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1.
Konstantinos Spyrou Matteo Calvaresi Evmorfia K. Diamanti Theodoros Tsoufis Dimitrios Gournis Petra Rudolf Francesco Zerbetto 《Advanced functional materials》2015,25(2):263-269
Experimental and theoretical studies are performed in order to illuminate, for first time, the intercalation mechanism of polycyclic aromatic molecules into graphite oxide. Two representative molecules of this family, aniline and naphthalene amine are investigated. After intercalation, aniline molecules prefer to covalently connect to the graphene oxide matrix via chemical grafting, while napthalene amine molecules bind with the graphene oxide surface through π–π interactions. The presence of intercalated aromatic molecules between the graphene oxide layers is demonstrated by X‐ray diffraction, while the type of interaction between graphene oxide and polycyclic organic molecules is elucidated by X‐ray photoelectron spectroscopy. Combined quantum mechanical and molecular mechanical calculations describe the intercalation mechanism and the aniline grafting, rationalizing the experimental data. The present work opens new perspectives for the interaction of various aromatic molecules with graphite oxide and the so‐called “intercalation chemistry”. 相似文献
2.
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
3.
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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Sufficient conditions which guarantee that certain linear integro-differential equation cannot have a positive solution are
established. 相似文献
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Holger Poths Erik Wischerhoff Rudolf Zentel Axel Sch nfeld Guido Henn Friedrich Kremer 《Liquid crystals》1995,18(5):811-818
Two new ferroelectric oligosiloxanes, a cyclic tetramer and a twin, have been synthesized. By a comparative study with their corresponding monomer and side chain polysiloxanes, the influence of oligo- and polymerization on the liquid crystalline and ferroelectric properties have been investigated. Polymerization leads to a stabilization of LC phases through increase of the clearing temperatures and suppression of crystallization. Oligomerization also leads to mesophase broadening, but, due to the low degree of polymerization, the effect is inferior to the linear polysiloxanes. The low viscosity of the oligosiloxanes ensures response times in the microsecond region, thus being comparable with their monomer and conventional LMWFLCs. It is found that polymerization increases the spontaneous polarization Ps. This is attributed to the density increase after polymerization, enhancing the inter-mesogenic interactions. The collective and local dynamics of the OFLCs are influenced differently with respect to their molecular structures. Each oligomer is already a good model for its corresponding polymer concerning the soft mode dynamics. For the local β-relaxation a similar temperature dependence of the relaxation times τ for the cyclic tetramer and for the side chain polysiloxanes is observed. The long axial rotation of the twin, having a very efficient decoupling, is significantly faster, thus resembling the monomer. 相似文献