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Disparate Downstream Reactions Mediated by an Ionically Controlled Supramolecular Tristate Switch.
Park, Jung Su; Park, Jihye; Yang, Yun Jae; Tran, Trang Thu; Kim, In Su; Sessler, Jonathan L.
Afiliação
  • Park JS; Department of Chemistry , Sookmyung Women's University , 100 Cheongpa-ro 47-gil , Yongsan-gu, Seoul 04310 , Republic of Korea.
  • Park J; School of Pharmacy , Sungkyunkwan University , Suwon 16419 , Republic of Korea.
  • Yang YJ; Department of Chemistry , Sookmyung Women's University , 100 Cheongpa-ro 47-gil , Yongsan-gu, Seoul 04310 , Republic of Korea.
  • Tran TT; Department of Chemistry , Sookmyung Women's University , 100 Cheongpa-ro 47-gil , Yongsan-gu, Seoul 04310 , Republic of Korea.
  • Kim IS; School of Pharmacy , Sungkyunkwan University , Suwon 16419 , Republic of Korea.
  • Sessler JL; Department of Chemistry , The University of Texas at Austin , 105 East 24th Street, Stop A5300 , Austin , Texas 78712-1224 , United States.
J Am Chem Soc ; 140(24): 7598-7604, 2018 06 20.
Article em En | MEDLINE | ID: mdl-29809007
The use of chemical messengers to control multiple and often disparate downstream events is a hallmark of biological signaling. Here, we report a synthetic supramolecular construct that gives rise to bifurcated downstream events mediated by different stimulus-induced chemical messengers. The system in question consists of a supramolecular redox-ensemble made up of a tetrathiafulvalene (TTF)-based macrocycle, benzo-TTF-calix[4]pyrrole, and an electron deficient partner, 7,7,8,8-tetracyanoquinodimethane (TCNQ). Different tetraalkylammonium halide salts are used to trigger the reversible switching between neutral (No-ET), charge transfer (CT), and electron transfer (ET) states. The result is an effective tristate switch that provides chemical access to three different forms of TCNQ, namely, a released neutral, radical anionic (TCNQ•-), or bound CT forms. The ionically induced switching chemistry is linked separately through the neutral and radical anion TCNQ forms to two distinct follow-on reactions. These reactions consist, respectively, of styrene polymerization, which is triggered only in the "1" (TCNQ radical anion ET) state, and a cycloaddition-retroelectrocyclization (CA-RE) reaction, which is mediated only by the neutral TCNQ "0" (No-ET) state. Neither downstream reaction is promoted by the CT form, wherein the TCNQ is receptor bound. The three states that characterize this system, their interconversion, and the downstream reactions promoted by TCNQ•- and free TCNQ, respectively, have been characterized by single-crystal X-ray diffraction analyses and various solution phase spectroscopies.

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2018 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2018 Tipo de documento: Article