[ES] Las zeolitas tradicionalmente se han considerado silicoaluminatos microporosos formados por tetraedros TO4 (T = Si, Al) conectados entre sí, compartiendo átomos de oxígeno dando lugar a canales y cavidades de dimensiones moleculares. Debido al potencial que presentan como catalizadores en aplicaciones relevantes en la industria química y más recientemente en la industria medioambiental, ha habido un creciente interés en la síntesis de nuevos materiales zeolíticos. La incorporación de elementos diferentes al silicio y aluminio en su estructura (P, Ge, Fe, Ti, B etc.) ha dado lugar a la aparición de nuevos tamices moleculares zeolíticos, entre los que destacan los aluminofosfatos (AlPOs), siendo la primera familia de tamices moleculares con composiciones en las que no participa el silicio. El elevado número de nuevas estructuras de aluminofosfatos sintetizados, con tamaños de poro de hasta 13 Å, así como la facilidad con que el aluminio y el fósforo pueden ser sustituidos por otros elementos químicos, ha despertado un gran interés en estos materiales, al abrir un amplio rango de aplicaciones, especialmente en procesos de adsorción y catálisis. La presente tesis doctoral se centra en la síntesis de nuevos aluminofosfatos, empleando nuevas moléculas orgánicas como agentes directores de estructura, para su posterior aplicación como catalizadores en reacciones químicas de interés. En el Capítulo 1, se presenta una introducción general sobre las zeolitas y más concretamente los aluminofosfatos, su síntesis, propiedades y aplicaciones. En el Capítulo 2, se presentan los objetivos generales de este trabajo. En el Capítulo 3, se muestra la síntesis de los diferentes agentes directores de estructura orgánicos, así como de los principales materiales sintetizados, junto con los equipos de caracterización y procedimientos catalíticos utilizados. El Capítulo 4, se centra en la síntesis del primer aluminofosfato con estructura SAO (AlPO-SAO) y sus derivados incorporando silicio (SAPO-SAO) y germanio (GeAPO-SAO), siendo éste último, el primer germanoaluminofosfato tridimensional de poro grande descrito hasta la actualidad. La actividad catalítica de los catalizadores preparados es evaluada en la reacción de transposición de Beckmann y comparada con el material SAPO-37 (FAU). En el Capítulo 5, se estudian mediante síntesis de co-template los silicoaluminfosfatos erionita (ERI) y chabacita (CHA), ambos pertenecientes a la familia ABC-6, preparados a partir de dos nuevas familias de agentes directores de estructura orgánicos. En el Capítulo 6, se propone una nueva ruta de síntesis basada en la síntesis de co-template anterior, para la preparación del silicoaluminofosfato SAPO-34 empleando una mezcla de agentes directores de estructura orgánicos de tipo amina y tetraalquilfosfonio, estudiándose la naturaleza de las especies de fósforo localizadas en las cavidades de la estructura chabacita. Finalmente, se han evaluado las propiedades catalíticas del catalizador activado en distintas condiciones en el proceso de metanol a olefinas comparándolas con un material SAPO-34 sintetizado únicamente mediante un agente director de estructura orgánico nitrogenado. Por otra parte, se ha estudiado la estabilidad de todos los catalizadores en presencia de vapor de agua (100% steaming) a elevada temperatura. / [CA] Les zeolites tradicionalment s'han considerat silicoaluminats microporosos formats per tetraedres TO4 (T=Si, Al) connectats entre sí, compartint àtoms d'oxigen donant lloc a Canals i cavitats de dimensions moleculars. Degut al potencial que presenten com a catalitzadors en aplicacions rellevants en la industria química i més recentment en la industria mediambiental, hi ha hagut un creixent interès en la síntesis de nous materials zeolítics. La incorporació d'elements diferents al silici i alumini en la seua estructura (P, Ge, Fe, Ti, B etc.) ha donat lloc a l'aparició de nous tamisos moleculars zeolítics, entre els que destaquen els aluminofosfats (AlPOs), siguent la primera família de tamisos moleculars amb composicions en les que no participa el silici. L'elevat nombre de noves estructures d'aluminofosfats sintetitzats, amb tamany de porus de fins a 13 Å, així com la facilitat amb que l'alumini i el fòsfor puguen ser substituïts per altres elements químics, ha despertat un gran interès en estos materials, a l'obrir un ampli rang d'aplicacions, especialment en processos d'adsorció i catàlisi. La present tesi doctoral es centra en la síntesi de nous aluminofosfats, emprant noves molècules orgàniques com agents directors d'estructura, per a la seua posterior aplicació com a catalitzadors en reaccions químiques d'interès. Al Capítol 1, es presenta una introducció general sobre les zeolites i més concretament els aluminofosfats, la seua síntesi, propietats i aplicacions. Al Capítol 2, es presenten els objectius generals d'este treball. Al Capítol 3, es mostra la síntesis dels diferents agents directors d'estructura orgànics, així com dels principals materials sintetitzats, junt amb els equips de caracterització i procediments catalítics utilitzats. El Capítol 4, es centra en la síntesi del primer aluminofosfat amb estructura SAO (AlPO-SAO) i els seus derivats incorporant silici (SAPO-SAO) i germani (GeAPO-SAO), siguent este últim, el primer germanoaluminofosfat tridimensional de porus gran descrit fins l'actualitat. L'activitat catalítica dels catalitzadors preparats és avaluada en la reacció de transposició de Beckmann i comparada amb el material SAPO-37 (FAU). Al Capítol 5, s'estudien mitjançant síntesi de co-template els silicoaluminofosfats eritonita (ERI) i chabazita (CHA), ambdós pertanyents a la família ABC-6, preparats a partir de dos noves famílies d'agents directors d'estructura orgànics. Al Capítol 6, es proposa una nova ruta sintètica basada en la síntesi de co-template anterior, per a la preparació del silicoaluminofosfat SAPO-34 emprant una mescla d'agents directors d'estructura orgànics de tipus amina i tetraalquilfosfoni, estudiant-se la natura de les espècies de fòsfor localitzades en les cavitats de l'estructura chabazita. Finalment, s'han avaluat les propietats catalítiques del catalitzador activat en diverses condicions en el procés de metanol a olefines comparant-les amb un material SAPO-34 sintetitzat únicament mitjançant un agent director d'estructura orgànic nitrogenat. Per altra banda, s'ha estudiat l'estabilitat de tots els catalitzadors en presència de vapor d'aigua (100% steaming) a elevada temperatura. ¿ / [EN] Zeolites have traditionally been considered as microporous silicoaluminates formed by TO4 (T= Si, Al) tetrahedras connected, sharing oxygen atoms, giving rise to channels and cavities of molecular dimensions. Due to their potential as catalysts in relevant applications in the chemical industry, and more recently in the environmental industry, there has been a growing interest in the synthesis of new zeolitc. The incorporation of elements other than silicon and aluminum in their structure (P, Ge, Fe, Ti, B, etc) has led to appearance of new zeolitic molecular sieves, among which the aluminophosphates (AlPOs) stand out, being the first family of molecular sieves with compositions in which silicon does not participate. The high number of new structures of synthesized AlPOs, with pore sizes up to 13 Å, along with the ease in which the aluminum and phosphorus can be substituted by other chemical elements, has awakened a great interest in these materials, opening a wide range of applications, especiallly in adsorption and catalysis processes. This doctoral thesis focuses on the synthesis of new aluminophosphates, using new organic molecules as structure directing agents, for their further application as catalysts in chemical reactions of interest. In Chapter 1, a general introduction about zeolites and, more specifically, aluminophosphates, as well as their synthesis, properties and applications are presented. In Chapter 2, the general objectives of this work are presented. In Chapter 3, the synthesis of the different organic structure agents is shown. Furthermore, the main materials synthesized, together with the characterization equipment and catalytic procedures used are also displayed. Chapter 4 focuses on the synthesis of the first aluminophosphate with SAO structure (AlPO-SAO) and its derivatives incorporating silicon (SAPO-SAO) and germanium (GeAPO-SAO), being the latter the first three-dimensional large pore germaniumaluminophosphate reported until now. The catalytic activity of the prepared catalysts is evaluated in the Beckmann transposition reaction and compared with the SAPO-37 (FAU) material. In Chapter 5, erionite (ERI) and chabazite (CHA) silicoaluminophosphates, both belonging to the ABC-6 family, prepared from two new families of organic structures directing agentes, are studied by co-template synthesis. In Chapter 6, a new synthesis route based on the previous co-template synthesis is proposed for the preparation of the silicoaluminophosphate SAPO-34 using a mixture of organic structure directing agents of amine and tetraalkylphosphonium type, studying the nature of the phosphorus species located of the cavities chabazite structure. Finally, the catalytic properties of the catalysts activated under different conditions have been evaluated in the methanol process, comparing them with a SAPO-34 material synthesized only using a nitrogenous organic structure directing agent. On the other hand, the stability of all catalysts in the presence of water steam (100% steaming) at elevated temperatures has been studied. / González Camuñas, N. (2022). Síntesis, caracterización y aplicaciones catalíticas de aluminofosfatos y silicoaluminofosfatos zeolíticos obtenidos empleando nuevos agentes directores de estructura [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/184308 / TESIS

The preparation of a new group of functionalized conjugated polymer networks has been described based on spontaneous quaternization polymerization of ethynylpyridines with bis(bromomethyl)arenes. The networks consisted of polyacetylene chains with pyridyl and pyridiniumyl pendants cross-linked with -CH2(arylene)CH2- links. The variation of the ratio of monomer and quaternization agent in the feed modified the ratio of pyridyl and pyridiniumyl groups in the networks (pyridyl/pyridiniumyl ratios from 0 to 1.32). The networks did not exhibit a permanent microporosity that could be confirmed by nitrogen adsorption at 77 K. Nevertheless, all networks were active in capture of CO2 at 293 K (up to 0.73 mmol CO2/g, 750 Torr). It has been hypothesized that CO2 capture reflected formation of a temporary porous texture of the networks through conformational changes of the network segments enabled by the segments mobility at room temperature. The preparation of functionalized conjugated polymer networks with permanent micro/mesoporosity (SBET up to 667 m2 /g) has been described that was based on chain coordination copolymerization of acetylenic monomers. The copolymerization of 1,4-diethynylbenzene or 4,4'-diethynylbiphenyl with mono or diethynylbenzenes bearing NO2 or CH2OH groups has been demonstrated as...

Im Fokus dieser Arbeit standen zwei Ziele. Zum einem war es Forschungsgegenstand, dass Konzept der Zwillingspolymerisation auf germaniumhaltige, molekulare Vorstufen wie zum Beispiel Germylene, spirozyklische Germaniumverbindungen und molekulare Germanate zu erweitern und somit organisch-anorganische Komposite beziehungsweise Hybridmaterialien darzustellen. Dazu wurden neuartige Germaniumalkoxide auf der Basis von Benzylalkoholaten, Salicylalkoholaten sowie Benzylthiolaten synthetisiert, charakterisiert und auf ihre Fähigkeit Komposite beziehungsweise Hybridmaterialien über den Prozess der Zwillingspolymerisation zu erhalten studiert. Ein zweites Ziel dieser Arbeit war es, Beziehungen zwischen der Struktur und der Reaktivität dieser molekularen Vorstufen sowie deren Einfluss auf die Eigenschaften der erhaltenen Polymerisationsprodukte zu identifizieren und systematisch zu untersuchen. Hierfür wurden zum einen verschiedene Substituenten, welche unterschiedliche elektronische sowie sterische Eigenschaften aufweisen, an den aromatischen Einheiten der molekularen Vorstufen eingeführt. Die Effekte der Substituenten auf den Prozess der Zwillingspolymerisation und auf die Eigenschaften der Komposite beziehungsweise Hybridmaterialien wurden für die Verbindungsklasse der Germanium(II)salicylalkoholate, der molekularen Germanate sowie der spiro-zyklischen Siliziumsalicylalkoholate untersucht. Spirozyklische Siliziumsalicylalkoholate, wie zum Beispiel 4H,4’H-2,2‘-Spirobi[benzo[d][1,3,2]dioxasilin], wurden im Rahmen dieser Arbeit mit einbezogen, da sie aufgrund ihres nahezu idealen Zwillingspolymerisationsprozesses geeignete Modelverbindungen für Reaktivitätsstudien darstellen. Zudem wurde der Einfluss der Substituenten auf die Charakteristika der aus den Kompositen beziehungsweise Hybridmaterialien erhaltenen Folgeprodukte (poröse Kohlenstoffmaterialien und oxydische Materialien) studiert. Des Weiteren wurde eine Serie von spirozyklischen Germaniumthiolaten, welche isostrukturell zu 4H,4’H-2,2‘-Spirobi[benzo[d][1,3,2]dioxasilin] sind, synthetisiert, um systematisch den Einfluss der Chalkogenide, Sauerstoff und Schwefel, in benzylständiger sowie phenylständiger Position auf deren Reaktionsvermögen im Polymerisationsprozess zu untersuchen. Die experimentellen Ergebnisse zu den Struktur-Reaktivitätsbeziehungsstudien wurden, soweit es jeweils durchführbar war, mittels quantenchemische Rechnungen validiert und die daraus gezogenen Schlüsse in die Diskussion zur Interpretation der experimentellen Ergebnisse mit einbezogen.:Contents List of Abbreviations S. 11 1 Introduction S.14 2 Germanium alkoxides and germanium thiolates S. 18 2.1 Preamble S. 18 2.2 Germanium alkoxides S. 18 2.2.1 Germanium(II) alkoxides S. 20 2.2.2 Germanium(IV) alkoxides S. 23 2.2.3 Alkoxidogermanates S. 29 2.3 Germanium thiolates S. 31 2.3.1 Germanium(II) thiolates S. 33 2.3.2 Germanium(IV) thiolates S. 34 2.3.3 Thiolatogermanates and cationic germanium thiolato transition metal complexes S. 36 2.4 Germanium alkoxido thiolates S. 38 2.5 Concluding remarks S. 40 3 Individual Contributions S. 43 4 Microporous Carbon and Mesoporous Silica by Use of Twin Polymerization: An integrated Experimental and Theoretical Approach on Precursor Reactivity S. 46 4.1 Abstract S. 46 4.2 Introduction S.46 4.3 Results and Discussion S. 48 4.3.1 Synthesis and Characterization S. 48 4.3.2 Thermally induced twin polymerization of monosubstituted Precursors (para position) S.49 4.3.2.1 Studies on reactivity according to thermally induced twin polymerization S. 50 4.3.2.2 Characterization of the hybrid materials as obtained by thermally induced twin polymerization S. 51 4.3.2.3 Thermally induced twin polymerization of di-substituted precursors (ortho and para position) S. 52 4.3.2.4 Conclusions drawn for the thermally induced twin polymerization S. 54 4.3.3 Proton-assisted twin polymerization S. 54 4.3.3.1 Studies on the reactivity according to proton-assisted twin polymerization S.55 4.3.3.2 Characterization of the hybrid materials as obtained by proton-assisted twin polymerization S.56 4.3.3.3 Computational studies on proton-assisted twin polymerization S. 58 4.3.3.4 Conclusions drawn for the process of proton-assisted twin polymerization S. 60 4.3.4 Characterization of the porous materials S.61 4.4 Conclusions S.64 4.5 Experimental Section S. 65 4.5.1 General S.65 4.5.2 General procedure for the synthesis of phenolic resin-silica hybrid materials by thermally induced twin polymerization in melt - exemplified for compound 1 S. 66 4.5.3 General procedure for the synthesis of phenolic resin-silica hybrid materials by proton-assisted twin polymerization in solution - exemplified for compound 1 S. 66 4.5.4 General procedure for the synthesis of microporous carbon - exemplified for hybrid material HM-1T S. 66 4.5.5 General procedure for the synthesis of mesoporous silica - exemplified for hybrid material HM-1T S. 67 4.5.6 Single-Crystal X-ray Diffraction Analyses S. 67 4.5.7 Computational Details S. 67 4.6 Acknowledgments S. 68 4.7 Keywords S.68 4.8 Supporting Information Chapter 4 S. 69 5 Synthesis of germanium dioxide nanoparticles in benzyl alcohols – a comparison S. 82 5.1 Abstract S. 82 5.2 Introduction S. 82 5.3 Results and Discussion S.83 5.4 Conclusions S. 87 5.5 Experimental Section S. 87 5.5.1 General S. 87 5.5.2 Syntheses S. 88 5.5.3 Synthesis of GeO2 in ortho-methoxy benzyl alcohol – sample A S. 88 5.5.4 Synthesis of GeO2 in benzyl alcohol under inert conditions – sample B S. 89 5.5.5 Synthesis of GeO2 in benzyl alcohol under ambient conditions – sample C S. 89 5.6 Acknowledgments S. 89 5.7 Keywords S.89 5.8 Supporting Information Chapter 5 S. 90 6 From a Germylene to an “Inorganic Adamantane”: [{Ge₄(μ-O)₂(μ-OH)₄}{W(CO)₅}₄]∙4THF S. 93 6.1 Abstract S.93 6.2 Introduction S. 93 6.3 Results and Discussion S. 94 6.4 Conclusions S. 98 6.5 Experimental Section S. 99 6.5.1 General S.99 6.5.2 Synthesis of germanium(II) (2-methoxyphenyl)methoxide (9) S. 99 6.5.3 Synthesis of [{Ge4(μ-O)2(μ-OH)4}{W(CO)5}4]·4THF (10·4THF) S. 100 6.5.4 Single-Crystal X-ray Diffraction Analyses S. 100 6.5.4.1 Crystal Data for (9)2 S. 101 6.5.4.2 Crystal Data for 10·4THF S. 101 6.5.5 Computational Details S. 101 6.6 Acknowledgments S. 101 6.7 Keywords S.101 6.8 Supporting Information Chapter 6 S. 102 7 Synthesis, characterization and Twin Polymerization of a novel dioxagermine S. 110 7.1 Abstract S. 110 7.2 Introduction S.110 7.3 Results and Discussion S. 111 7.3.1 Single-crystal X-ray diffraction analysis S. 111 7.3.2 IR spectroscopy S. 112 7.3.3 Mass spectrum S. 114 7.3.4 DSC/TGA analysis S. 116 7.3.5 Polymerization S. 117 7.4 Conclusions S. 118 7.5 Materials and Methods S.118 7.5.1 General S. 118 7.5.2 Synthesis of 5-bromo-2-hydroxybenzyl alcohol S. 119 7.5.3 Synthesis of di-tert-butyl-di-ethoxy germane S.119 7.5.4 Synthesis of 6-bromo-2,2-di-tert-butyl-4H-1,3,2-benzo[d]dioxagermine (11) S. 120 7.5.5 Polymerization of compound 11 S. 120 7.5.6 X-ray diffraction analysis of compound 11 S.120 7.5.6.1 Crystal data for compound 11 S.120 7.5.7 Computational Details S.121 7.6 Acknowledgments S.121 7.7 Keywords S. 121 7.8 Supporting Information Chapter 7 S. 122 8 Intramolecular C-O Insertion of a Germanium(II) Salicyl Alcoholate: A Combined Experimental and Theoretical Study S. 125 8.1 Abstract S.125 8.2 Introduction S. 125 8.3 Results and Discussion S.126 8.3.1 Syntheses and Characterization S. 126 8.3.2 1H NMR Spectroscopic Studies S.132 8.3.3 DFT-D Calculations S.134 8.4 Conclusions S. 137 8.5 Experimental Section S. 138 8.5.1 General S. 138 8.5.2 Synthesis of germanium(II) 2-tert-butyl-4-methyl-6-(oxidomethyl)phenolate (12) S. 139 8.5.3 Synthesis of 2,4,6,8-tetrakis(3-tert-butyl-5-methyl-2-oxidophenyl)methanide-1,3,5,7,2,4,6,8-tetraoxidogermocane (13) S. 139 8.5.3.1 Method a) S.139 8.5.3.2 Method b) S. 140 8.5.4 Synthesis of 7,8'-di-tert-butyl-5,6'-dimethyl-3H,4'H-spiro[benzo[d][1,2]oxager-mole-2,2'-benzo[d][1,3,2]dioxagermine] (14) S. 140 8.5.4.1 Method a) S. 140 8.5.4.2 Method b) S. 141 8.5.4.3 Method c) S. 141 8.5.5 Synthesis of the [4-(dimethylamino)pyridine][germanium(II)-2-tert-butyl-4-meth-yl-6-(oxidomethyl)phenolate] (15) S. 141 8.5.6 1H NMR spectroscopic study i) S. 142 8.5.7 1H NMR spectroscopic study ii) S. 142 8.5.7.1 Method a) S. 142 8.5.7.2 Method b) S. 142 8.5.8 1H NMR spectroscopic study iii) S. 142 8.5.8.1 Method a) S. 142 8.5.8.2 Method b) S. 142 8.5.9 1H NMR spectroscopic study iv) S. 143 8.5.10 1H NMR spectroscopic study of the mixture of complex 15 and 3-tert-butyl-2-hydroxy-5-methylbenzyl alcohol in CDCl3 S. 143 8.5.11 1H NMR spectroscopic study of complex 15 in CDCl3 at elevated temperature S. 143 8.5.12 Reaction of complex 15 at elevated temperature S. 143 8.5.13 Single-crystal X-ray diffraction analyses S. 143 8.5.14 Computational Details S.144 8.6 Acknowledgments S. 145 8.7 Keywords S.145 8.8 Supporting Information Chapter 8 S. 146 9 Porous Ge@C materials via twin polymerization of germanium(II) salicyl alcoholates for Li-ion batteries S. 159 9.1 Abstract S. 159 9.2 Introduction S. 159 9.3 Results and Discussion S. 160 9.3.1 Synthesis and Characterization of germylenes S. 160 9.3.2 Twin polymerization S. 164 9.3.2.1 Studies on the reactivity S. 164 9.3.2.2 Characterization of the hybrid materials obtained by thermally induced twin polymerization S. 166 9.3.3 Synthesis and characterization of porous materials S. 168 9.3.4 Electrochemical measurements S. 170 9.4 Conclusions S. 172 9.5 Experimental Section S.172 9.5.1 General S.172 9.5.2 Synthesis of germanium(II) 2-(oxidomethyl)phenolate (16) S. 174 9.5.3 Synthesis of germanium(II) 4-methyl-2-(oxidomethyl)phenolate (17) S. 174 9.5.4 Synthesis of germanium(II) 4-bromo-2-(oxidomethyl)phenolate (18) S. 175 9.5.5 General procedure for the synthesis of phenolic resin-germanium oxide hybrid materials by thermally induced twin polymerization in melt - exemplified for compound 16 S. 175 9.5.6 General procedure for the synthesis of porous Ge@C materials - exemplified for hybrid material HM-16 S.175 9.5.7 General procedure for the synthesis of germanium oxide - exemplified for hybrid material HM-16 S.176 9.5.8 Single-crystal X-ray diffraction analyses S. 176 9.5.9 Computational Details S. 177 9.5.10 Electrode fabrication, cell assembly and electrochemical measurements S. 178 9.6 Acknowledgments S.178 9.7 Keywords S. 178 9.8 Supporting Information Chapter 9 S.179 10 From molecular germanates to microporous Ge@C via twin polymerization S.199 10.1 Abstract S.199 10.2 Introduction 199 10.3 Results and Discussion S. 201 10.3.1 Syntheses and Characterization S. 201 10.3.2 Twin polymerization of germanate 19 S. 204 10.3.3 Synthesis and characterization of the porous materials S. 205 10.3.4 Electrochemical measurements S.206 10.4 Conclusions S. 207 10.5 Experimental Section S. 208 10.5.1 General S. 208 10.5.2 Synthesis of bis(dimethylammonium) tris[2-(oxidomethyl)phenolate(2-)]germa-nate (19) S. 209 10.5.3 Synthesis of bis(dimethylammonium) tris[4-methyl-2-(oxidomethyl)pheno-late(2-)]germanate (20) S. 210 10.5.4 Synthesis of bis(dimethylammonium) tris[4-bromo-2-(oxidomethyl)pheno-late(2-)]germanate (21) S.210 10.5.5 Synthesis of dimethylammonium bis[2-tert-butyl-4-methyl-6-(oxidomethyl)phe-nolate(2-)][2-tert-butyl-4-methyl-6-(hydroxymethyl)phenolate(1-)]germanate (22) S. 211 10.5.6 Synthesis of phenolic resin-germanium dioxide hybrid materials by thermally induced twin polymerization in melt - HM-19 S. 211 10.5.7 Synthesis of porous Ge@C material C-19 starting from HM-19 S. 212 10.5.8 Synthesis of germanium dioxide material Ox-19 - starting from HM-19 S.212 10.5.9 Single-crystal X-ray diffraction analyses S. 212 10.5.10 Electrode fabrication, cell assembly and electrochemical measurements S.213 10.6 Acknowledgments S. 214 10.7 Keywords S. 214 10.8 Supporting Information Chapter 10 S.215 11 Chiral Spirocyclic Germanium Thiolates – An Evaluation of Their Suitability for Twin Polymerization based on A Combined Experimental and Theoretical Study S.226 11.1 Abstract S.226 11.2 Introduction S. 226 11.3 Results and Discussion S.227 11.3.1 Syntheses and Characterization S. 227 11.3.2 Studies on twin polymerization S.229 11.3.3 Computational studies on proton-assisted twin polymerization S. 232 11.4 Conclusions S. 235 11.5 Acknowledgments S. 236 11.6 Keywords S.236 11.7 Supporting Information Chapter 11 S.237 12 Concluding remarks S. 257 12.1 Discussion S.257 12.1.1 Twin polymerization of germanium-containing precursors S. 257 12.1.2 Reactivity studies of precursors towards their twin polymerization S.260 12.2 Summary and Outlook S. 264 Selbständigkeitserklärung S.266 Curriculum Vitae S.267 Publications S. 268 List of Publications in Peer-Reviewed Journals S. 268 List of Conference Contributions S.269 Research proposals, additional conference and summer school participations S. 270 Acknowledgments S. 271 References S. 272