化学综合实验3.新型金属Co(配合物原位水热合成、结构表征及性能研究
3. 新型金属Co(II)配合物原位水热合成、结构表征及性能研究 化学综合实验
实验课时具体安排如下：1、实验相关内容讲解，进行实验（B312)2、所合成产物的后处理（B312)红外光谱测定（B308)荧光光谱测定（B307)磁性测定（B306)热失重测定（B333）3、相关软件讲解，实验报告处理（B332）
实验课时具体安排如下： 1、实验相关内容讲解，进行实验(B312) 2、所合成产物的后处理（B312） 红外光谱测定(B308) 荧光光谱测定(B307) 磁性测定(B306) 热失重测定(B333) 3、 相关软件讲解，实验报告处理（B332）
配合物配位原子2+NH3SO.2[Cu（NH3]4]SO4的结构式：H,N+Cu+NH3NH3中心离子配位数
2+ Cu NH3 H3N NH3 [Cu(NH3 )4 ] SO4的结构式： NH3 SO4 2- 中心离子 配位数 配位原子 配合物
不同结构的有机配体Simple: commerciallyExo-bidentate:availablePyridyl-typeComplicated: chiral,carboxylateX=(CHn,Smulti-dentateNH2NH2000LOHChelate:terminal ligandMonodentate ligands can alsoact as terminalligands
不同结构的有机配体 N N N N N X N N N N N N N N N N N O O O O O O N O O X = (CH2 )n, S O O O O N X O O Exo-bidentate: Pyridyl-type carboxylate Simple: commercially available Complicated: chiral, multi-dentate O OH O O O O N N N N O O O O O O O O N N NH2 NH2 Chelate: terminal ligand, Monodentate ligands can also act as terminal ligands
不同金属离子的配位构型a-c)Ag', Cu', HgDT-shapedTrigonalplanarLineard)Pd,Pt,Cull,Nila)b)RSquare anti-prismatice)Znl,Coll,Cdl!j) Ln', Lanthanidef)CulZnlCd,Mn!l(rare-earth)g) Cu, Zn,Mnl!TetrahedralSquareplanarTrigonal bipyramidale)d)f)h,i) Cu, Zn",Mn!大Cd,Fell,Fe,ColNil,etcOctahedralSquarepyramidalTrigonalprismatich)g)D
不同金属离子的配位构型 Linear Trigonal planar T-shaped Square planar Tetrahedral Square pyramidal Trigonal bipyramidal Octahedral Trigonal prismatic a) b) c) d) e) f) g) h) i) Square anti-prismatic j) a-c) AgI , CuI , HgII d) PdII , PtII, CuII, NiII e) ZnII, CoII, CdII f) CuII, ZnII, CdII, MnII g) CuII, ZnII, MnII j) LnIII, Lanthanide (rare-earth) h,i) CuII , ZnII, MnII , CdII, FeII, FeIII, CoII , NiII , etc
配位聚合物O-D:triangles, squares,wheels,brackets,etc.1-D:zigzaglinearrailroadladderhelical3-D:cubicdiamondoid
M M M M M M M M M M M M M M M M M M M M linear zigzag helical ladder railroad M M M M M M M M M M M M M M M M M M diamondoid cubic 0-D: triangles, squares, wheels, brackets, etc. 1-D: 3-D: 2-D: 配位聚合物
配位聚合物作为一类重要的分子基材料，在吸附分离、能量存储、分子磁性、分子识别与组装、药物缓释、光电材料等方面有重要的应用前景，是当今化学学科最活跃的前沿领域之一Mn12吸附分离分子磁性能量存储(3)(2)UV5501m300ammdiaticrweadno分子识别与组装药物缓释光致变色材料
配位聚合物作为一类重要的分子基材料，在吸附分离、能量 存储、分子磁性、分子识别与组装、药物缓释、光电材料等方面 有重要的应用前景，是当今化学学科最活跃的前沿领域之一。 分子识别与组装 药物缓释 吸附分离 能量存储 分子磁性 Mn12 光致变色材料
Microporous Coordination Polymersinoganic MaterlasCarbon MaterialsPorousMaterialsCoodintonPolymenCrystallineHybridinorganic-organic(MetalOrganicFrameworks)PermanentporosityandadsorptioncapacityPorevolumesupto91%S.Kitagawaetal.Densitiesaslowas0.21g/cm3Angew.Chem.2004,432334
Microporous Coordination Polymers • Crystalline • Hybrid inorganic-organic (Metal Organic Frameworks) • Permanent porosity and adsorption capacity • Pore volumes up to 91% • Densities as low as 0.21 g/cm3 S. Kitagawa et al., Angew. Chem. 2004, 43, 2334
微孔配合物储氢2nm50nm0.7nmMicropore'MesoporeMacroporeThe US department ofEnergy's targetShort-term:6.0wt % by 2010Long-term: 9.0wt % by 2015Additional goal: store hydrogen nearambient temperature and reasonableMOF5[ZnO(BDC)3(DMF)(CH,CI)lpressures(<100bar)Nature 1999276
0.7nm 2nm 50nm Micropore Mesopore Macropore 微孔配合物储氢 MOF 5 [Zn4O(BDC)3 (DMF)8 (C6H5Cl)]n The US department of Energy’s target Short-term: 6.0wt % by 2010 Long-term: 9.0wt % by 2015 Additional goal: store hydrogen near ambient temperature and reasonable pressures (<100bar) Nature 1999 276
OPZOCDPYZPORECNR-BDCR-BDCR-BDC2,6NDCHPDCBPDCPDCTPDCNOW7.2wt % at 77K
7.2wt % at 77K