高等無機化學(xué)英文課件：ppt-for-finalexam2013

1、Classically: Chemists: a kind of low entropy container atoms, molecules or ions neatly packed in 3D order covalent solids extended covalent bonds, ionic crystals Coulombic interaction, molecular crystals weak intermolecular interactions Many synthetic chemists and crystallographers: chemical cemeter

2、ies, static, lifeless fundamental and unbeatable tools to obtain hyperfine structural information by diffraction collective behavior of billion of billion atoms and molecules,top: in solution or gas, “alive”; bottom: in crystal, i.e.,solid, “died,If we see crystal supramolecularly, molecular crystal

3、 is very large supermolecule, hypermolecule, or extended but periodic supramolecular entity, whose formation (through non-covalent bonds) is based on molecular recognition and self-assembly or self-organization processes and may have collective physical and chemical properties,1989. Gautam R. Desira

4、ju: in his book “ Crystal Engineering: The Design of Organic Solid,Definition by Dario Braga, 2000,D. Braga, J. C. S. Dalton Trans., 2000, 21, 3705,Birth or rebirth of CE due to 1.success of supramolecular chemistry shift of interest from molecular based chemistry to the chemistry of molecular aggre

5、gates 2.the urge for more utilitarian objectives for chemical science 3.the progress in computing and diffraction tools,The initial but the central idea of CE: making crystals with a purpose constructing intelligent materialssmart materials with useful properties, by choosing adequate building block

6、s Crystal Synthesis,Crystal synthesis vs Molecular synthesis,Macroscopic Molecules Non-covalent Recognition-directed self-assembly Long-range ordering and bulk (collective) properties Difficult in prediction and control,Microscopic Atoms + Molecular Fragments Covalent Molecular properties, no long-r

7、ange-ordering Well developed in prediction and control,CE is at the intersection of,The Process of Crystal Engineering,some idea, goal,look at what an interesting and attractive three-dimensional structures I have just determined, and called the molecular chess board ”- newly discovered Penny Blacks

8、 in Angew. Chem. BeF2 a=6.67 ; C a=3.567 Bond-strength: CC 607; SiO 798; BeF 577 kJ/mol,Hoffmann, et al., JACS 1994, 116, 9634,Interpenetrated diamond network of SiO2BeF2: material harder than diamond,S. R. Batten, CrystEngComm, 2001, 18, 1-7,Schematic illustration of spin coupling behaviors,Advanta

9、ges of Molecular Magnetic Materials over Conventional Magnetic Materials (metal / intermetallic and metal oxides): Transparency Low density Electrical insulation Low temperature fabrication Abundance in magnetism Combined or multi-functionalities Chemical fabrication Disadvantage: Low TC, in most ca

10、ses,4.10 Porous coordination polymers or metal-organic frameworks (MOFs) See O. M. Yaghi et al., Acc. Chem. Res., 2001, 34, 319-330 J. Solid State Chem., 2000, 152, 3-20 Science, 2002, 295, 469 Science, 2001, 291, 1021 S. L. James et al., Angew. Chem. Int. Ed., 2002, 41, 764 etc,Nature hates vacuum,

11、Strategies for construction of porous frameworks Interpenetration should be avoided. Using large nodes Using long, rigid and bulky bridging ligands Pillared layers Using short ligands but forming thick walls Using removable guest,Decoration of node replacement of a vertex of framework by a group of

12、vertex node: from metal ion to metal clustersecondary building units (SBUs) carboxylic acid used M-O-C clusters,Using large nodes and long, rigid and bulky bridging ligands by O. Yaghi et al,X-ray structures of porous crystalline materials,4Cr3O tetrahedron unit, a90 , V700,000 3, pore30 to 34,MIL10

13、1,Pillared layers, by S. Kitagawa et al. Recent reviews: Chem. Soc. Rev., 2005, 34, 109 J. Solid. State Chem., 2005, 178, 2420,Angew Chem. Int. Ed., 1999, 38, 140,pillar,Angew Chem. Int. Ed., 2002, 41, 134,One dimensional array of oxygen molecules (Science, 2002, 298, 2358,S. Kitagawa et al., Highly

14、 controlled acetylene accommodation in a metalorganic microporous material Nature, 2005, 436, 238, C Drillon, M. Ed., Magnetism: Molecules to Materials, v. 5, Wiley-VCH, 2005, pp269-270,Guest = Iodine, CH3COOH, C6H6, Furan, DMF, etc,R-, S-, and R/S- CH3C*HClCH2OH,手性客體的包合 手性磁體 Adv. Funct. Mater., 200

15、7, 17, 577,Photo Magnets,SPMnCr(ox)3 Adv. Mater., 2001, 13, 1411,Angew. Chem. Int. Ed., 2003, 42, 4810,Green NeedleCr(CN)6Mn(S)-pnH(H2O)(H2O)(TC = 38 K,Orthorhombic, space group P212121, a=7.6280(17), b=14.510(3), c=14.935(3), V=1653.1(6)3, Z=4, R1=0.0265 for 2377 data (I2(I), wR2=0.0709 for 2383 un

16、ique data, Flack parameter =0.01(3,S,S,7.31,7.77,8,Inorganic Polymers non-carbon elements (B, N, Si, P, etc.,Why IOPs? Predicted decrease in petroleum industry Long-term stability of organic polymers Pollution concerns Plus Inherently interesting properties of metal elements redox, magnetic, optical

17、, etc,Poly(siloxanes) - Silicones,Mark. J. E. Acc. Chem. Res. 2004, 37, 946,Si-O bond strength thermal stability,Poly(siloxanes) - Silicones,Flexibility: torsion flexibility and bending flexibility. Low glass transition temperature, Tg, (ca. -127C,Non-medical uses: adhesive, coating, less cracking a

18、nd chipping,Cauliflower,Broccoli,Making Connections,/chudler/synapse.html,Dendrimer are highly branched,monodisperse macromolecules emanatingfrom a central core,What Are Dendrimers,A Third-Generation PAMAM Dendrimer,Microreactors Molecular Boxes Separation Agents Enzymati

19、c Models Novel Catalysts,A Dendritic Nanoreactor Providing Both Catalysis and Rapid Mass Transfer,Frchet, J. M. J. PNAS 2002, 99, 4782,Frchet et al. Angew. Chem. Int. Ed. 1999, 38, 1422,Light-Harvesting Dendrimers,Synthesis of bona fide Metallodendrimers of Clusters,Mg,Al)5(Si,Al)8O20(OH)28H2O Palyg

20、orskite (clay, layered,Indigo,From Maya Blue to 21st Century Materials,Scratch-Resistant Coating,Easy-to-Clean Stainless Steel,Dental Applications Filling Materials,Poly(siloxanes) - Silicones,Leisure Applications Gas Barrier,Chemistry of Nanomaterials,1996 Nobel Prize in Chemistry Robert F. Curl, Jr. Sir Harold W. Kroto Richard E. Smalley for their discovery of fullerenes,Supramolecular Design and Construction,Building Blocks Non-covalent Interactions,Collective Prop