DC Field | Value | Language |
---|---|---|
dc.contributor.author | Wang, Cheng | ko |
dc.contributor.author | Dyar, Scott M. | ko |
dc.contributor.author | Cao, Dennis | ko |
dc.contributor.author | Fahrenbach, Albert C. | ko |
dc.contributor.author | Horwitz, Noah | ko |
dc.contributor.author | Colvin, Michael T. | ko |
dc.contributor.author | Carmieli, Raanan | ko |
dc.contributor.author | Stern, Charlotte L. | ko |
dc.contributor.author | Dey, Sanjeev K. | ko |
dc.contributor.author | Wasielewski, Michael R. | ko |
dc.contributor.author | Stoddart, J. Fraser | ko |
dc.date.accessioned | 2013-03-12T21:08:33Z | - |
dc.date.available | 2013-03-12T21:08:33Z | - |
dc.date.created | 2012-12-26 | - |
dc.date.created | 2012-12-26 | - |
dc.date.issued | 2012-11 | - |
dc.identifier.citation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.134, no.46, pp.19136 - 19145 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10203/103517 | - |
dc.description.abstract | The electronic properties of tetrathiafulvalene (TTF) can be tuned by attaching electron-donating or electron-withdrawing substituents. An electron-rich macrocyclic polyether containing two TTF units of different constitutions, namely 4,4'-bis(hydroxymethyl)-tetrathiafulvalene (OTTFO) and 4,4'-bisthiotetrathiafulvalene (STTFS), has been synthesized. On two-electron oxidation, a hetero radical dimer is formed between OTTFO center dot+ and STTFS center dot+. The redox behavior of the macrocyclic polyether has been investigated by electrochemical techniques and UV-vis and electron paramagnetic resonance (EPR) spectroscopies. The [2]catenane in which the macrocyclic polyether is mechanically interlocked with the cyclobis(paraquat-p-phenylene) (CBPQT(4+)) ring has also been prepared using template-directed protocols. In the case of the [2]catenane, the formation of the TTF hetero radical dimer is prevented sterically by the CBPQT(4+) ring. After a one-electron oxidation, a 70:30 ratio of OTTFO center dot+ to STTFS center dot+ is present at equilibrium, and, as a result, two translational isomers of the [2]catenane associated with these electronically different isomeric states transpire. EPR titration spectroscopy and simulations reveal that the radical states of the two constitutionally different TTF units in the [2]catenane still experience long-range electronic intramolecular coupling interactions, despite the presence of the CBPQT(4+) ring, when one or both of them are oxidized to the radical cationic state. These findings in the case of both the free macrocyclic polyether and the [2]catenane have led to a deeper fundamental understanding of the mechanism of radical cation dimer formation between constitutionally different TTF units. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | MESOPOROUS SILICA NANOPARTICLES | - |
dc.subject | FIELD EFFECT TRANSISTORS | - |
dc.subject | LIGHT-EMITTING-DIODES | - |
dc.subject | MIXED-VALENCE | - |
dc.subject | BUILDING-BLOCKS | - |
dc.subject | SUPRAMOLECULAR CHEMISTRY | - |
dc.subject | CONDUCTING POLYMERS | - |
dc.subject | CONJUGATED POLYMERS | - |
dc.subject | ROOM-TEMPERATURE | - |
dc.subject | PI-DIMERS | - |
dc.title | Tetrathiafulvalene Hetero Radical Cation Dimerization in a Redox-Active [2]Catenane | - |
dc.type | Article | - |
dc.identifier.wosid | 000311324900040 | - |
dc.identifier.scopusid | 2-s2.0-84869412858 | - |
dc.type.rims | ART | - |
dc.citation.volume | 134 | - |
dc.citation.issue | 46 | - |
dc.citation.beginningpage | 19136 | - |
dc.citation.endingpage | 19145 | - |
dc.citation.publicationname | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1021/ja307577t | - |
dc.contributor.nonIdAuthor | Wang, Cheng | - |
dc.contributor.nonIdAuthor | Dyar, Scott M. | - |
dc.contributor.nonIdAuthor | Cao, Dennis | - |
dc.contributor.nonIdAuthor | Fahrenbach, Albert C. | - |
dc.contributor.nonIdAuthor | Horwitz, Noah | - |
dc.contributor.nonIdAuthor | Colvin, Michael T. | - |
dc.contributor.nonIdAuthor | Carmieli, Raanan | - |
dc.contributor.nonIdAuthor | Stern, Charlotte L. | - |
dc.contributor.nonIdAuthor | Dey, Sanjeev K. | - |
dc.contributor.nonIdAuthor | Wasielewski, Michael R. | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | MESOPOROUS SILICA NANOPARTICLES | - |
dc.subject.keywordPlus | FIELD EFFECT TRANSISTORS | - |
dc.subject.keywordPlus | LIGHT-EMITTING-DIODES | - |
dc.subject.keywordPlus | MIXED-VALENCE | - |
dc.subject.keywordPlus | BUILDING-BLOCKS | - |
dc.subject.keywordPlus | SUPRAMOLECULAR CHEMISTRY | - |
dc.subject.keywordPlus | CONDUCTING POLYMERS | - |
dc.subject.keywordPlus | CONJUGATED POLYMERS | - |
dc.subject.keywordPlus | ROOM-TEMPERATURE | - |
dc.subject.keywordPlus | PI-DIMERS | - |
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