A long road to a bright future

Dear pss readers, “This year's Nobel Prize in Physics recognizes the pioneering work of Professors Isamu Akasaki, Hiroshi Amano and Shuji Nakamura for the breakthrough developments in GaN materials and devices that enabled the field of solid state lighting. Blue LEDs have revolutionized display technology and enabled high efficiency white light sources.” said our Editorial Advisory Board member Jim Speck in response to our enthusiastic congratulations to his colleague at University of California, Santa Barbara. It was certainly an exceptional moment for a journal that has extensively documented GaN‐related research for decades. Isamu Akasaki and Hiroshi Amano, then both Meijo University and Nagoya University, published in pss on dislocations and stress in AlGaN/GaN thin films, e.g. [1, 2], Hiroshi Amano repeatedly acted as a guest editor [3–5], and all three laureates together have more than a 150 articles in pss and continue to publish on the topic. Obviously, though these contributions have gathered more than 1400 citations to date, not all are “breakthroughs”. Most are documenting continuous achievements in an important and highly specialized area. But together they witness the exceptional persistence required to master the growth of GaN to the degree of perfection that enabled blue LEDs. It is an example for the amount of patient, high‐level work that is necessary to turn a brilliant idea into a widespread invention, and pss is proud to accompany such progress along the way. Regarding today's promising trends in materials physics, we would like to showcase some of the special issues and topical sections that appeared in pss sister journals in 2014: “Oxide materials might form the basis for the next technological revolutions” according to J. M. Knaup, T. Frauenheim, P. Broqvist, and S. Ramanathan, the guest editors of the pss (RRL) Focus issue “Functional Oxides” [6]. These materials' enhanced complexity proposes both a greater challenge and greater benefits for future electronics and energy applications, and the 3 Reviews and 20 Letters offer computational and experimental perspectives on the current understanding. A topical section “Nanoscaled Magnetism and Applications”, guest‐edited by A. Zhukov, features contributions on magnetocaloric materials, spin relaxation, magnetization processes and magnetic nanostructures in pss (a) [7]. Another bustling topic in pss (a) are the recurring annual diamond and nanocarbon special issues, this time focused on “Advances on Diamond Surfaces and Devices” edited by B. Rezek, M. Nesládek, and K. Haenen [8], and kicked‐off by a Feature Article “Photoelectron emission from lithiated diamond” by K. M. O'Donnell, L. Ley, and others [9].

The logo of our journal assembled with blue GaN‐on‐Si LEDs (courtesy of Armin Dadgar, Otto‐von Guericke‐Universität, Magdeburg, Germany)     

Uplifting the Iwasawa

The Iwasawa manifold is uplifted to seven‐folds of either G₂ holonomy or SU(3) structure, explicit new metrics for the same having been constructed in this work. We uplift the Iwasawa manifold to a G₂ manifold through “size” deformation (of the Iwasawa metric), via Hitchin's Flow equations, showing also the impossibility of the uplift for “shape” and “size” deformations (of the Iwasawa metric). Using results of Dall'Agata and Prezas, Phys. Rev. D 69 , 066004 (2004) [arXiv:hep‐th/0311146] [1], we also uplift the Iwasawa manifold to a 7‐fold with SU(3) structure through “size” and “shape” deformations via generalisation of Hitchin's Flow equations. For seven‐folds with SU(3)‐structure, the result could be interpreted as M5‐branes wrapping two‐cycles embedded in the seven‐fold (as in [1]) ‐ a warped product of either a special hermitian six‐fold or a balanced six‐fold with the unit interval. There can be no uplift to seven‐folds of SU(3) structure involving non‐trivial “size” and “shape” deformations (of the Iwasawa metric) retaining the “standard complex structure” ‐ the uplift generically makes one move in the space of almost complex structures such that one is neither at the standard complex structure point nor at the “edge”. Using the results of Konopelchenko and Landolfi, J. Geom. Phys. 29 , 319 (1999) [arXiv:math.DG/9804144] [2], we show that given two “shape deformation” functions, and the dilaton, one can construct a Riemann surface obtained via Weierstraß representation for the conformal immersion of a surface in R ^l, for a suitable l, with the condition of having conformal immersion being a quadric in CP ^l‐1.     

Welcome to the future of solid state physics publishing

Dear readers, authors and referees of physica status solidi, With the present issue and the start of the New Year following our 50th anniversary the editorial structure of pss undergoes some important formal changes. As already announced in the previous Editorial [1] twelve months ago, our former Editor‐in‐Chief Martin Stutzmann, Technische Universität München, has retired from the Editorial Board. This happens after 16 very successful years during which the journal has been brought back to prosperity. It is with deep gratitude to Martin for his strong vision, engagement, support and cooperation over one and a half decade that we meet this moment of changing duties. The fundamental transformation that the progress of electronic publishing brought to the business and the growth of pss to its current amount of output over the last years have resulted in an immense increase of workload for the editors, requiring practically full‐time dedication. Therefore, the role of an academic Editor‐in‐Chief will not be continued, transferring the central responsibility for pss to the hands of the Editors at the Wiley‐VCH office in Berlin and colleagues worldwide. We believe that this is a necessary modification to adapt to the changing publishing environment and habits, putting pss in a position to dynamically respond to ongoing developments. In fact, we currently observe the same policy change for other large journals in our publishing house, e.g. in polymer physics or quantum chemistry, not to mention successful Wiley‐VCH titles such as Advanced Materials or Angewandte Chemie which have been led by ‘in‐house’ Editorials for many years. Despite or even because of these present changes, close contacts of our editorial team to the scientific community will be ever more important for pss. This is why we strive to maintain and further develop a strong and active Board of the journal. Moreover, regardless of the differences in scope between pss (a) and (b), the trend of overlapping basic and applied research aspects in solid state physics has further manifested. Besides, our two other journals pss (RRL) and pss (c) cover the full spectrum of the field by definition. Therefore we have decided to create, from 2012, one joint Editorial Advisory Board for the entire pss family which will embrace many members of the previous separate Boards of the four journals (see ‘Issue Information’ online and inside front cover in the print edition, respectively). We are particularly pleased to welcome, at this moment, five new members to the Advisory Board: David A. Drabold , Ohio University, OH, USA; Sebastian T. B. Gönnenwein , Walther‐Meissner‐Institut and Technische Universität München, Garching, Germany; Nicholas Grandjean , École Polytechnique Fédérale de Lausanne, Switzerland; J. Marty Gregg , Queen’s University Belfast, UK; Ferdinand Scholz , Universität Ulm, Germany; and G. Jeffrey Snyder , California Institute of Technology, Pasadena, CA, USA. We will present them with photographs and short biographies in one of the forthcoming issues, and you should also look out for additional new Board members to join in the near future.

     

Amphiphilic p‐tert‐butylthiacalix[4]arenes containing quaternary ammonium groups: from small molecules toward water‐soluble nanoscale associates

The formation of supramolecular associates based on water‐soluble p‐tert‐butylthiacalix[4]arenes with amino acids has been studied. It was shown that amphiphilic p‐tert‐butylthiacalix[4]arenes preferably formed supramolecular associates with aromatic α‐amino acids (tyrosine and tryptophan). Increasing size of the substituents of p‐tert‐butylthiacalix[4]arenes led to increase molecular weight of supramolecular associates based on the macrocycles and “guest” molecules. The spatial structures of p‐tert‐butylthiacalix[4]arenes and their associates with phenylalanine were studied by two‐dimensional ¹H‐¹H nuclear Overhauser effect NMR spectroscopy. The ability of aggregates based on p‐tert‐butylthiacalix[4]arenes and amino acids to effectively interact with bovine serum albumin with the formation of 7‐ to 8‐nm nanoparticles was shown. Copyright © 2015 John Wiley & Sons, Ltd.     

Comparison of InGaN/GaN light emitting diodes grown on m ‐plane and a ‐plane bulk GaN substrates

InGaN/GaN‐based light emitting diodes (LEDs) grown on m ‐plane, a ‐plane and off‐axis between m ‐ and a ‐plane GaN bulk substrates were investigated. A smooth surface was obtained when a ‐plane substrate was applied; however, large amounts of defects were observed. Photoluminescence measurements of the LEDs with a well thickness of 2.5 nm revealed that all the LEDs showed the peak emission wavelength at 389 nm. The PL intensity of the a ‐plane LED is one order of magnitude lower than that of the m ‐plane LED. The a ‐plane LEDs showed significant lower electroluminescence output powers than m ‐plane LEDs, suggesting that excitons are trapped by the defects, which act as non‐radiative recombination centers. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of cation–anion interaction in 1‐(2‐hydroxyethyl)‐3‐methylimidazolium‐based ion pairs by density functional theory calculations and experiments

Gas‐phase structure, hydrogen bonding, and cation–anion interactions of a series of 1‐(2‐hydroxyethyl)‐3‐methylimidazolium ([HOEMIm]⁺)‐based ionic liquids (hereafter called hydroxyl ILs) with different anions (X = [NTf₂]^–, [PF₆]^–, [ClO₄]^–, [BF₄]^–, [DCA]^–, [NO₃]^–, [AC]^– and [Cl]^–), as well as 1‐ethyl‐3‐methylimizolium ([EMIm]⁺)‐based ionic liquids (hereafter called nonhydroxyl ILs), were investigated by density functional theory calculations and experiments. Electrostatic potential surfaces and optimized structures of isolated ions, and ion pairs of all ILs have been obtained through calculations at the Becke, three‐parameter, Lee–Yang–Parr/6‐31 + G(d,p) level and their hydrogen bonding behavior was further studied by the polarity and Kamlet–Taft Parameters, and ¹H‐NMR analysis. In [EMIm]⁺‐based nonhydroxyl ILs, hydrogen bonding preferred to be formed between anions and C2–H on the imidazolium ring, while in [HOEMIm]⁺‐based hydroxyl ILs, it was replaced by a much stronger one that preferably formed between anions and OH. The O–H···X hydrogen bonding is much more anion‐dependent than the C2–H···X, and it is weakened when the anion is changed from [AC]^– to [NTf₂]^–. The different interaction between [HOEMIm]⁺ and variable anion involving O–H···X hydrogen bonding resulted in significant effect on their bulk phase properties such as ¹H‐NMR shift, polarity and hydrogen‐bond donor ability (acidity, α). Copyright © 2011 John Wiley & Sons, Ltd.     

On Island Formation in a Locally Perturbed Tokamak Equilibrium

To control the plasma transport at the edge of a tokamak the outer flux surfaces can be artificially destroyed by applying a resonant helical magnetic field, as it is demonstrated at Pulsator [1],[2], [3], Tore Supra [4],[5] and proposed for TEXTOR-94 [6] in the concept of “ergodic divertors”. As a measure of the efficiency of the perturbation field e.g. the level of the field line diffusion coefficient DFL the width Δ_i of the magnetic islands and the related Chirikov parameter are of importance [7],[8],[9],[10]. For the planned Dynamic Ergodic Divertor (DED) at TEXTOR-94 where the perturbation coils are located at the high field side the standard expression for Δ_i using the Fourier components of the magnetic field perturbation [7] leads to results significantly different from field line tracing calculations [11]. The standard expression is commonly used in terms of the perturbation magnetic field δB [5],[7],[8],[9],[12],[13]. But when replacing the Fourier components of the perturbation vector potential by those of the magnetic field finite aspect ratio effects have been neglected so far. For present tokamaks with ? = r/R ? 0.3 this can lead to an error in the field line diffusion of one to two orders of magnitude. In this paper it is shown that taking into account the finite aspect ratio at this point leads to correct results compared to the highly precise field line tracing calculations by the Gourdon code. The island width then is recognized to depend significantly on the poloidal position of the perturbation field. This is in contrast to the standard expression. Also the role of the choice of the magnetic coordinate system is considered.     

Remote substituent effects on homolytic Fe‐N bond energies of p‐G‐C6H4NHFe(CO)2(η5‐C5H5) and p‐G‐C6H4(COMe)NFe(CO)2(η5‐C5H5) studied using Hartree–Fock and density functional theory methods

The nature and strength of metal–ligand bonds in organotransition–metal complexes is crucial to the understanding of organometallic reactions and catalysis. The Fe‐N homolytic bond dissociation energies [ΔH_homo(Fe‐N)′s] of two series of para‐substituted Fp anilines p‐G‐C₆H₄NHFp [1] and p‐G‐C₆H₄N(COMe)Fp [2] were studied using the Hartree–Fock (HF) and the density functional theory methods with large basis sets. In this study, Fp is (η⁵‐C₅H₅)Fe(CO)₂ and G are NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO and NMe₂. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and accurate predictions of ΔH_homo(Fe‐N)′s. B3LYP can also satisfactorily predict the α and remote substituent effects on ΔH_homo(Fe‐N)′s [ΔΔH_homo(Fe‐N)′s]. The good correlations [r = 0.96 (g, 1), 0.99(g, 2)] of ΔΔH_homo(Fe‐N)′s in series 1 and 2 with the substituent σ_p⁺ constants imply that the para‐substituent effects on ΔH_homo(Fe‐N)′s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. ΔΔH_homo(Fe‐N)′s(1,2) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes. Copyright © 2012 John Wiley & Sons, Ltd.     

On (orientifold of) type IIA on a compact Calabi‐Yau

We study the gauged sigma model and its mirror Landau‐Ginsburg model corresponding to type IIA on the Fermat degree‐24 hypersurface in WCP ⁴[1,1,2,8,12] (whose blow‐up gives the smooth CY₃(3,243)) away from the orbifold singularities, and its orientifold by a freely‐acting antiholomorphic involution. We derive the Picard‐Fuchs equation obeyed by the period integral as defined in [1, 2], of the parent 𝒩 = 2 type IIA theory of [3]. We obtain the Meijer's basis of solutions to the equation in the large and small complex structure limits (on the mirror Landau‐Ginsburg side) of the abovementioned Calabi‐Yau, and make some remarks about the monodromy properties associated based on [4], at the same and another MATHEMATICAlly interesting point. Based on a recently shown 𝒩 = 1 four‐dimensional triality [6] between Heterotic on the self‐mirror Calabi‐Yau CY₃(11,11), M theory on and F‐theory on an elliptically fibered CY₄ with the base given by CP ¹ × Enriques surface, we first give a heuristic argument that there can be no superpotential generated in the orientifold of of CY₃(3,243), and then explicitly verify the same using mirror symmetry formulation of [2] for the abovementioned hypersurface away from its orbifold singularities. We then discuss briefly the sigma model and the mirror Landau‐Ginsburg model corresponding to the resolved Calabi‐Yau as well.     

Thermal reaction of electron deficient 4‐oxo‐4H‐pyrazole 1,2‐dioxide with cycloheptatriene: the first examples of the formation of an endo‐[4π + 6π]‐cycloadduct and an intramolecular 1,3‐dipolar reaction leading to a heterocage

The reaction of 3,5‐bis(methoxycarbonyl)‐4‐oxo‐4H‐pyrazole 1,2‐dioxide (1a) with 1,3,5‐cycloheptatriene (2b) gave a mixture of the novel endo‐[4 + 6]‐cycloadduct (4ab), anti‐exo‐[4 + 2]‐cycloadduct (5ab), and the heterocage (6ab) derived from the intramolecular 1,3‐dipolar cycloaddition reaction of the syn‐endo‐[4 + 2]‐cycloadduct. Analogous endo‐[4 + 6] selectivity in 1,3‐dipolar cycloadditions has not been reported previously. The X‐ray analysis indicates that 6ab has a very long N_sp3–N_sp3 bond distance of 1.617(4) Å. The cycloaddition behaviour is discussed on the basis of transition‐state structures optimized at the B3LYP/6‐31G(d) level of theory, from which predictions of the peri‐, regio‐, and stereoselectivities agreed well with the experimental results. Copyright © 2012 John Wiley & Sons, Ltd.     

Preface – Focus on Sustainable Electronics

Today's society uses up to 35 tons of material per capita and year for basic needs, luxury or consumer goods, hightech products, etc. Much of it is used in form of functional materials employed in highly specialized devices such as mobile phones. Cumulated sales up to 2008 correspond to 7.2 billions of mobile phones. A new generation of mobile phones comes up every half a year. More than 30 different metals are employed in this device and are essential for its functioning. The fraction of some of these metals in a mobile phone is higher than the typical content in corresponding mineral ores. The life cycle analysis of such a device technology ranging from the acquisition and supply of materials via purification, manufacturing and fabrication, via commercial uses to end‐of‐life disposition and recycling needs to be carried out carefully to ensure a commercial success of the product. Such an analysis comprises a number of quantitative criteria (e.g. reserves and resources of the materials employed, energy consumption of the production process, recyclability), but also qualitative criteria (e.g. social and socio‐cultural aspects, ecological risks, political issues). Thus a life cycle analysis must go beyond a mere techno‐economic analysis to yield resource‐efficient, socio‐economically liable and ecologically benign technologies. The first two articles of this series of six articles on “sustainable electronics” discuss how life cycle analysis needs to be conducted properly. Reller focuses on the case of strategic metals whereas Theis et al. discuss the case of nanostructures. It will become clear to the reader that the principal approach is very similar, but distinct differences occur due to specific properties of different classes of materials. The articles on photovoltaics and thermoelectrics focus on a scenario where the corresponding device modules become mass products. Simple estimates based on element reserves in case of thermoelectric devices easily reveal that materials scarcity will impose major restrictions on the deployment of the established key materials (e.g. PbTe, Bi₂Te₃ as well as Si_xGe_1–x) in mass‐produced modules. Thus, depending on the type of application, a compromise between best efficiency and materials availability needs to be made. The situation in photovoltaics is somewhat different. The analysis makes it clear that all types of mass‐produced solar modules, in particular novel thin‐film technologies, need to compete with the Si‐technology in the end. Nevertheless, there are promising alternatives for absorption materials on the horizon. The last two articles by Fortunato and Martins and by Martins et al. discuss the advances and advantages of oxide semiconductors as abundantly available materials in the context of transparent electronics and electronics on paper, respectively. Conventional Si‐based CMOS electronics cannot compete with oxide electronics in these two areas of application. The example of oxide semiconductors shows the potential of developing sustainable and ecologically benign technologies for specific applications which are compatible with or even better than conventional technologies. The idea for this series of articles was developed during the discussions at the WE‐Heraeus Summerschool “Sustainable Electronics” organized by us at the Physik‐Zentrum in Bad Honnef in August 2010. The issue of sustainable resources management is of major importance for maintaining the wealth of human society. Therefore, it should concern all of us working in materials science in academia or industry. Only few people are specialists in this novel and very interdisciplinary field of research. The six articles cover different facets of the problem. Hopefully, together they will give valuable insight into modern materials resource management and shed some light on its complexity. We would like to thank Stefan Hildebrandt for his help and support in assembling this series of articles as expert opinions. We chose the pss‐format “Expert Opinion” as best suited for our purposes as it allows us to express somewhat personal views on this novel research field of “Sustainable Electronics”, to reach a broader audience and, thus, to hopefully generate useful and intense discussions on the subject (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical characterization of atmospheric‐pressure plasma needle

The atmospheric‐pressure plasma needle is a promising source that can be used efficiently for different industrial applications. A radio frequency (RF) (13.56 MHz) generator was used to generate a He–O₂/Ar mixture plasma. The ground‐state oxygen atomic density [O] was calculated as a function of discharge parameters by “actinometry”. The Ar‐I (2p₁ → 1s₂) line at 750 nm and the O‐I (³P → ³S) line at 844 nm were used to estimate the [O] atomic density. The rotational temperature T _R of He–O₂/Ar mixture was measured from the rotational levels of the “first negative system” (FNS) by using the “Boltzmann plot”. The effect of discharge parameters on the atomic oxygen density [O] and the gas temperature was monitored. These results show that [O] density increases with RF power and O₂ concentration, but decreases with the gas flow rate. Whereas the gas temperature increases with increase in the input RF power, it decreases with increase in the gas flow rate and O₂ concentration in the mixture. Since the [O] atomic density contributes to plasma‐based biomedical applications, the proposed optimum conditions for plasma‐based decontamination of heat‐sensitive materials in the present study are 0.6% oxygen, 500 sccm flow rate, and 26 W RF power.     

Role of gemini surfactants (m‐s‐m type; m = 16, s = 4–6) on the reaction of [Zn(II)‐Gly‐Phe]+ with ninhydrin

In the present paper, reaction of zinc‐glycylphenylalanine ([Zn(II)‐Gly‐Phe]⁺) with ninhydrin has been investigated in gemini (m‐s‐m type; m = 16, s = 4–6) surfactants at temperature (70 °C) and pH (5.0). Monitoring the appearance of product at 400 nm was used to follow the kinetics, spectrophotometrically. The order of the reaction with respect to [Zn(II)‐Gly‐Phe]⁺ was unity while with respect to [ninhydrin] was fractional. The reaction constants involved in the mechanism were obtained. In addition to the rate constant (k_Ψ) increase and leveling‐off regions are observed with the geminis, just like as seen with conventional surfactant hexadecyltrimethylammonium bromide (CTAB), the former produced a third region of increasing k_Ψ at higher concentrations. A close agreement between observed and calculated rate constants was found under varying experimental conditions. A suitable mechanism consistent with the experimental findings has been proposed. Copyright © 2014 John Wiley & Sons, Ltd.     

Completing the web of ℤ3‐quotients of complete intersection Calabi‐Yau manifolds

We complete the study [1] of smooth ℤ₃‐quotients of complete intersection Calabi‐Yau threefolds by discussing the six new manifolds that admit free ℤ₃ actions that were discovered in [2]. These manifolds were missed in [1] and complete the web of smooth ℤ₃‐quotients in a nice way. We discuss the transitions between these manifolds and include also the other manifolds of the web. This leads to the conclusion that the web of ℤ₃‐free quotients of complete intersection Calabi‐Yau threefolds is connected by conifold transitions.     

Structure and properties of α‐cyclo[N]thiophenes as potential electronic materials – a theoretical study

Density functional theory (DFT) calculations of ring‐shaped α‐cyclo[N]thiophenes with N = 2 to N = 18 have been performed for ideal structures of high symmetry (point groups C_nv and D_nh) and for optimum energy structures of lower symmetry (D_2d, C_s, C_2v, C_i or C₁). Whereas the first three members of the series behave exceptionally the higher members are typical cyclothiophenes consisting of weakly interacting thiophene rings. In contrast to neutral compounds, cations and dications of cyclothiophenes with N ≥5 exhibit pronounced electron delocalizations along the carbon backbone. However, if the functional B3LYP is replaced by BH cations of large ring‐size cations show polaron‐type charge defects. According to broken symmetry DFT calculations dications with N = 14 and N = 18 have biradical character. These structures correspond to two‐polaron‐type structures rather than to dipolarons. The calculated vertical ionization energies of cyclo[N]thiophene are comparable with those of oligo[N]thiophenes of the same number of thiophene rings but the calculated absolute energies are probably too low at large ring size. Cyclothiophenes absorb light of lower energies than the related oligothiophenes. Cyclothiophenes belong to the strongly absorbing organic chromophores. In case of high molecular symmetry some of the excited states of cyclothiophenes are degenerate. The degeneracy is lifted with lower symmetries but the general absorption feature remains. The theoretical results are discussed with respect to recent experimental findings. Copyright © 2007 John Wiley & Sons, Ltd.     

Plastic relaxation of mixed dislocation in axial nanowire heterostructures using Peach–Koehler approach

In this Letter, the plastic relaxation introduced by typical 60° mixed dislocation in zinc‐blende axial nanowire (NW) heterostructures is evaluated by numerical Peach–Koehler approach which reflects the interaction between coherent strain field and misfit dislocation. Cylindrical NW epilayers grown on NW and bulk substrate are separately modeled. We reveal that straight 60° dislocation with Burgers vector (a /2) 〈101〉 would always generate at NW center orienting [111], while aspect ratio dependent off‐center equilibrium position should be expected for NW epilayer along [001]. Moreover, the critical diameters, below which coherency is maintained, are predicted based on energy balance criterion for axial NW heterostructures along predominating growth direction [111]. The results are compared with existing theory and experimental observations. Our work provides a necessary quantitative complement to the understanding of plastic relaxation and coherency limit in axial NW heteroepitaxy. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Homo‐Diels–Alder reaction of a very inactive diene,bicyclo[2,2,1]hepta‐2,5‐diene,with the most active dienophile, 4‐phenyl‐1,2,4‐triazolin‐3,5‐dione. Solvent,temperature, and high pressure influence on the reaction rate

Solvent, temperature, and high pressure influence on the rate constant of homo‐Diels–Alder cycloaddition reactions of the very active hetero‐dienophile, 4‐phenyl‐1,2,4‐triazolin‐3,5‐dione (1), with the very inactive unconjugated diene, bicyclo[2,2,1]hepta‐2,5‐diene (2), and of 1 with some substituted anthracenes have been studied. The rate constants change amounts to about seven orders of magnitude: from 3.95^.10^?3 for reaction (1+2) to 12200 L mol^?1 s^?1 for reaction of 1 with 9,10‐dimethylanthracene (4e) in toluene solution at 298 K. A comparison of the reactivity (ln k₂) and the heat of reactions (?_r‐nH) of maleic anhydride, tetracyanoethylene and of 1 with several dienes has been performed. The heat of reaction (1+2) is ?218 ± 2 kJ mol^?1, of 1 with 9,10‐dimethylanthracene ?117.8 ± 0.7 kJ mol^?1, and of 1 with 9,10‐dimethoxyanthracene ?91.6 ±0.2 kJ mol^?1. From these data, it follows that the exothermicity of reaction (1+2) is higher than that with 1,3‐butadiene. However, the heat of reaction of 9,10‐dimethylanthracene with 1 (?117.8 kJ mol^?1) is nearly the same as that found for the reaction with the structural C=C counterpart, N‐phenylmaleimide (?117.0 kJ mol^?1). Since the energy of the N=N bond is considerably lower (418 kJ/bond) than that of the C=C bond (611 kJ/bond), it was proposed that this difference in the bond energy can generate a lower barrier of activation in the Diels–Alder cycloaddition reaction with 1. Linear correlation (R = 0.94) of the solvent effect on the rate constants of reaction (1+2) and on the heat of solution of 1 has been observed. The ratio of the volume of activation (?V^≠) and the volume of reaction (?V_r‐n) of the homo‐Diels–Alder reaction (1+2) is considered as “normal”: ?V^≠/?V_r‐n = ?25.1/?30.95 = 0.81. Copyright © 2012 John Wiley & Sons, Ltd.     

Stereoselectivity and kinetics of [4 + 2] cycloaddition reaction of cyclopentadiene to para‐substituted E‐2‐arylnitroethenes

In spite of diversified electrophilicity of E‐2‐arylnitroethenes, their [4 + 2] cycloaddition reactions with cyclopentadiene leads to the corresponding 6‐endo‐aryl‐5‐exo‐nitronorbornenes and 6‐exo‐aryl‐5‐endo‐nitronorbornenes as the only reaction products. Stereoselectivity, substituent and solvent effects, and activation parameters, suggest that these reactions occur via a synchronous concerted mechanism on both competing pathways. The experimental results obtained are consistent with the data from B3LYP/6‐31G(d) calculations. Due to high electrophilicity of E‐2‐arylnitroethenes, the reactions studied should be considered as polar [4 + 2] cycloadditions. Copyright © 2011 John Wiley & Sons, Ltd.