Table of contents. 1. Introduction... 4

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1 Table of contents 0. Motivation Introduction Inclusion compounds of [Al(OH)(bdc)] n and [V(O)(bdc)] n [(η 5 -C 5 H 5 ) 2 Fe] and [(η 5 -C 5 H 5 ) 2 Co] Synthesis and characterization TG studies FT-IR spectroscopic measurements N 2 -adsorption data C and 1 H MAS NMR Structural analysis [(η 5 -C 5 H 5 ) 2 Co] [metallocenes] Mono-substituted ferrocene derivatives Di-subsituted ferrocene derivatives Analytical and spectroscopic characterization Thermal properties of [metallocenes] Electrochemical properties of [metallocenes] [metallocenes] Synthesis Comparative discussion of [metallocenes] and [metallocenes] [(η 5 -C 5 H 5 ) 2 Co] TG studies and elemental analysis FT-IR spectroscopic measurements Structural analysis Electron spin resonance Magnetic susceptibility Electrochemical properties Release of cobaltocene from MIL-47(V). 44 ix

2 2.5.8 Co-adsorption experiments Theoretical calculations of spin orientations CO 2, N 2 and CH 4 uptake of [(η 5 -C 5 H 5 ) 2 Co] Conclusion References Postsynthetic modification of [Al(OH)(bdc)] n Incorporation of 1,1 -ferrocenediyl-dimethylsilane in MIL-53(Al) Synthesis Characterization Elemental/AAS analysis TG studies Differential scanning calorimetry Powder X-ray diffraction H-, 2 H-, 13 C-, 27 Al-, and 29 Si MAS NMR FT-IR spectroscopic measurements Testing electrochemical and catalytic properties Electrochemical properties Catalytic test reaction Trials to incorporate FDS into other PCPs Loading of [Al(OH)(ndc)] n with FDS Loading of [Ni 2 (dhtp)(h 2 O) 2 ] n with FDS Conclusion References Deposition of thin PCP films on different substrates Reaction cell [Cu 2 (ndc) 2 (dabco)] n as model system for deposition experiments Estimation of the right conditions via QCM Step-by-step deposition of oriented films of [Cu 2 (ndc) 2 (dabco)] n Out-of-plane PXRD analysis of the PCP thin films In-of-plane PXRD analysis of the PCP thin films AFM characterization FT-IR spectroscopic measurements 105 x

3 4.3.5 SEM characterization Deposition of 15, 25, and 40 layers of [Cu 2 (ndc) 2 (dabco)] n Modification of the washing process during the step-by-step deposition Growth mode of [Cu 2 (ndc) 2 (dabco)] n on bare substrate surfaces Domain size of single crystallites of [Cu 2 (ndc) 2 (dabco)] n Deposition of [Cu 2 (ndc) 2 (dabco)] n crystals via direct solvothermal method Seeding layer approach for fabrication of thick, oriented PCP films Characterization of PCP films produced by seeding layer approach Deposition of [Cu 3 (btc) 2 ] n on flexible polymer surfaces UV-vis monitoring of the deposition of first 10 layers Estimation of Cu concentration in films with different thickness PXRD analysis of films on flexible polymers FT-IR spectroscopic measurements AFM, SEM and EDX analysis Testing the porosity of the films Conclusion References Synthesis of polyacenes inside 1D and 2D PCPs Synthesis PCP host materials Sample preparation and nomenclature Properties of 2,4-Hexadiyne-1,6-diol Structural characterization FT-IR spectroscopy Thermal gravimetry analysis UV-vis spectroscopy C solid state MAS NMR Characterization of isolated PHDiD FT-IR spectroscopy Thermal gravimetry analysis UV-vis spectroscopy C solid state MAS NMR xi

4 5.4 Conclusion References Experimental section Analytical methods X-ray powder diffraction Gas adsorption measurements Quartz crystal microbalance Solid state nuclear magnetic resonance Instrumental details Powder X-ray diffraction Bulk samples Thin PCP films deposited on different substrate surfaces Solid state nuclear magnetic resonance FT-IR spectroscopy Elemental analysis / atomic absorption spectroscopy Differential pulse voltammetry and cyclovoltammetry Gas chromatography - mass spectrometry Gas chromatography Scanning electron microscopy Quartz crystal microbalance Thermogravimetric analysis Atomic force microscopy Magnetic susceptibility Electron spin resonance Sorption measurements UV-vis spectroscopy Calculations DFT calculations of spin orientation DFT calculations of CO 2 molecular complexes GCMC calculations of adsorption isotherms Syntheses of the materials Synthesis of Ferrocene n Synthesis of 1-Formylferrocene n 189 xii

5 6.4.3 Synthesis of 1,1 -Dimethylferrocene n Synthesis of 1,1 -Diformylferrocene n Synthesis of 1,1 -Diethylferrocene n Synthesis of Cobaltocene n Synthesis of Ferrocene n Synthesis of Cobaltocene n Washing out of cobaltocene FT-IR spectroscopy Powder XRD data Synthesis of Ferrocene 0.35 /Cobaltocene n Synthesis of Ferrocene 0.1 /Cobaltocene n Synthesis of 1,1 -ferrocenediyl-dimethylsilane n Catalytic test reaction Preparation of PCP thin films Substrate preparation PCP film growth Synthesis of [HDiD] n (80) samples Thermal treatment of [HDiD] n (80) samples Decomposition procedure for the PCP matrix SEM study of [PHDiD] n samples FT-IR spectroscopy Thermal gravimetry analysis References Appendix A List of figures, schemes and tables. 212 A-1 List of figures A-2 List of schemes A-3 List of tables B List of publications and conference contributions B-1 List of publications. 219 B-2 Oral presentations B-3 Poster presentations 221 xiii

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