| 查看: 1458 | 回复: 13 | |||
| 【奖励】 本帖被评价5次，作者cc136520增加金币 4.25 个 | |||
| 当前主题已经存档。 | |||
| 当前只显示满足指定条件的回帖，点击这里查看本话题的所有回帖 | |||
[资源]
超分子建筑：从分子到材料
|
|||
|
书籍名称 超分子建筑：从分子到材料 书籍分类 材料 书籍作者 徐筱杰 编 ISBN 750233499 书籍出版社 科学技术文献出版社 书籍格式 pdf(scanned) 书籍版本 第一版 下载地址 http://www.box.net/shared/hx10et2z2m 书籍大小 7.6M 第一章 从分子到材料 第二章 分子间的相互作用 第三章 分子识别原理及机制 第四章 超分子模型的构造 第五章 介观模型方法及其在超分子化学中的应用 第六章 超分子体系中的电子及能量转移反应 第七章 基于金属配位作用的超分子建筑——自组装的金属模板控制 第八章 两亲分子聚集体的活性控制 第九章 基于自组织的超分子建筑 第十章 固态超分子体系的构筑——晶体工程 from : http://chem8.org/bbs/viewthread. ... fromuid=10#pid38299 password: www.chem8.org |
回复此楼» 猜你喜欢
二苯甲酮亚胺的合成
已经有1人回复
-
聚左旋乳酸的作用与机制：从胶原再生到组织修复
已经有0人回复
-
有机高分子材料论文润色/翻译怎么收费?
已经有224人回复
-
可生物降解聚酯聚己内酯的性能分析与发展趋势
已经有0人回复
-
带膜支架的膜和支架之间的结合力如何测试
已经有2人回复
-
西交利物浦大学奖学金博士招生（生物传感或机器学习方向）
已经有1人回复
-
南方科技大学招收金属材料方向博士生
已经有23人回复
-
可降解聚酯材料在医疗器械中的应用趋势与创新方向
已经有0人回复
-
可降解微球如何提升药物精准治疗效果
已经有0人回复
-
静电纺丝膜分层问题
已经有0人回复
-
什么脱膜剂可以完全清洗干净啊？
已经有2人回复
» 本主题相关商家推荐: (我也要在这里推广)
|
Raymond Group: Supramolecular Chemistry researchtitle.jpg (13.14 KB) 2007-6-15 08:46 http://www.cchem.berkeley.edu/knrgrp/sup.html Supramolecular Coordination Chemistry Introduction The Raymond group has developed a predictive design strategy resulting in the synthesis of various high-symmetry coordination clusters including M2L3 helicates and mesocates, M4L6 and M4L4 tetrahedra, M6L6 and M8L8 cylinders, and M8L6 octahedra. These examples all focus on the coordination of three bidentate chelators to a tri- or tetravalent metal ion in a pseudo-octahedral fashion at the apices of the clusters to generate local three-fold symmetry at these metal centers. These chelators are contained in rigid, symmetric multi(bidentate)-ligands which supply the other symmetry elements of the cluster (2-fold, 3-fold, or mirror plane). By simultaneously fulfilling the symmetry requirements of both the ligand and metal centers, discrete high-symmetry clusters are generated under thermodynamic control. We are exploring the self-assembly of new clusters, thermodynamics and kinetics of cluster formation and host-guest interactions, electrochemistry, luminescence, ligand exchange, and chiral resolution and isomerization in the context of these supramolecular clusters. Cluster Design and Synthesis Our design strategy has already allowed us to generate many different cluster architectures, as mentioned above. Self-assembly of helicate complexes of the formula [M2L3]6- and tetrahedral complexes with the formula [M4L6]12- can be achieved via the self-assembly of an octahedrally coordinating, trivalent metal ion (e.g., Fe3+ or Ga3+) with an appropriate bis-bidentate ligand, L. The use of diamagnetic Ga3+ in the synthesis of these clusters has enabled study of these novel molecules by NMR spectroscopy, as these highly symmetric molecules have a distinctly simple spectrum, shifted from that of the free ligand. suprafig1.jpg (28.82 KB) 2007-6-15 08:46 Three-fold symmetric tris-bidentate ligands have been used to synthesize clusters with triangular faces, such as M4L4 tetrahedra, M6L6 and M8L8 rings, and M6L8 octahedra. Again a labile tri- or tetra-valent metal ions is used as the vertex of the given topology, but the ligand comprises a face of the cluster, rather than an edge as in the earlier example. A continuing pursuit in our laboratories focuses on the synthesis of new cluster topologies, as well as generating larger versions of the clusters we already have in hand. For example, the use of a five-fold symmetric ligand, may allow for formation of a cluster with icosahedral symmetry, whereas using "expanded" versions of our new ligands, we hope to synthesize clusters with larger cavities. suprafig2.jpg (28.07 KB) 2007-6-15 08:46 Host-Guest Chemistry A Capsule with a Dangling Guest Normally, a molecule must be either inside or outside the cavity at any given time. But when a molecule with both cationic guest and repulsive negative terminus components is used, one end of the molecule is encapsulated by the host, while the other end remains outside the capsule. Since doing chemistry inside the chiral, nanoscale environment of the cluster requires reactants to enter and product to leave, it is important to demonstrate the feasibility and mechanism of this process. Thus, guests were designed, which would be encapsulated but would dangle one end out of the cavity. A hydrocarbon chain served as the linker, with a positively-charged group 鈥?known to act as a guest by itself 鈥?at one end, and a negatively-charged group at the other. When dissolved in water with the negatively-charged host cluster, the positive end winds up inside the capsule, but the negative end of the same molecule remains outside. The slender hydrocarbon chain pokes through one of the expandable gaps, allowing the negative tail to dangle in the water surrounding the capsule. The NMR signals of the exterior and interior methylene protons clearly show these relative positions, and mass spectra show that the guest flies with the host cluster. While simple, this approach is extremely effective 鈥?with the right chain length, binding constants upwards of 104 have been achieved! --Bryan E.F. Tiedemann dangling.jpg (41.74 KB) 2007-6-15 08:46 Enantioselective Encapsulation of Reactive Ruthenium Complexes In collaboration with the Bergman Group react1.jpg (4.28 KB) 2007-6-15 08:46The naphthalene-based M4L6 metal-ligand assembly can encapsulate a variety of ruthenium based sandwich- and half sandwich-complexes into its chiral, well-defined cavity. The encapsulations of the chiral ruthenium complexes proceed with diastereoselectivities up to 70%, and the resolved assembly can be exploited for a dynamic resolution of the organometallic species. Fiedler, D.; Pagliero, D.; Brumaghim, J. L.; Bergman, R. G.; Raymond, K. N. Inorg. Chem. 2004, 43, 846. Fiedler, D.; Leung, D. H.; Bergman, R. G.; Raymond, K. N. J. Am. Chem. Soc. 2004, 126, 3674. Organometallic Reactivity within a Supramolecular Host In collaboration with the Bergman Group Since many of these supramolecular assemblies provide large cavities that can encapsulate monocationic guests, we have turned towards the encapsulation of chemically reactive monocationic organometallic species. The cavity of the nanovessel may provide a well-ordered second sphere environment that may affect the reactivity of the encapsulated metal complex. The naphthalene-based chiral supramolecular [Ga4L6]12- tetrahedral host has been shown to encapsulate a variety of organometallic half-sandwich iridium complexes in aqueous solution. This encapsulatoin has been shown to be highly dependent on both the size and shape of the iridium guest. Modest to good diastereoselectivities of encapsulation can be observed. In addition, some of these iridium host-guest assemblies react with organic substrates such as aldehydes and ethers via C-H bond activation, which occurs within the host interior. The well-defined shape of the host cavity serves to direct the reactivityof the guest with high size and shape selectivity as well as modest diastereoselectivity that is not seen with the unencapsulated species. iridium.jpg (57.19 KB) 2007-6-15 08:46 Leung, D. H.; Fiedler, D.; Raymond, K. N.; Bergman, R. G. Angew. Chem. Int. Ed. 2004, 43, 963. Supramolecular Acceleration of an Organic Reaction In collaboration with the Bergman Group react2.gif (4.78 KB) 2007-6-15 08:46The supramolecular metal-ligand assembly can also be employed as a catalytic host for the unimolecular carbon-carbon bond-forming rearrangement of enammonium cations. The restricted reaction space of the supramolecular structure forces the substrates to adopt a reactive conformation upon binding to the interior. With no transition state-stabilizing functional groups within the cavity, the assembly achieves up to 1000-fold rate acceleration of the rearrangement. Release and hydrolysis of the product allow for catalytic turnover. Solution Dynamics and Cluster Resolution As the design and synthesis of supramolecular assemblies becomes more accessible, we are interested in characterizing their solution behavior. Understanding of the dynamic behavior of these species may be particularly important as we endeavor to develop the chemistry of nanoscale reaction flasks. An intriguing feature of some of our supramolecular assemblies is that they are chiral; we have reported formation of homochiral supramolecular assemblies from achiral, labile metal-ligand systems. Study of the racemization of these species advances our description of the dynamic behavior of supramolecular coordination clusters in general. Initially, racemization of a homochiral M2L36- cluster (a helicate) was investigated and characterized as proceeding by a Bailar Twist mechanism. Proton independent and proton dependent mechanisms were elucidated and reported. suprafig3.jpg (6.1 KB) 2007-6-15 08:46 Chiral resolution of a racemic (DDDD and LLLL mixture) homochiral M4L612- cluster (3) with a chiral counter ion allowed for investigation of the racemization of a larger system. We predicted that the mechanical coupling between metal centers which forces the structure to be homochiral, would also inhibit cluster racemization. A solution (at pH = 10) of the resolved DDDD-[(Et4N)Ì M4L6]11- was monitored by CD spectroscopy for three months, and indeed, no cluster racemization was observed. From labile metal-ligand components an inert chiral species is created! Another dynamic behavior exhibited by certain supramolecular species is the interconversion between two discrete assembly forms. Such a process has been reported in several labile systems. The driving force is often thermodynamic stabilization of the new form through host-guest interaction. We have reported two such examples: conversion of M2L3 helicate (8) to M4L6 tetrahedron (2) and conversion of (DL) mesocate to (DD, LL) helicate (1). In both processes, guest encapsulation was determined to be the driving force. Thermodynamic parameters were reported for the mesocate-helicate system, and we have begun to investigate the helicate-tetrahedron conversion process. suprafig4.jpg (11.69 KB) 2007-6-15 08:46 8 2 Electrochemical Studies The versatile catecholamide chelating group, featured in many supramolecular assemblies, coordinates a variety of hard metal ions in several oxidation states. By incorporating a metal ion with multiple accessible oxidation states, electrochemically active clusters may be prepared. Stable vanadium tris catechol complexes are known to exist for tri-, tetra-, and pentavalent vanadium, and cyclic voltammetry measurements reveal one-electron redox waves for the [V(cat)3]-/2- and [V(cat)3]2-/3- redox couples.1 If similar one electron redox reactions occur at the vertices of the V4L6 tetrahedron, cycling between [VIII4L6]12- and [VV4L6]4- involves eight individual electron transfer reactions with a single complex. Such behavior may lead to applications using V4L6 as an electron shuttle species. An in-depth study electrochemical study is underway to investigate the redox behavior for vanadium supramolecular assemblies in both aqueous and DMF solutions. The V4+ catecholamide complex [V(cam)3]2- (H2cam = 2,3-dihydroxy-N-methyl-benzamide) was synthesized as a mononuclear model complex for the dinuclear [V2L3]4- helicate and the tetranuclear [V4L6]8- tetrahedron. In DMF, the V4+/3+ redox couple behaved almost reversibly for all three compounds, with [V2L3]4-/6- and [V4L6]8-/12- exhibiting a single broad wave in the CV. This is consistent with an overall redox process that proceeds via individual one-electron transfer steps from identical, non-interacting sites, and is supported by CV simulations. Aqueous solutions exhibit more complicated redox activity, caused by processes occurring on the mercury electrode surface and possibly dissociation reactions upon partial reduction of the cluster sites. Cooper, S. R.; Koh, Y. B.; Raymond, K. N. J. Am. Chem. Soc. 1982, 104, 5092-5102. [ Last edited by cc136520 on 2008-1-12 at 22:33 ] |
6楼2008-01-12 22:32:07
more about supraolecular
|
书籍名称 超分子化学-合成受体的分子识别与组装 书籍分类 书籍作者 刘育 ISBN 7310016416 书籍出版社 南开大学出版社 书籍格式 pdf(scanned) 书籍版本 第一版 书籍大小 17.6M download from http://chem8.org/bbs/viewthread. ... fromuid=10#pid38305 超分子层状结构——组装与功能 347.jpg (9.08 KB) 2007-12-5 10:42 作 者 沈家骢 出 版 社 科学出版社 书 号 03-012081-7 丛 书 21世纪科学版化学专著系列 责任编辑 周巧龙 出版时间 2004年3月 内容提要 超分子化学是关于分子聚集体与分子间相互作用的化学，它与其他学科交叉融合形成超分子科学，被认为是21世纪新概念和高技术的一个重要源头。本书集沈家骢院士研究集体及合作者近10年的科研积累，详细介绍了超分子结构与功能这一交叉前沿领域的研究成果及发展趋势。内容包括一维、二维及三维层状组装技术，界面组装与表面图案化，无机/有机纳米复合体，新型超分子构筑基元，分子间相互作用的单分子力谱研究等。 本书可供从事超分子化学、材料科学、纳米科学、胶体与界面化学、高分子化学与物理和生命科学等领域的科研人员及研究生阅读、参考。 http://chem8.org/bbs/viewthread. ... fromuid=10#pid38307 |
2楼2008-01-10 14:31:26
3楼2008-01-10 20:45:47
★ 一星级,一般
|
http://muchong.com/bbs/viewthread.php?tid=683680 http://muchong.com/bbs/viewthread.php?tid=661146 已经有了两本，谢谢第3本！ |
4楼2008-01-10 21:14:29