高等无机化学英文课件：Zheng_lecture001

1、Chemistry of Supramolecular Systems and Nanomaterials,Advanced Inorganic Chemistry,Supramolecular Chemistry,1987 Nobel Prize in Chemistry Charles J. Pedersen, Donald J. Cram, and Jean-Marie Lehn for syntheses of molecules that mimic important biological processes,1904-1989,1919-2001,1939,Jean-Marie

2、Lehn, PNAS, 2002, 99, 4763-68,Chemistry of Nanomaterials,1996 Nobel Prize in Chemistry Robert F. Curl, Jr. Sir Harold W. Kroto Richard E. Smalley for their discovery of fullerenes,Chemistry of Supramolecular Structures functions of individual molecules,Molecular Supramolecular,molecular or ionic bui

3、lding blocks held together by noncovalent interactions described by constitution, relative orientation, and extended structures. characterised (mostly) by physical properties properties possibly predictable from structure; functions, overall structure, cooperativity, and other factors,Examples of Su

4、pramolecular Design and Construction,Hydrogen Bonding,p-p Interaction,Metal Coordination,Two General Principles of Supramolecular Chemistry,Assumption: Non-covalent interactions do not significantly affect the intrinsic properties of the individual molecule. The supramolecular property or function i

5、s then a consequence of the collective property of the individual molecular components AND more,host-guest chemistry or molecular recognition self-assembly,A Brain Teaser,Have you ever put a bottle of into a freezer,If yes, what have you observed,Hydrogen Bonding in Ice,As compared with liquid water

6、, ice is porous and less dense due to the more ordered hydrogen-bonded network structure,Sure, you can! It all depends on how creative you are,Novel Supramolecular Interaction of Water,Ghosh, P. et al. J. Am. Chem. Soc. 2005, 127, ASAP,A Water Crown,The Water Wallpaper,A Beautiful Water Wallpaper,Ga

7、o, S. et al. Angew. Chem., Int. Ed. 2004, 43, 1374,Ice Structure It is simply beautiful,Where and when did it come from,inspired by biological systems, by nature in general built on synthetic organic and coordination chemistry originated from the “lock Stoddart, J. F. Angew. Chem. Int. Ed. 1996, 35,

8、 1155,Emil Fischer: The Lock 7017-7026,wavelength, nm,Effect of NaOH on Ultraviolet Spectrum,wavelength, nm,Effect of NaOH on the Ultraviolet Spectrum of Dibenzo-18-Crown-6 in Methanol,First Synthetic Compound Capable of Forming Stable Complexes with Na+ or K,Serendipity is happy chance. It is what

9、happens when you go looking for the needle in the haystack and find the farmers daughter.,accidental discovery extremely low yield surprising coordinating ability,accidental discovery,rational synthesis,Challenges and Opportunities,extremely low yield,surprising coordinating ability,reasonable yield

10、,designed coordinating ability,mechanistic studies,optimal reaction conditions,template effect,selective binding (Pedersen,improved stability (Lehn,novel phenomena (Cram,Charles J. Pedersen: Further Contributions,Prepared a series of crown-ethers, each with their own particular selectivity for vario

11、us cations Selectivity base primarily on size: Li 1.36 14-crown-41.2 - 1.5 Na 1.94 15-crown-51.7 - 2.2 K 2.66 18-crown-62.6 - 3.2,Its easy: some fit, some dont,One Practical Application,Benzene a colorless organic solvent,KMnO4 a purple inorganic solid, strong oxidant,KMnO4 is essentially insoluble

12、in benzene,Oxidation of Organic Substrates with KMnO4,A phase-transfer agent allows mixing of water-soluble reactants with organically soluble substrates in a two-phase mixture of solutions. The role of the agent is primarily that of an ion shuttle. The cation forms a tight ion pair with the reagent

13、 anion, permitting the anion to be transferred into the organic phase. The catalyst is a true catalyst in the classical sense and is not consumed in the reaction,Phase-Transfer Agents (Catalysts,Jean-Marie Lehn: 2.2.2 Cryptand,K+2.2.2 cryptate,Structural Re-organization - enthalpically unfavorable,D

14、onald J. Cram: Pre-organization,Spherands,Spherand” - preorganized binding site Selectivity for Li+ Na+ K,G023 kcal/mol,G0=19.3 kcal/mol,G06 kcal/mol, K: 1010-13 less than Spherand,Podand,Jean-Marie Lehn: Self-Assembly,3 Cu(I,2,Q: In what way are these complexes fundamentally different from Crams mu

15、tual recognition,Can be divided into four groups: 0, 1, 2, and 3 dimensional,micelle,reversed micelle,vesicle,Zero-Dimensional Assemblies,Object has no dimensions that are “infinite” in length. Has roughly a particular size,cylindrical micelle,One- and Two-Dimensional Assemblies,One dimension is muc

16、h longer (infinite) compared to the other two dimensions,Two dimensions are much longer (infinite) compared to the other dimension. One dimension is finite and relatively constant,layered structure,Three-Dimensional Assemblies,All three dimensions are very large (infinite) on the molecular scale,Why

17、 does it deserve to be a field of its own,The next logical step in synthetic chemistry Expression of collective properties Creation of new properties due to component synergism Interfacing with the biological Deng, B. L.; Ribbe, A. E. J. Am. Chem. Soc. 2002, 124, 11064,Self-Assembly of Nanoscopic Si

18、ngle-Molecule Magnets,Christou, G. et al. Angew. Chem. Int. Ed. 2004, 43, 2117,Mn84O72(O2CMe)78(OMe)24(MeOH)12(H2O)42(OH)6,Routes to Materials Previously Unattainable,Molecular data storage & transmission Molecular machinery Molecular sensors Advanced materials Drug & gene delivery Next-generation medicine (artificial organs/tissues, etc.,Envisioned Applications,Cancer Treatment Using a Self-Assembled System,From Clever Molecules to Smart Materials,Stoddart, J. F. et al Angew. Chem. Int. Ed. 2004, 43, 6486,binary network material from 8-nm and 30-nm gold nanoparticles with DNA,Nano-Assembly