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| NANOARCHITECTURES .5. GEOMETRICALLY-CONTROLLED AND SITE-SPECIFICALLY-FUNCTIONALIZED PHENYLACETYLENE MACROCYCLES |
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| Author(s): ZHANG JS, PESAK DJ, LUDWICK JL, MOORE JS |
| Source: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Volume: 116 Issue: 10 Pages: 4227-4239 Published: MAY 18 1994 |
| Times Cited: 135 References: 62 |
| Abstract: A convergent, stepwise synthesis of linear phenylacetylene sequences (PASs) is described. The methodology allows for complete control over chain length, sequence order of monomers, and functional group placement. Chain growth follows geometric progression thus allowing sequences of length 2(n), where n is the number of repetitive cycles, to be assembled in a total of just 3.n steps (two deprotections and one coupling for each cycle). Sequences of length other than 2(n) as well as sequences having a particular arrangement of co-monomer units, can also be realized by merging parallel repetitive cycles. Upon deprotection of the termini, these PASs can be cyclized to phenylacetylene macrocycles (PAMs) in high yield. Control over the ring structure of PAMs is determined by the chemistry of precursor PASs; the size of the macrocycle is related to the sequence length, while the geometry of the macrocycle and the position of the pendant functional groups on the macrocycle is governed by co-monomer sequence order. PAMs with four, five, six, seven, and twelve phenylacetylene monomer units, as well as a variety of site-specifically-functionalized PAMs, have been synthesized with this method. Finally, functional group transformations have been performed on some of the PAMs which lead to PAMs with new functionality. The versatile and efficient approach to this family of geometrically well-defined macrocycles offers potential for producing st set of modular building blocks to rationally assemble molecular crystals and liquid crystals. For this reason, the solid-state characteristics of the hydrocarbon skeletons are of interest. In spite of their solubility in common solvents, hydrocarbon PAMs are shown to yield crystals with remarkable thermal stability and high melting points. Three PAM hydrocarbons are shown not to exhibit melting transitions up to ca 400 degrees C, at which point an abrupt thermal irreversible reaction occurs, apparently involving a solid-state polymerization of the acetylene units. |
| Document Type: Article |
| Language: English |
Addresses:
1. UNIV MICHIGAN, DEPT CHEM, WILLARD H DOW LABS, ANN ARBOR, MI 48109 USA
2. UNIV ILLINOIS, DEPT MAT SCI & ENGN, URBANA, IL 61801 USA
3. UNIV ILLINOIS, DEPT CHEM, ROGER ADAMS LAB, URBANA, IL 61801 USA |
| Publisher: AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 |
| Subject Category: Chemistry, Multidisciplinary |
| IDS Number: NM988 |
| ISSN: 0002-7863 |
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