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RISS 인기검색어
- 검색키워드
- 저자 : Dyar, S. M. (검색결과 4 건)
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Tetrathiafulvalene Hetero Radical Cation Dimerization in a Redox-Active [2]Catenane
Wang, Cheng,Dyar, Scott M.,Cao, Dennis,Fahrenbach, Albert C.,Horwitz, Noah,Colvin, Michael T.,Carmieli, Raanan,Stern, Charlotte L.,Dey, Sanjeev K.,Wasielewski, Michael R.,Stoddart, J. Fraser American Chemical Society 2012 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.134 No.46
<P>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<SUP>•+</SUP> and STTFS<SUP>•+</SUP>. 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-<I>p</I>-phenylene) (CBPQT<SUP>4+</SUP>) 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<SUP>4+</SUP> ring. After a one-electron oxidation, a 70:30 ratio of OTTFO<SUP>•+</SUP> to STTFS<SUP>•+</SUP> 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<SUP>4+</SUP> 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.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2012/jacsat.2012.134.issue-46/ja307577t/production/images/medium/ja-2012-07577t_0013.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja307577t'>ACS Electronic Supporting Info</A></P>
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Zhu, Zhixue,Fahrenbach, Albert C.,Li, Hao,Barnes, Jonathan C.,Liu, Zhichang,Dyar, Scott M.,Zhang, Huacheng,Lei, Juying,Carmieli, Raanan,Sarjeant, Amy A.,Stern, Charlotte L.,Wasielewski, Michael R.,Sto American Chemical Society 2012 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.134 No.28
<P>Two redox-active bistable [2]catenanes composed of macrocyclic polyethers of different sizes incorporating both electron-rich 1,5-dioxynaphthalene (DNP) and electron-deficient 4,4′-bipyridinium (BIPY<SUP>2+</SUP>) units, interlocked mechanically with the tetracationic cyclophane cyclobis(paraquat-<I>p</I>-phenylene) (CBPQT<SUP>4+</SUP>), were obtained by donor–acceptor template-directed syntheses in a threading-followed-by-cyclization protocol employing Cu(I)-catalyzed azide–alkyne 1,3-dipolar cycloadditions in the final mechanical-bond forming steps. These bistable [2]catenanes exemplify a design strategy for achieving redox-active switching between two translational isomers, which are driven (i) by donor–acceptor interactions between the CBPQT<SUP>4+</SUP> ring and DNP, or (ii) radical–radical interactions between CBPQT<SUP>2(•+)</SUP> and BIPY<SUP>•+</SUP>, respectively. The switching processes, as well as the nature of the donor–acceptor interactions in the ground states and the radical–radical interactions in the reduced states, were investigated by single-crystal X-ray crystallography, dynamic <SUP>1</SUP>H NMR spectroscopy, cyclic voltammetry, UV/vis spectroelectrochemistry, and electron paramagnetic resonance (EPR) spectroscopy. The crystal structure of one of the [2]catenanes in its trisradical tricationic redox state provides direct evidence for the radical–radical interactions which drive the switching processes for these types of mechanically interlocked molecules (MIMs). Variable-temperature <SUP>1</SUP>H NMR spectroscopy reveals a degenerate rotational motion of the BIPY<SUP>2+</SUP> units in the CBPQT<SUP>4+</SUP> ring for both of the two [2]catenanes, that is governed by a free energy barrier of 14.4 kcal mol<SUP>–1</SUP> for the larger catenane and 17.0 kcal mol<SUP>–1</SUP> for the smaller one. Cyclic voltammetry provides evidence for the reversibility of the switching processes which occurs following a three-electron reduction of the three BIPY<SUP>2+</SUP> units to their radical cationic forms. UV/vis spectroscopy confirms that the processes driving the switching are (i) of the donor–acceptor type, by the observation of a 530 nm charge-transfer band in the ground state, and (ii) of the radical–radical ilk in the switched state as indicated by an intense visible absorption (ca. 530 nm) and near-infrared (ca. 1100 nm) bands. EPR spectroscopic data reveal that, in the switched state, the interacting BIPY<SUP>•+</SUP> radical cations are in a fast exchange regime. In general, the findings lay the foundations for future investigations where this radical–radical recognition motif is harnessed in bistable redox-active MIMs in order to achieve close to homogeneous populations of co-conformations in both the ground and switched states.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2012/jacsat.2012.134.issue-28/ja3037355/production/images/medium/ja-2012-037355_0011.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja3037355'>ACS Electronic Supporting Info</A></P>
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A Radically Configurable Six-State Compound
Barnes, J. C.,Fahrenbach, A. C.,Cao, D.,Dyar, S. M.,Frasconi, M.,Giesener, M. A.,Benitez, D.,Tkatchouk, E.,Chernyashevskyy, O.,Shin, W. H.,Li, H.,Sampath, S.,Stern, C. L.,Sarjeant, A. A.,Hartlieb, K. American Association for the Advancement of Scienc 2013 Science Vol.339 No.6118
<P>Most organic radicals possess short lifetimes and quickly undergo dimerization or oxidation. Here, we report on the synthesis by radical templation of a class of air- and water-stable organic radicals, trapped within a homo[2]catenane composed of two rigid and fixed cyclobis(paraquat-p-phenylene) rings. The highly energetic octacationic homo[2]catenane, which is capable of accepting up to eight electrons, can be configured reversibly, both chemically and electrochemically, between each one of six experimentally accessible redox states (0, 2+, 4+, 6+, 7+, and 8+) from within the total of nine states evaluated by quantum mechanical methods. All six of the observable redox states have been identified by electrochemical techniques, three (4+, 6+, and 7+) have been characterized by x-ray crystallography, four (4+, 6+, 7+, and 8+) by electron paramagnetic resonance spectroscopy, one (7+) by superconducting quantum interference device magnetometry, and one (8+) by nuclear magnetic resonance spectroscopy.</P>
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