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Structural and Co-conformational Effects of Alkyne-Derived Subunits in Charged Donor−Acceptor [2]Catenanes

Miljanić, Ognjen Š. and Dichtel, William R. and Khan, Saeed I. and Mortezaei, Shahab and Heath, James R. and Stoddart, J. Fraser (2007) Structural and Co-conformational Effects of Alkyne-Derived Subunits in Charged Donor−Acceptor [2]Catenanes. Journal of the American Chemical Society, 129 (26). pp. 8236-8246. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170426-150614423

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Abstract

Four donor−acceptor [2]catenanes with cyclobis(paraquat-p-phenylene) (CBPQT^(4+)) as the π-electron-accepting cyclophane and 1,5-dioxynaphthalene (DNP)-containing macrocyclic polyethers as π-electron donor rings have been synthesized under mild conditions, employing Cu^+-catalyzed Huisgen 1,3-dipolar cycloaddition and Cu^(2+)-mediated Eglinton coupling in the final steps of their syntheses. Oligoether chains carrying terminal alkynes or azides were used as the key structural features in template-directed cyclizations of [2]pseudorotaxanes to give the [2]catenanes. Both reactions proceed well with precursors of appropriate oligoether chain lengths but fail when there are only three oxygen atoms in the oligoether chains between the DNP units and the reactive functional groups. The solid-state structures of the donor−acceptor [2]catenanes confirm their mechanically interlocked nature, stabilized by [π···π], [C−H···π], and [C−H···Ο] interactions, and point to secondary noncovalent contacts between 1,3-butadiyne and 1,2,3-triazole subunits and one of the bipyridinum units of the CBPQT^(4+) ring. These contacts are characterized by the roughly parallel orientation of the inner bipyridinium ring system and the 1,2,3-triazole and 1,3-butadiyne units, as well as by the short [π···π] distances of 3.50 and 3.60 Å, respectively. Variable-temperature ^1H NMR spectroscopy has been used to identify and quantify the barriers to the conformationally and co-conformationally dynamic processes. The former include the rotations of the phenylene and the bipyridinium ring systems around their substituent axes, whereas the latter are confined to the circumrotation of the CBPQT^(4+) ring around the DNP binding site. The barriers for the three processes were found to be successively 14.4, 14.5−17.5, and 13.1−15.8 kcal mol^(-1). Within the limitations of the small dataset investigated, emergent trends in the barrier heights can be recognized:  the values decrease with the increasing size of the π-electron-donating macrocycle and tend to be lower in the sterically less encumbered series of [2]catenanes containing the 1,3-butadiyne moiety.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/ja071319nDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja071319nPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja071319nPublisherSupporting Information
ORCID:
AuthorORCID
Heath, James R.0000-0001-5356-4385
Stoddart, J. Fraser0000-0003-3161-3697
Additional Information:© 2007 American Chemical Society. Received February 24, 2007. Publication Date (Web): June 9, 2007. This work was supported by the Microelectronics Advanced Research Corporation (MARCO) and its focus center on Functional Engineered NanoArchitectonics (FENA), and also by the Defense Advanced Research Projects Agency (DARPA) and the Center for Nanoscale Innovation for Defense (CNID). Dr. Ivan Aprahamian (UCLA) is acknowledged gratefully for insightful discussions.
Funders:
Funding AgencyGrant Number
Microelectronics Advanced Research Corporation (MARCO)UNSPECIFIED
Defense Advanced Research Projects Agency (DARPA)UNSPECIFIED
Center on Functional Engineered NanoArchitectonics (FENA)UNSPECIFIED
Center for Nanoscale Innovation for Defense (CNID)UNSPECIFIED
Issue or Number:26
Record Number:CaltechAUTHORS:20170426-150614423
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170426-150614423
Official Citation:Structural and Co-conformational Effects of Alkyne-Derived Subunits in Charged Donor−Acceptor [2]Catenanes Ognjen Š. Miljanić, William R. Dichtel, Saeed I. Khan, Shahab Mortezaei, James R. Heath, and J. Fraser Stoddart Journal of the American Chemical Society 2007 129 (26), 8236-8246 DOI: 10.1021/ja071319n
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76961
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:26 Apr 2017 23:03
Last Modified:03 Oct 2019 17:51

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