In Situ Reaction And Iodine Adsorption Of Porous Supramolecular Networks Constructed By ?-substituted Benzimidazole Derivative Ligands

As a very important research field in both coordination and organic chemistry,in-situ reactions have been extensively investigated for many decades and led to the discovery of new organic reactions,elucidation of reaction mechanisms,as well as generation of novel coordination compounds,especially those that are inaccessible by direct synthesis from the ligands.The research of in-situ reactions always focuses on the characterization of their single crystal structures,then,analysis its mechanism.But both solution and crystallography were still limited.That makes the information of mechanism investigation incompleted.In this thesis,one hand,we have choosen a ligand(1-methyl-lH-benzo[d]imidazol-2-yl)methanamine(L1)and FeCl3·6H2O to construct a series of organics and coordination compounds by solvothermal or microwave-assisted,such as,C37H30N10(L4),[CssH12N15]·Cl(L6+),[Fe(C9H8N3)3]·2ClO4(Fe(L1)3),etc.The X-ray diffraction and high-resolution electrospray ionization mass spectrometry(ESI-MS)are used for tracking the formation of the products.On the other hand,we were using two one-dimensional chains for selective sorption and iodine inclusion constructed by Hebic and Zn(NO3)2-6H2O or Co(NO3)2·6H2O.Its iodine content and crystal conversion were systematic investigated.This thesis is divided into four chapters:The first chapter was the introduction,the research background and hot issues of in situ reaction and free radicals inclueding.Simultaneously,we have introduced the application of ESI-MS technique in organic catalysis and solution chemistry of coordination complexes,which provides new ideas and new methods to the reaction mechanism.The thesis showed the soft materials and its application,and some results about iodine inclusion in our group,as well as the significance of the topic of this issue.In chapter 2,we reported the synthesis,structure and thermal,optical and magnetic properties of a stable radical,tris(4-methyl-l-(1-methyl-IH-benzo[d]imidazol-2-yl)-4H-benzo[d]imidazo[1,5-a]imidazol-3-yl)methylium(L6+),the crystallography,EPR(g=2.057)and magnetic[?=29.5(5)K]measument indicated that the organic compound was a cation radical.and it was ferromagnetic.Cyclic voltammetry reversible reduction between-1.8 and-0.5 V.Theoretical calculations of IR,UV are basically the same with the measured values.Interestingly,the UV-vis showed colour changes tardily from blue to colourless when the L6+ added into methanol dissolved with KOH,and it becomes to be(L6-OCH3)K+(m/z=982.36).As the synthesis of L6+,there are series of compounds during the synthesis.Such as,Fe(C9H8N3)2(OCH3)CI(Fe(L1)2(OCH3)CI)?[Fe(C9H8N3)2(H2O)2]·Cl2(Fe(L1)2(H2O)2)?[Fe(C9H8N3)2O]2·xsolvent([Fe(L1)2O]2)?Fe(C9H8N3)2Cl2(Fe(L1)2Cl2)?[Fe(C9H8N3)3]·2ClO4(Fe(L1)3)?[C37H31N10]·(H2O)3Cl(L4)?[C55H42N15]·(CH3OH)3Cl(L6+).In chapter 3,in search of the mechanism of the reaction,both crystallography and ESI-MS were used.The single crystals were determined by crystallography,and the reaction mixture solution were diluted with methanol analyzed by ESI-MS.The ongoing reaction ESI-MS showed the species C18H,6N5+(HL2+,m/z=302.14)?C19H16N5+(L2+C+,m/z=314.14)?[Fe(C9H8N3)2-H]+([Fe(L1)2-H]+,m/z=377.12)?C37H29N10(L4,m/z=615.27)were important for the synthesis of L6+.Structurally,as one part of L6+,L4 is key intermediate can direct synthesis of L6+in methanol under solvothermal.These methods are very useful for investigating the reaction mechanism,also for novel and feature compounds,moreover,this study can provide us more theoretical basis to controlled synthesis of the compounds.In chapter 4,in search of porous materials for selective sorption and iodine inclusion,we have found two networks made of chains with a kink at the metal nodes held together by supramolecular interactions(H-bond and ?…? stacking).The solvent can be removed and replaced reversibly without loss of crystallinity,as demonstrated by single-crystal-to-single-crystal crystallography.In contrast,iodine uptake degrades the crystallinity to amorphous,and it regains its crystalline state after removal of the iodine at 200?.Slight differences in behavior of the sorption and inclusion properties between the tetrahedral metal nodes,Zn and Co,are associated with the size of the nodes.An important feature is the extent of iodine that can be included between the chains that is doubled with temperature from 30 to 100? and exceeds the weight in mass of the compounds.