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1.
Synthesis and Photophysical Properties of a Sc3N@C80‐Corrole Electron Donor–Acceptor Conjugate 下载免费PDF全文
Bin Liu Hongyun Fang Prof. Xiaofang Li Wenting Cai Lipiao Bao Marc Rudolf Fabian Plass Prof. Louzhen Fan Prof. Xing Lu Prof. Dirk M. Guldi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(2):746-752
Embedding endohdedral metallofullerenes (EMFs) into electron donor–acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3‐dipolar cycloaddition reaction of a corrole‐based precursor with Sc3N@C80 to regioselectively form a [5,6]‐adduct ( 1 ). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]‐bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1 . In the electronically excited state, which is probed in photophysical assays with 1 , a fast electron‐transfer yields the radical ion pair state consisting of the one‐electron‐reduced Sc3N@C80 and of the one‐electron‐oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics. 相似文献
2.
To incorporate an acceptor type polythiophene segment onto a supramolecular block copolymer for potential light harvesting applications, effective synthetic routes for the end‐functionalized and acceptor‐substituted polythiophenes are critical. The Ullmann coupling reaction can be utilized to obtain electron‐deficient polythiophenes and to attach terminal thiophene units that carry functional groups. In this article, the reactions involving a 2,5‐dibromothiophene monomer containing an electron‐withdrawing fluorinated ester and 5‐bromo‐2‐thiophenecarboxaldehyde (the end‐capper) were studied in detail. It was found that the Ullmann coupling reaction of the dibromide is very fast (completed in a few minutes) and the terminal bromine group does not survive long under the reaction condition. These findings lead to the development of an effective procedure for aldehyde end‐capping of electron‐deficient polythiophenes. Polymers with molecular weights around 4000 Da are routinely obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 41–47, 2007 相似文献
3.
Yoshitomo Ono Naoyuki Kawashima Hiroto Kudo Tadatomi Nishikubo Takabumi Nagai 《Journal of polymer science. Part A, Polymer chemistry》2007,45(14):2978-2988
The ring‐opening copolymerization of a glycidyl ester derivative having a benzophenone group and the donor–acceptor norbornadiene (D‐A NBD) dicarboxylic acid, 5‐(4‐methoxyphenyl)‐1,4,6,7,7‐pentamethyl‐2,5‐norbornadiene‐2,3‐dicarboxylic acid, monoglycidyl ester derivatives with D‐A NBD dicarboxylic anhydride using tetraphenylphosphonium bromide as a catalyst proceeded smoothly to give novel self‐photosensitizing NBD polymers in good yields. The molecular weight of these polyesters was about 4,000, and lower than that of analogous NBD polymers having no benzophenone group. All the synthesized NBD polymers isomerized smoothly to the corresponding quadricyclane (QC) polymers upon UV irradiation in tetrahydrofuran (THF) solution and in the film state. The rate of the photoisomerization of the D‐A NBD moieties in these polymers was higher than that of the D‐A NBD moieties in the polymer having no photosensitizing group. Furthermore, the rate of the photoisomerization of the D‐A NBD moieties in these polymers was also higher than that of the NBD polymer with low molecular weight photosensitizer in dilute solution. The photo‐irradiated polymers having QC moieties released thermal energies of 146–180 J/g. The D‐A NBD moieties contained in these NBD polymers possessed fair to good fatigue resistance. The degradation of the NBD moieties in these polymers was 15–30% after 50 repeated cycles of interconversion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2978–2988, 2007 相似文献
4.
4-Aminophthalimide Derivatives as Environment-Sensitive Probes 总被引:2,自引:0,他引:2
The potential of 4-aminophthalimide (AP) and its derivatives as fluorescence probes for organized media is highlighted. The fluorescence response of AP, as measured from the position of the fluorescence maximum, fluorescence intensity and lifetime, is highly sensitive to the polarity of the medium. The sensitivity of the fluorescence parameters is further enhanced due to the involvement of the emitting intramolecular charge transfer state in hydrogen bonding interaction with the solvent molecules containing hydroxyl groups. It is shown that the microheterogeneous environments of organized media such as cyclodextrins and micelles can be very conveniently monitored using this probe. The results of the investigations carried out employing AP and its derivatives as fluorescence probe molecules in these media clearly suggest that a combination of the hydrophobic interaction with the host media and hydrogen bonding interaction with the solvent molecules determine the location of the fluorophore, which in all cases is found to be the interfacial region separating the nonpolar core of the micelle or the cyclodextrin cavity and the polar aqueous environment. Guidelines for the design of probes of this class of systems for the nonpolar core region of the micelles are provided and possible ways to increase the sensitivity of the fluorescence response of the systems are suggested. 相似文献
5.
6.
Hiroki Higuchi Hidetoshi Kawai Masakazu Ohkita Takanori Suzuki 《Tetrahedron letters》2004,45(15):3027-3030
The newly prepared tetracyanoanthraquinodimethane (TCNAQ) derivatives 1a,b with a chiral auxiliary are good electron acceptors and exhibit weak circular dichroism (CD) based on the absorption of TCNAQ. The twin-type electron acceptor 1c with two TCNAQ units shows larger ellipticity by exciton coupling. UV-vis, CD, and fluorescence spectra were changed drastically upon electrochemical reduction of 1c, which demonstrates the unprecedented three-way-output response system. 相似文献
7.
Summary The optimized Wittig reaction of selectively functionalized 3-acylindoles yield new, and for Diels-Alder reactions highly reactive donor- and acceptor substituted 3-vinylindoles, respectively. 相似文献
8.
The rates of photoinduced electron transfer (ET) reactions across two oligo-norbornyl spacer groups (S), that is, structure 1 fused by two norbornadiene (NBD) units and structure 2 fused by three NBD units, are examined. Substituted naphthalene acted as an electron donor (D), whilst ethylene-1,2-dicarboxylate as an electron acceptor (A). ET rates were measured by fluorescence quenching experiments on these D-S-A dyads, and the results were correlated with reaction free energies according to the Marcus relationship. It was found that naphthalene with phenyl substituents showed relatively slower ET rates. The conformational flexibility of phenyl substituents may cause a hindrance on the electronic coupling between D and A. Another salient feature was the abnormally high quenching rates observed in nonpolar solvents such as cyclohexane, the results of which may be ascribed to a competing energy transfer process. 相似文献
9.
Alternative Ligands. XXIII Rhodium(I) Complexes with Donor/Acceptor Ligands of the Type (Me2PCH2CH2)2SiX2 and (2-Me2PC6H4)SiXMe2 (X = F, Cl) Donor/acceptor ligands of the type (Me2PCH2CH2)2SiX2 and (2-Me2PC6H4)SiXMe2 (X = F, Cl) react with [Rh(CO)2Cl]2 (1) to give the mononuclear complexes RhCl(CO)(Me2PCH2CH2)2SiX2 [X = F( 4 ), Cl ( 5 )] and RhCl(CO)[2-Me2PC6H4)SixMe2]2 [X = F ( 8 ), Cl ( 9 )], respectively. In case of the ligands (Me2PCH2CH2)2SiCl2 ( 3 ) and (2-Me2PC6H6)SiClMe2 ( 7 ) the Rh(I) complexes formed in the first step partly undergo oxidative addition reactions of SiCl bonds yielding rhodium(III) compounds of low solubility. Only for 8 the coordination shifts Δδ = δ(complex)?δ(ligand) and coupling constants give some indication to possible Rh→Si interactions. However, the molecular structure of 8 determined by X-ray diffraction does not show RhSi or RhF bonding contacts. The new compounds were characterized by analytical (C, H) and spectroscopic investigations (MS, IR,-NMR). 相似文献
10.
Francis D. de Kőrösy 《Mikrochimica acta》1989,97(1-2):25-29
Donor or acceptor compounds in apolar organic solvents become charged at a high-field strength electrode and are driven to a surrounding low-field strength electrode of opposite sign. At 10 kV per cm the solutions conduct 3–7 times better when the highly charged electrode is positive in donor solutions. The opposite situation occurs in acceptor solutions. 相似文献