Table of contents 0. Motivation.... 1 1. Introduction... 4 2. Inclusion compounds of [Al(OH)(bdc)] n and [V(O)(bdc)] n... 11 2.1 [(η 5 -C 5 H 5 ) 2 Fe] 0.5 @MIL-53(Al) and [(η 5 -C 5 H 5 ) 2 Co] 0.25 @MIL-53(Al) 15 2.1.1 Synthesis and characterization.. 15 2.1.2 TG studies. 16 2.1.3 FT-IR spectroscopic measurements.. 16 2.1.4 N 2 -adsorption data 18 2.1.5 13 C and 1 H MAS NMR..... 18 2.1.6 Structural analysis. 20 2.1.7 [(η 5 -C 5 H 5 ) 2 Co].. 23 2.2 [metallocenes] x @MIL-53(Al).. 24 2.2.1 Mono-substituted ferrocene derivatives... 24 2.2.2 Di-subsituted ferrocene derivatives.. 27 2.2.2.1 Analytical and spectroscopic characterization.. 27 2.2.3 Thermal properties of [metallocenes] x @MIL-53(Al)... 29 2.2.4 Electrochemical properties of [metallocenes] x @MIL-53(Al)... 30 2.3 [metallocenes] x @MIL-47(V)... 32 2.3.1 Synthesis... 32 2.4 Comparative discussion of [metallocenes] x @MIL-53(Al) and [metallocenes] x @MIL-47(V)... 33 2.5 [(η 5 -C 5 H 5 ) 2 Co] 0.5 @MIL-47(V). 37 2.5.1 TG studies and elemental analysis...... 37 2.5.2 FT-IR spectroscopic measurements.. 38 2.5.3 Structural analysis...... 39 2.5.4 Electron spin resonance 41 2.5.5 Magnetic susceptibility..... 42 2.5.6 Electrochemical properties... 43 2.5.7 Release of cobaltocene from MIL-47(V). 44 ix
2.5.8 Co-adsorption experiments... 44 2.5.9. Theoretical calculations of spin orientations 45 2.6 CO 2, N 2 and CH 4 uptake of [(η 5 -C 5 H 5 ) 2 Co] 0.5 @MIL-47(V) 49 2.7 Conclusion 58 2.8 References 61 3. Postsynthetic modification of [Al(OH)(bdc)] n.. 65 3.1 Incorporation of 1,1 -ferrocenediyl-dimethylsilane in MIL-53(Al). 69 3.1.1 Synthesis... 69 3.2 Characterization 71 3.2.1 Elemental/AAS analysis... 71 3.2.2 TG studies..... 71 3.2.3 Differential scanning calorimetry..... 73 3.2.4 Powder X-ray diffraction...... 74 3.2.5 1 H-, 2 H-, 13 C-, 27 Al-, and 29 Si MAS NMR 76 3.2.6 FT-IR spectroscopic measurements..... 79 3.3 Testing electrochemical and catalytic properties.. 80 3.3.1 Electrochemical properties... 80 3.3.2 Catalytic test reaction....... 81 3.4 Trials to incorporate FDS into other PCPs... 84 3.4.1 Loading of [Al(OH)(ndc)] n with FDS.. 84 3.4.2 Loading of [Ni 2 (dhtp)(h 2 O) 2 ] n with FDS. 85 3.5 Conclusion 86 3.6 References 88 4. Deposition of thin PCP films on different substrates... 90 4.1 Reaction cell. 96 4.2 [Cu 2 (ndc) 2 (dabco)] n as model system for deposition experiments... 98 4.2.1 Estimation of the right conditions via QCM 99 4.3 Step-by-step deposition of oriented films of [Cu 2 (ndc) 2 (dabco)] n. 101 4.3.1 Out-of-plane PXRD analysis of the PCP thin films... 101 4.3.2 In-of-plane PXRD analysis of the PCP thin films.. 102 4.3.3 AFM characterization..... 105 4.3.4 FT-IR spectroscopic measurements 105 x
4.3.5 SEM characterization...... 107 4.3.6 Deposition of 15, 25, and 40 layers of [Cu 2 (ndc) 2 (dabco)] n... 108 4.3.7 Modification of the washing process during the step-by-step deposition 110 4.3.8 Growth mode of [Cu 2 (ndc) 2 (dabco)] n on bare substrate surfaces... 111 4.3.9 Domain size of single crystallites of [Cu 2 (ndc) 2 (dabco)] n.. 112 4.4 Deposition of [Cu 2 (ndc) 2 (dabco)] n crystals via direct solvothermal method. 113 4.5 Seeding layer approach for fabrication of thick, oriented PCP films. 114 4.5.1 Characterization of PCP films produced by seeding layer approach. 114 4.6 Deposition of [Cu 3 (btc) 2 ] n on flexible polymer surfaces 116 4.6.1 UV-vis monitoring of the deposition of first 10 layers... 118 4.6.2 Estimation of Cu concentration in films with different thickness.. 120 4.6.3 PXRD analysis of films on flexible polymers.... 120 4.6.4 FT-IR spectroscopic measurements.... 121 4.6.5 AFM, SEM and EDX analysis.... 122 4.6.6 Testing the porosity of the films. 125 4.7 Conclusion.. 127 4.8 References.. 130 5. Synthesis of polyacenes inside 1D and 2D PCPs... 130 5.1 Synthesis. 141 5.1.1 PCP host materials.. 141 5.1.2 Sample preparation and nomenclature 143 5.1.3 Properties of 2,4-Hexadiyne-1,6-diol. 146 5.2 Structural characterization.. 150 5.2.1 FT-IR spectroscopy 152 5.2.2 Thermal gravimetry analysis.. 155 5.2.3 UV-vis spectroscopy... 155 5.2.4 13 C solid state MAS NMR.. 156 5.3 Characterization of isolated PHDiD... 158 5.3.1 FT-IR spectroscopy 158 5.3.2 Thermal gravimetry analysis.. 160 5.3.3 UV-vis spectroscopy... 160 5.3.4 13 C solid state MAS NMR.. 161 xi
5.4 Conclusion.. 163 5.5 References.. 164 6. Experimental section. 167 6.1 Analytical methods. 168 6.1.1 X-ray powder diffraction 168 6.1.2 Gas adsorption measurements 173 6.1.3 Quartz crystal microbalance... 175 6.1.4 Solid state nuclear magnetic resonance.. 176 6.2 Instrumental details 177 6.2.1 Powder X-ray diffraction 177 6.2.2.1 Bulk samples... 177 6.2.2.2 Thin PCP films deposited on different substrate surfaces.. 178 6.2.2 Solid state nuclear magnetic resonance.. 179 6.2.3 FT-IR spectroscopy 179 6.2.4 Elemental analysis / atomic absorption spectroscopy 179 6.2.5 Differential pulse voltammetry and cyclovoltammetry.. 180 6.2.6 Gas chromatography - mass spectrometry.. 180 6.2.7 Gas chromatography... 180 6.2.8 Scanning electron microscopy 180 6.2.9 Quartz crystal microbalance... 181 6.2.10 Thermogravimetric analysis... 181 6.2.11 Atomic force microscopy... 181 6.2.12 Magnetic susceptibility... 182 6.2.13 Electron spin resonance.. 182 6.2.14 Sorption measurements... 182 6.2.15 UV-vis spectroscopy... 182 6.3 Calculations 183 6.3.1 DFT calculations of spin orientation.. 183 6.3.2 DFT calculations of CO 2 molecular complexes. 184 6.3.3 GCMC calculations of adsorption isotherms.. 184 6.4 Syntheses of the materials.. 187 6.4.1 Synthesis of Ferrocene 0.5 @[Al(OH)(bdc)] n 188 6.4.2 Synthesis of 1-Formylferrocene 0.33 @[Al(OH)(bdc)] n 189 xii
6.4.3 Synthesis of 1,1 -Dimethylferrocene 0.33 @[Al(OH)(bdc)] n 190 6.4.4 Synthesis of 1,1 -Diformylferrocene 0.5 @[Al(OH)(bdc)] n.. 191 6.4.5 Synthesis of 1,1 -Diethylferrocene 0.33 @[Al(OH)(bdc)] n 192 6.4.6 Synthesis of Cobaltocene 0.25 @[(@[Al(OH)(bdc)] n 193 6.4.7 Synthesis of Ferrocene 0.25 @[V(O)(bdc)] n.. 194 6.4.8 Synthesis of Cobaltocene 0.5 @[V(O)(bdc)] n 195 6.4.9 Washing out of cobaltocene 196 6.4.9.1 FT-IR spectroscopy. 196 6.4.9.2 Powder XRD data... 197 6.4.10 Synthesis of Ferrocene 0.35 /Cobaltocene 0.15 @[Al(OH)(bdc)] n. 198 6.4.11 Synthesis of Ferrocene 0.1 /Cobaltocene 0.2 @[Al(OH)(bdc)] n... 198 6.4.12 Synthesis of 1,1 -ferrocenediyl-dimethylsilane 0.25 @[Al(OH)(bdc)] n. 198 6.4.13 Catalytic test reaction. 200 6.4.14 Preparation of PCP thin films. 201 6.4.14.1 Substrate preparation... 201 6.4.14.2 PCP film growth.. 201 6.4.15 Synthesis of [HDiD] x @[PCP] n (80) samples.. 202 6.4.16 Thermal treatment of [HDiD] m @[PCP] n (80) samples... 204 6.4.17 Decomposition procedure for the PCP matrix 205 6.4.18 SEM study of [PHDiD] p @[PCP] n samples 205 6.4.19 FT-IR spectroscopy 206 6.4.20 Thermal gravimetry analysis.. 209 6.5 References.. 210 Appendix... 212 A List of figures, schemes and tables. 212 A-1 List of figures.. 212 A-2 List of schemes... 217 A-3 List of tables... 218 B List of publications and conference contributions.. 219 B-1 List of publications. 219 B-2 Oral presentations... 220 B-3 Poster presentations 221 xiii