Self-Association and Electron Transfer in Donor-Acceptor Dyads Connected by meta-Substituted Oligomers

被引:48
作者
Molina-Ontoria, Agustin [1 ]
Fernandez, Gustavo [1 ]
Wielopolski, Mateusz [2 ,3 ,4 ,5 ]
Atienza, Carmen [2 ,3 ]
Sanchez, Luis [1 ]
Gouloumis, Andreas [1 ]
Clark, Timothy [4 ,5 ]
Martin, Nazario [1 ,6 ]
Guldi, Dirk M. [2 ,3 ]
机构
[1] Univ Complutense, Dept Quim Organ, Fac Quim, E-28040 Madrid, Spain
[2] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany
[3] Univ Erlangen Nurnberg, ICMM, D-91058 Erlangen, Germany
[4] Univ Erlangen Nurnberg, Comp Chem Ctr, D-91052 Erlangen, Germany
[5] Univ Erlangen Nurnberg, ICMM, Dept Chem & Pharm, D-91052 Erlangen, Germany
[6] IMDEA Nanociencia, E-28049 Madrid, Spain
关键词
SUPRAMOLECULAR SYSTEMS; AZOMETHINE YLIDES; CHARGE SEPARATION; FULLERENES; FERROCENE; UNITS; C-60; FUNCTIONALIZATION; COMMUNICATION; CONJUGATION;
D O I
10.1021/ja9024269
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The synthesis of a new series of electron donor-acceptor conjugates (5, 10, 13, and 16) in which the electron acceptor-C-60-and the electron donor-pi-extended tetrathiafulvalene (exTTF)-are bridged by means of m-phenyleneethynylene spacers of variable length is reported. The unexpected self-association of these hybrids was first detected to occur in the gas phase by means of MALDI-TOF spectrometry and subsequently corroborated in solution by utilizing concentration-dependent and variable-temperature H-1 NMR experiments. Furthermore, the ability of these new conjugates to form wirelike structures upon deposition onto a mica surface has been demonstrated by AFM spectroscopy. In light of their photoactivity and redoxactivity, 5,10,13, and 16 were probed in concentration-dependent photophysical experiments. Importantly, absorption and fluorescence revealed subtle dissimilarities for the association constants, that is, a dependence on the length of the m-phenylene spacers. The binding strength is in 5 greatly reduced when compared with those in 10, 13, and 16. Not only that, the spacer length also plays a decisive role in governing excited-state interactions in the corresponding electron donor-acceptor conjugates (5,10,13, and 16). To this end, 5, in which the photo- and electroactive constituents are bridged by just one aromatic ring, displays-exclusively and independent of the concentration (10(-1) to 10(-4) M)-efficient intramolecular electron transfer events on the basis of a "through-bond" mechanism. On the contrary, the lack of conjugation throughout the bridges in 10 (two m-phenyleneethynylene rings), 13 (three m-phenyleneethynylene rings), and 16 (four m-phenyleneethynylene rings) favors at low concentration (10(-6) M) "through space" intramolecular electron transfer events. These are, however, quite ineffective and, in turn, lead to excited-state deactivations that are at high concentrations (10(-4) M) dominated by intracomplex electron transfer events, namely, between exTTF of one molecule and C-60 of another molecule, and that stabilize the resulting radical ion pair state with lifetimes reaching 4.0 mu s.
引用
收藏
页码:12218 / 12229
页数:12
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