Synthesis And Properties Of Charge-Transfer Germenate-Sulfur Cluster And Metal Halide Compounds With Tetra(4-pyridyl)porphyrin

Porphyrin compounds widely exist in nature.Because of their unique structures,performance and special physiological activities,porphyrins have been applied in the fields of hybrid organic-inorganic materials chemistry and energy.In most cases,porphyrins derivatives usually act as electron donors in D-A ensembles.Such properties can be tuned as electron acceptors by introducing strongly electron-withdrawing substituents,such as high-valent metal ions,and protopyridine to the macrocycles.To date,intramolecular charge transfer systems have been mainly studied,but few reports have addressed supermolecular ionic D-A porphyrin system,especially the organic-inorganic hybrid system.Recently,the main group element germanium sulfide and lead iodine compounds have been widely used in semiconductor,nonlinear optics and photoelectric materials.We introduce the main group metal sulfides and halides into porphyrin system in order to obtain porphyrin compounds with novel structures and D-A properties,which is meaningful to research the photoelectric characteristics.In this thesis,(Ge₄S₁₀)^4-and metal manganese and lead ions were assembled with 5,10,15,20-tetrakis-?N-methyl-4-pyridyl?porphyrin to study the charge-transfer properties.This thesis includes the following contents:In introduction,properties and research progress of porphyrins reviewed briefly.The applications of porphyrins in hybrid organic-inorganic materials chemistry and energy utilization were summarized.Besides,the applications in optical,electrical fields of porphyrin charge transfer compounds were reviewed briefly.Finally,the research ideas and the main contents of the thesis are introduced.In Chapter 2,a germanium chalcogenide cluster(Ge₄S₁₀^4-)is chosen as an electron donor and a methylated tetrakis?4-pyridyl?porphyrin?5,10,15,20-tetrakis-?N-methyl-4-pyridyl?porphyrin,TMPyP?is selected as an electron acceptor to create chalcogenide cluster-porphyrin CT compounds(TMPyP-Ge₄S₁₀)·5H₂O?1?and(MnTMPyPGe₄S₁₀)·13H₂O?2?.Their crystal structures have been characterized by single-crystal X-ray diffraction.Compound 1 is an ionic CT salt assembled through interion interactions,and compound 2 is a neutral CT dyad formed by metal-ligand axial coordination of the chalcogenide cluster with manganese porphyrin.The strong charge transfer properties are revealed by electronic spectra,theoretical calculations,¹H NMR,and ESR.The CT intensity of the chalcogenide cluster-porphyrin system can be modulated by metalation.The fluorescence and photocurrent response properties of 1 and 2 are related to the CT intensity.These compounds would be promising material for inorganic-organic photoelectronic devices.In Chapter 3,three Tetra?4-pyridyl?porphyrin with different alkyl chains,TMPyP?PF₆?_4?[H₂T?N-C₄-4-Py?P][PF₆]_4?[H₂T?N-C₈-4-Py?P][PF₆]₄,were synthesized and PbI₂ was introduced into the porphyrin system to obtain compounds[TMPyPPb]₂[Pb₆I₂₀]?3?,{?TC₄PyP?(Pb₄I₁₂)·2DMF}_n?4?,and{?TC₈PyP?(Pb₄I₁₂)·8DMF·2H₂O}_n?5?.Their crystal structures have been characterized by single-crystal X-ray diffraction,3 contained Pb₆I₂₀^8-independent anion units,while{Pb₄I₁₂}_n chain was formed in 4 and 5.The relationship between the length of alkyl chains and crystal structures,charge transfer,and photocurrent response properties were discussed.Electron spectra results show that 3,4 and 5 are charge transfer compounds.The ESR results confirmed that charge transfer occurred in 3.3,4 and 5 showed a photocurrent response,in the order of 3>4>5.These indicate that 3,4 and 5,especially 3,would be promising material for inorganic-organic photoelectronic devices.