Dans le cadre de cette thèse de doctorat nous nous sommes intéressés à la préparation de composés moléculaires magnétiques chiraux dont le centre métallique, siège de l'anisotropie magnétique, est également centre de chiralité. Notre étude a porté sur le contrôle de la stéréochimie du polyèdre de coordination d'un ion Ln, en particulier dans des complexes base de Schiff 3d-4f. L'approche originale que nous avons explorée consiste à induire la stéréochimie du centre Ln par un ligand-chélate anionique chiral directement lié au métal. L'anion-ligand que nous avons considéré est la forme déprotonée du trifluoroacétyl-3-camphre (abrégée Camph-). Pour des complexes de type base de Schiff 3d-4f, deux anions chiraux viennent s'ancrer sur l'ion Ln et, par transfert de chiralité, permettent de fixer la stéréochimie de la sphère de coordination de la terre-rare. Une stéréochimie Delta ou Lambda est ainsi obtenue en fonction de l'énantiomère de l'anion-chiral mis en œuvre dans la synthèse. Cette approche a permis la synthèse de plusieurs familles de composés énantiopurs (ex. [LMe2Ni(H2O)Ln(camph)2(CF3SO3)]; [LMe2Zn(Cl)Ln(camph)2(MeOH)]). Dans chaque cas une stéréochimie Lambda est associée à l'énantiomère R-(+) de l'anion chiral et une stéréochimie Delta à l'énantiomère S-(-). Cependant une telle stéréo-sélectivité n'est pas systématique, la dissymétrie de l'espace de la sphère de coordination de la terre-rare associée à son troisième anion ou à un ligand ancillaire semble jouer un rôle important.Selon la même approche, nous avons également considéré la préparation de complexes 4f mono-métalliques chiraux de formulation [Ln(Camph)4]-. L'étude des comportements magnétiques a mis en évidence des comportements de type SMM (Single Molecule Magnet) pour plusieurs composés contenant les ions Tb ou Dy. / The research work described in this thesis deals with the design, the synthesis and magnetic property investigation of magnetic low dimensional molecular materials (i.e. single Molecule Magnets, SMM), especially in 3d-4f Schiff-base complexes, involving magnetically anisotropic lanthanide (Ln) metal centers in conjunction with chirality. The aim of this investigation was to provide an efficient access to enantiopure SMMs chiral at metal (Ln). We developed an original chemical approach that consists in introducing a chiral chelating diketonate ligand directly bonded to the Ln metal center. Thus transfer of chirality from chiral ligand to the coordination polyhedron of the metal center can be achieved. Deprotonated 3-trifluoroacetyl-camphor (Camph-) has been utilized as the chiral chelating ligand to synthesize several 3d-4f Schiff-base complexes, where two chiral anions are anchored on Ln ion rendering chiral coordination sphere around the rare-earth metal center. Depending on the enantiomer of the ligand employed in the synthesis, either Delta or LAmbda stereochemistry of the Ln polyhedron is obtained. This approach allowed synthesis of several families of enantiopurs SMMs chiral at Ln such as [LMe2Ni(H2O)Ln(camph)2(CF3SO3)] or [LMe2Zn(Cl)Ln(camph)2(MeOH)], where LMe2 = bicompartmental Schiff-base ligand. In each case, reaction with the R-(+) Camph ligand results in a Lambda stereochemistry, while a Delta stereochemistry is yielded upon reaction with the S-(-) Camph ligand. However, such a stereo-selectivity is not systematic. The third anion or an ancillary ligand associated with the rare-earth metal centers appears to play an important role in controlling the stereochemistry of the coordination sphere around the rare-earth metal centers. Using the same approach, we have also successfully isolated mono-metallic chiral 4f complexes of general formulae [Ln(Camph)4]-. The study of magnetic behaviors revealed Single Molecule Magnet (SMM) behavior for several complexes containing Tb or Dy ions.

Anisotropic magnetic materials have been proposed over the past twenty years or so as candidates for high density storage, so-called Single-Molecule Magnets (SMMs). These may in future be used to store data at the level of an individual molecule. Separately, isotropic materials may be harnessed for their large magnetocaloric effect which enables them to be used as refrigerants. This can potentially replace the increasingly rare and therefore expensive 3He and 4He currently employed either separately or in 3He-4He dilution refrigerators. This thesis examines the use of lanthanide(III) ions for these applications, by detailing the synthesis, characterisation and performance of three new classes of zero-dimensional compounds, {LnIII2}, {LnIII2ZnII4} and {LnIII7}. These are assessed by several techniques including SQUID magnetometry, heat capacity measurements luminescence spectroscopy, Electron Paramagnetic Resonance and ab initio calculations. In doing so we extended the use of a tripodal ligand widely employed in 3d chemistry to 4f ions, and found only the second 3d-4f phosphonate SMM. Investigating several members of a known three-dimensional lanthanide(III) polymer, {LnIII}n, showed the isotropic gadolinium(III) analogue is one of the very best of all known magnetic refrigerants in the low-temperature regime.

A family of new [PtM(SAc)4(pySMe)] (M = Mn (42), Fe (43), Co (44), Ni (45), Zn (46)) lanterns and an expansion of the [PtM(SAc)4(pyNH2)] family to include M = Mn (47) and Fe (48) lanterns have been synthesized and their detailed structural and magnetic characterization are reported. Compounds 43-45 have been found to contain exceptionally long Pt…Pt metallophilic contacts with antiferromagnetic coupling across the staggered dimers in the solid state. The utility of the [PtVO(SOCR)4] lanterns as monodentate, terminal oxo-bound ligands is proven in the formation of trimetallic lanthanide complexes [Ln(ODtbp)3{PtVO(SOCR)4}] (Ln = Ce, R = Me (49); Ln = Ce, R = Ph (50); Ln = Nd, R = Me (51); Ln = Nd, R = Ph (52)). Structural and magnetic studies are reported of the four, four-coordinate lanthanide complexes. All four complexes were found to exhibit antiferromagnetic coupling between the 3d-4f ions, the strongest of which is observed in 50. Through AC magnetic susceptibility studies, xii SMM behavior was also observed in all four complexes, with the slowest relaxation found in 52. A pair of [PtNi(SAc)4(L)] (L = pyCN (54), HpipCN (55)) and new {S,N} chelated mercaptopyridine lanterns [PtNi(mpyS)4(L)] (L = H2O (56), MeCN (57), pyCN (58)) have been synthesized and a detailed structural comparison of the systems made. The stronger field mercaptopyridine ligand is shown to decrease the Pt (donor) – M (acceptor) character within the lantern, reducing the Pt(II) Lewis acidity and therefore preventing the formation of intermolecular interactions in Ni(II) complexes 56-58. Additionally, the development of an improved air- and water-stable synthesis for the formation of the di-Pt mercaptopyridine para-hydro lantern, [Pt2(pyS)4], is reported along with its previously unknown crystal structure. In an attempt to make a diamagnetic [PtZn(mpyS)4(L)] analog to the previous Ni(II) mercaptopyridine lanterns, a new series of {PtnZn2} HEMACs has been discovered and structurally characterized with n = 1, 2, 3,. The discovery of a trimetallic {Pt(IV)Zn2} (60) para-methyl mercaptopyridine bridged complex with novel {Pt(IV)S6} ligation is discussed. The use of para-H substituted mercaptopyridine led to insoluble tetranuclear {Pt2Zn2} (61) while use of the para-methyl substituted ligand led to the insoluble pentanuclear {Pt3Zn2} (62) through solvothermal syntheses.

La plupart des métriques de qualité logicielle mesurables sont actuellement basées sur des mesures bas niveau, telles que la complexité cyclomatique, le nombre de lignes de commentaires ou le nombre de blocs dupliqués. De même, la qualité de l'ingénierie logicielle est davantage liée à des facteurs techniques ou de gestion, et devrait fournir des indicateurs utiles pour les exigences de qualité. Actuellement, l'évaluation de ces exigences de qualité n'est pas automatisée, elle n'est pas validée empiriquement dans des contextes réels et l'évaluation est définie sans tenir compte des principes de la théorie de la mesure. Par conséquent, il est difficile de comprendre où et comment améliorer le logiciel suivant le résultat obtenu. Dans ce domaine, les principaux défis consistent à définir des métriques adéquates et utiles pour les exigences de qualité, les documents de conception de logiciels et autres artefacts logiciels, y compris les activités de test.Les principales problématiques scientifiques abordées dans cette thèse sont les suivantes: définir des mesures et des outils de support pour mesurer les activités d'ingénierie logicielle modernes en termes d'efficacité et de qualité. La seconde consiste à analyser les résultats de mesure pour identifier quoi et comment s'améliorer automatiquement. Le dernier consiste en l'automatisation du processus de mesure afin de réduire le temps de développement. Une telle solution hautement automatisée et facile à déployer constituera une solution révolutionnaire, car les outils actuels ne le prennent pas en charge, sauf pour une portée très limitée. / Most of the measurable software quality metrics are currently based on low level metrics, such as cyclomatic complexity, number of comment lines or number of duplicated blocks. Likewise, quality of software engineering is more related to technical or management factoid, and should provide useful metrics for quality requirements. Currently the assessment of these quality requirements is not automated, not empirically validated in real contexts, and the assessment is defined without considering principles of measurement theory. Therefore it is difficult to understand where and how to improve the software following the obtained result. In this domain, the main challenges are to define adequate and useful metrics for quality requirements, software design documents and other software artifacts, including testing activities.The main scientific problematic that are tackled in this proposed thesis are the following : defining metrics and its supporting tools for measuring modern software engineering activities with respect to efficiency and quality. The second consists in analyzing measurement results for identifying what and how to improve automatically. The last one consists in the measurement process automation in order to reduce the development time. Such highly automated and easy to deploy solution will be a breakthrough solution, as current tools do not support it except for very limited scope.

Soziale Medien spielen gesellschaftlich eine immer bedeutendere Rolle. Sie lassen viele Lebensbereiche digitaler werden und sind meist nicht mehr wegzudenken (BVCM, 2014; Lumma et al., 2015). Sie erleichtern die Informationsteilung und -bearbeitung aller Art und dienen dem Austausch und der Pflege von Beziehungen (Schmidt, 2018). Social Media ist längst zum Standard geworden. Für Unternehmen ergeben sich neue Herausforderungen, denn soziale Netzwerke entwickeln sich rasant weiter. Vermehrt suchen Firmen nach erfahrenen Mitarbeitenden, die die Chancen und Risiken der digitalen Veränderungen managen können. Die Unternehmen lassen ihre Kanäle von eigens eingestellten Expert*innen betreuen, um sie im Hinblick auf ihre Zielerreichung bewusst einzusetzen (BVCM, 2014; BITKOM, 2015; Lumma et al., 2015). Social Media Manager*innen (SMM) nehmen dabei eine übergeordnete, strategische Position ein. SMM sind ein entscheidender Teil der Unternehmenskommunikation und tragen zu einer strategischen Kommunikation am Arbeitsplatz bei (Cyphert, 2009). Diese beinhaltet im Allgemeinen die Überwachung und Evaluierung der Kommunikation, ein thematisches Management, die Policy- und Strategieberatung sowie die Unterstützung zur Problemlösung (Moss et al., 2005). Konkret obliegen SMM nach dem Bundesverband Community Management e.V. (BVCM, 2014) die folgenden Aufgabenbereiche: Strategie, Change Management, Monitoring und Reporting, Koordination sämtlicher Social Media Aktivitäten, Qualitätssicherung von Inhalten sowie Führung des Community Teams. Zudem nehmen sie eine Schnittstellenfunktion zwischen den unterschiedlichen Bereichen des Unternehmens wahr (BVCM, 2014). Die Aufgabenbereiche sind interdisziplinär ausgestaltet und berücksichtigen neben Marketing und PR bspw. auch die Produktentwicklung (Lumma et al., 2015) ... [Aus: Einleitung]

The field of single-molecule magnetism studies nanoscopic objects which exhibit superparamagnetic behavior below a certain temperature. The molecular magnet consists of one or several magnetic metal ions and the surrounding ligands that form the desired environment. Manganese was the first from 3d metals to show a delayed relaxation of magnetization and magnetic hysteresis in Mn12AC molecule in 1993. Later 4f elements were found to be even better candidates for single-molecule magnets. Endohedral fullerenes show a wide potential in encapsulating 4f elements. Not only fullerenes with one or several 4f-block metal ions can be obtained but also various clusterfullerenes comprising several positively charged metal ions and up to several negatively charged ions like N-3, S-2, etc. Importantly not only 4f elements can form clusters inside the fullerene cage but also non-magnetic metals like Y and Sc. This allows to vary the number of magnetic ion in the cluster retaining almost similar structure. This thesis reports magnetic studies of various Dy endohedral fullerenes: DySc2N@C80 and Dy2ScN@C80, which are the pioneer endohedral fullerene single-molecule magnets. For DySc2N@C80, the intriguing process of quantum tunneling of magnetization was studied in detail for powder and single-crystal samples with different dilution methods. For Dy2ScN@C80, the coupling between two Dy ion is of the main interest. Magnetic studies of this compound revealed: that the quantum tunneling process is effectively suppressed due to exchange interactions in the cluster; and a large anisotropy barrier of 1735±21 K. Dy2S@C82-Cs, -C3v, Dy2S@C72-Cs, Dy2C2@C82-Cs fullerenes were studied in order to obtain a deeper understanding of the coupling of magnetic elements inside the cage. The investigation of a fullerene family with a similar cluster in cages of different symmetry and different clusters in the same fullerene cage allowed to separate the influence of the cluster composition and the cage structure on magnetic properties of endohedral metallofullerene single-molecule magnets. The cage structure was found to have a dominant influence. Dy2@C80(CH2Ph) is a special endohedral metallofullerene with a single-electron Dy Dy bond. It represents the ultimate case of magnetic coupling and exhibits a record-high blocking temperature (21.9 K) among di-metal single-molecule magnets. The comparison of obtained results allowed to understand how the quantum tunneling is influenced by of both intramolecular interactions and magnetic coupling inside the fullerene cage. Also, Dy2@C80(CH2Ph) endohedral metallofullerene with a single-electron lanthanide-lanthanide bond opens the new class of tunable single-molecule magnets, with outstanding magnetic properties.

In this thesis I present a complete and detailed guide for the development process and fabrication of efficient single-electron transistors (SETs) and a better single-molecule magnets (SMMs) deposition yield. Starting from a commercial Si/SiO2 wafer I show the steps for the deposition of different layers to fabricate a SET as well as the improvements achieved in those for a completely functional SET device. The development process is based on a combination of optical lithography and e-beam lithography with metal deposition in ultra-high vacuum. The improvements involve a better conductance in the Al gate component, with a controlled formation of the superficial oxide layer and a faster feedback electromigration-induced breaking of Au nanowires for the creation of nanogaps at room temperature. The gate component is improved by increasing its thickness and exposing it to plasma oxidation for the complete oxidation of its surface. The nanowire breaking is realized at room temperature to make use of the surface tension of Au, which, after a previous feedback procedure, eventually opens the final gap in the nanowire. Finally, I demonstrate a new technique that allows increasing the yield of having a SMM connected in the nanowire gap. This new technique is based on monitoring the resistance of the broken nanowires during the SMM deposition from a controlled liquid solution at room temperature. When the resistance ( > GΩ for open gaps) drops to values below Mega-ohms (characteristic resistance of a molecule bridging the gap) for a number of nanowires in the chip, the device is then ready for low temperature measurements.

Работа посвящена исследованию продвижения волонтерства в социальных сетях при помощи SMM-маркетинга на примере волонтерских центров в России в г. Екатеринбург. Объектом исследования выступают волонтерская деятельность в России, предметом – особенности продвижения волонтерских центров посредством социальных сетей. Цель исследования: изучить особенности продвижения волонтерской деятельности в России через использование социальных сетей, проанализировать влияние социальных сетей на бренд каждого из центров. Материал исследования составили англоязычные и русскоязычные авторы, которые рассматривали волонтерство с разных сторон, собранная статистика социальных сетей волонтерских центров, анализ интервью по теме волонтерства. В первой части работы раскрывается понятие, сущность и история становления волонтерства в мире и в России. Кроме того, рассматриваются и анализируются точки зрения российских и зарубежных авторов. Во второй части исследования показываются особенности инструментов SMM-маркетинга и изучаются механизмы его функционирования в продвижении организаций в социальных сетях. Проводится комплексный анализ социальных сетей и способов продвижения через них. Далее происходит сбор и анализ статистических данных по волонтерским центрам и сравнение специфики работы волонтерских центров. Обзор волонтерских центров и сравнительный анализ специфики продвижения, основных направлений работы центров, используемых в контенте их социальных сетей, на основе собранных данных. В данной части работы также представлена подробная специфика работы волонтерских центров, классификация задействованной аудитории, раскрытие стратегий и тактик в продвижении волонтерских организаций в социальных сетях. В третьей главе в соответствии с темой исследования проводится опрос целевой аудитории на тему волонтерства, далее анализируются полученные результаты. Результаты проведенного нами сравнительного анализа волонтерских центров и их статистики в социальных сетях, а также проведенных интервью для определения эффективности продвижения в социальных сетях могут быть использованы в ходе маркетингового анализа и улучшения продвижения и работы других волонтерских центров в социальных сетях. В приложениях приводятся дополнительные статистические данные волонтерских центров на русском языке, а также отобранные два индивидуальных интервью на английском языке. / The work is devoted to the study of the promotion of volunteering in social networks using SMM marketing on the example of volunteer centers in Russia in Yekaterinburg. The object of the study is volunteering in Russia, the subject is the features of promoting volunteer centers through social networks. The purpose of the study: to study the features of promoting volunteering in Russia using social networks, to analyze the impact of social networks on the brand of each of the centers. The research material was compiled by English-speaking and Russian-speaking authors who considered volunteering from different points, collected statistics from social networks of volunteer centers, and analysis of interviews on the topic of volunteering. The first part of the work reveals the concept, essence, and history of the formation of volunteering in the world and in Russia. In addition, the points of view of Russian and foreign authors are considered and analyzed. The second part of the study shows the features of SMM marketing tools and examines the mechanisms of its functioning in promoting organizations in social networks. A comprehensive analysis of social networks and ways to promote through them is carried out. Next, there is a collection and analysis of statistical data on volunteer centers and a comparison of the specifics of the work of volunteer centers. An overview of volunteer centers and a comparative analysis of the specifics of promotion, the main areas of work of the centers used in the content of their social networks, based on the collected data. This part of the work also presents the detailed specifics of the work of volunteer centers, the classification of the audience involved, the disclosure of strategies and tactics in promoting volunteer organizations in social networks. In the third chapter, in accordance with the topic of the study, a survey of the target audience on the topic of volunteering is conducted, and then the results are analyzed. The results of our comparative analysis of volunteer centers and their statistics in social networks, as well as interviews conducted to determine the effectiveness of promotion in social networks can be used while marketing analysis and improvement of the promotion and work of other volunteer centers in social networks. The appendices provide additional statistics from volunteer centers in Russian, as well as a selection of two individual interviews in English.

Yes / Social media facilitates and enhances communication between businesses and customers. Nowadays, although it is commonly recognised that companies implement social media into their marketing activities, it is also acknowledged that companies struggle to calculate the return on investment (ROI) from social media marketing efforts as most of them focus only on certain tangible outcomes such as the impact on sales and purchases. Attempts have been made by researchers to identify how to measure key impacts of social media in relation to marketing; however, there remains a lack of empirical data and no comprehensive overview of what “ROI” can mean for an organisation seeking returns on their social media adoption. By knowing how to measure ROI from social media, companies can produce valuable insights which can help enhance marketing strategies in promoting their products/services. Thus, the aim of this chapter is to provide a review of ROI in social media marketing with a particular focus on intangible outcomes such as brand awareness, customer engagement/relationship and eWOM.

Выстраивание компанией коммуникации с потенциальными потребителями через маркетинг социальных медиа может стать одним из основных путей поддерживания двухсторонней коммуникации в интернете. В нашей работе мы сфокусировались на формировании модели коммуникации компании с учетом характеристик социокультурных групп, а именно поколений. Работа посвящена изучению психологических, демографических и культурных особенностей поколений, а также особенностей их поведения в социальных сетях. Мы предложили SMM-модель, а также матрицу, которые могут упростить выбор основных элементов коммуникации в социальных сетях. Проведенная на основании сформулированной модели SMM-кампания показала высокие результаты и перспективность учета характеристик социокультурных групп для ведения коммуникации. / The company's building of communication with potential consumers through the marketing of social media can become one of the main ways to support two-way communication on the Internet. In our work we focused on the formation of the company's communication model, taking into account the characteristics of sociocultural groups, namely generations. The work is devoted to the study of psychological, demographic and cultural features of generations, as well as features of their behavior in social networks. We proposed an SMM-model, as well as a matrix, that can simplify the choice of the basic elements of communication in social networks. Based on the formulated model SMM-campaign showed high results and the prospect of taking into account the characteristics of sociocultural groups for communication.