, already widely developed for discrete systems, to field theory. We derive the general equations and solve analytically the stationary unidimensional case.

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Riassunto In questo articolo si generalizza lo studio del lavoro estraibile di Gibbs, che è già ampiamente sviluppato nel caso dei sistemi discreti, al formalismo della teoria continua di campo. Si formulano le equazioni differenziali in generale e si risolve analiticamente il caso del problema unidimensionale stazionario.

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Резюме В зтой работе мы обобщаем исследование необратимой доступности, развитое для дискретных систем, для формализма непрерывной теории поля. Мы выводим общие уравнения и решаем аналитически проблему в стационарном одномерном случае.

     

Crystal structure of N-m-tolyl phthalimide

N-m-tolyl phthalimide, C₁₅NO₂H₁₁ crystallizes in the space group Cc with unit cell dimensions,a=8·54(1),b=19·89(2),c = 7·59(1)A, β=114·53(1)° andZ=4.V=1173(2)A³,D _m =1·35(1),D _c = 1·344 mg.m⁻³,M _r =237 λCoK_a=1·7903A. The structure was solved byMULTAN and refined to an R-factor of 0·116 for 632 counter reflections. The molecules are held together by van der Waal’s forces. The angle between the tolyl plane and the plane through the phthalimide group is 53·4(4)°. Contribution No. 607.     

ComBn(m+n≤6)团簇的结构，电子特性和磁性研究

基于密度泛函理论和卡里普索结构预测方法,系统研究了ComBn(m+n≤6)团簇的结构,电子特性和磁性。首先,通过卡里普索结构预测方法获得了体系的基态和亚稳态结构。基于基态结构,利用HOMO-LUMO能隙,垂直电离势,垂直电子亲和势和化学硬度分析了掺杂体系的稳定性。最后,研究了基态结构对应的自然布局分布,自然电子组态等电子特性和磁性。