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1.
Synthesis and Photophysical Properties of a Sc3N@C80‐Corrole Electron Donor–Acceptor Conjugate
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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
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Robin F. Weitkamp Beate Neumann Hans‐Georg Stammler Berthold Hoge 《Angewandte Chemie (International ed. in English)》2020,59(14):5494-5499
We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization. 相似文献
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Let A be a symmetric matrix of size n×n with entries in some (commutative) field K. We study the possibility of decomposing A into two blocks by conjugation by an orthogonal matrix T∈Matn(K). We say that A is absolutely indecomposable if it is indecomposable over every extension of the base field. If K is formally real then every symmetric matrix A diagonalizes orthogonally over the real closure of K. Assume that K is a not formally real and of level s. We prove that in Matn(K) there exist symmetric, absolutely indecomposable matrices iff n is congruent to 0, 1 or −1 modulo 2s. 相似文献
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P. Rudolf R. Raval P. Dumas G.P. Williams 《Applied Physics A: Materials Science & Processing》2002,75(1):147-153
Infrared (IR) spectroscopy of chemisorbed C60 on Ag (111), Au (110) and Cu (100) reveals that a non-IR-active mode becomes active upon adsorption, and that its frequency
shifts proportionally with the charge transferred from the metal to the molecule by about 5 cm-1 per electron. The temperature dependence of the frequency and the width of this IR feature have also been followed for C60/Cu (100) and were found to agree well with a weak anharmonic coupling (dephasing) to a low-frequency mode, which we suggest
to be the frustrated translational mode of the adsorbed molecules.
Additionally, the adsorption is accompanied by a broadband reflectance change, which is interpreted as due to the scattering
of conduction electrons of the metal surface by the adsorbate. The reflectance change allows determination of the friction
coefficient of the C60 molecules, which results in rather small values (∼2×109 s-1 for Ag and Au, and ∼1.6×109 s-1for Cu), consistent with a marked metallic character of the adsorbed molecules.
Pre-dosing of alkali atoms onto the metal substrates drastically changes the IR spectra recorded during subsequent C60 deposition: anti-absorption bands, as well as an increase of the broadband reflectance, occur and are interpreted as due
to strong electron–phonon coupling with induced surface states.
Received: 6 June 2001 / Accepted: 23 October 2001 / Published online: 3 April 2002 相似文献
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Ohne Zusammenfassung 相似文献
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