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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.
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
3.
4.
5.
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
6.
Each convex planar set K has a perimeter C, a minimum width E, an area A, and a diameter D. The set of points (E,C, A1/2, D) corresponding to
all such sets is shown to occupy a cone in the non-negative orthant of R4with its vertex at the origin. Its three-dimensional cross section S in the
plane D = 1 is investigated. S lies in a rectangular parallelepiped in R3. Results of Lebesgue, Kubota, Fukasawa, Sholander, and Hemmi are used to
determine some of the boundary surfaces of S, and new results are given for the other boundary surfaces. From knowledge of S, all inequalities among
E, C ,A, and D can be found. 相似文献
7.
Experimental and theoretical investigations of the spectroscopy of molecules in superfluid helium droplets provide evidence for the key role of the first helium layer surrounding the dopant molecule in determining the molecule's spectroscopic features. Recent investigations of emission spectra of phthalocyanine in helium droplets revealed a doubling of all transitions. Herein, we present the emission spectra of Mg-phthalocyanine and of phthalocyanine-argon clusters in helium droplets, which confirm the splitting as a general effect of the helium environment. A scheme of levels is deduced from the emission spectra and attributed to quantized states of the first helium layer surrounding the dopant molecule. 相似文献
8.
B. Pümpin H. Keller W. Kündig I. M. Savić J. W. Schneider H. Simmler P. Zimmermann E. Kaldis S. Rusiecki C. Rossel 《Hyperfine Interactions》1991,63(1-4):25-31
A systematic μSR study of the local magnetic field distribution in a series of oxygen deficient YBa2Cu3O
x
samples with 6.5⩽x⩽7.0 is reported. Special attention was given to perform the experiments under the same conditions, so that the oxygen content
of the measured samples was the only parameter varied. The behavior of the depolarization rate σ as a function of the oxygen
contentx was found to have strong similarities with the behavior of the critical temperatureT
c
as a function ofx. In particular, two step-like increases of σ were observed abovex=6.7 and 6.9. The temperature dependence of the normalized depolarization rate σ(T)/σ(0) is well described by the two-fluid model forx⩾6.781(1) and clearly deviates from this behavior forx⩽6.704(1). Our results are compared to those obtained by other groups. 相似文献
9.
Based on the SU(n)-algebra the Markoff master equation in discrete product space is reformulated to explicitly deal with composite systems. The resulting local (single node) and nonlocal (multi-node) state parameters allow a systematic approach to non-classical features of the state, like variance and covariance tensors. For local optical driving forces, inter-node interactions, and local damping channels the solution of the master equation is unraveled into stochastic quantum trajectories. Sampling leads to a joint distribution function in terms of those state parameters. Its linear moments define the ensemble-density matrix. The average variance and covariance are in terms of non-linear moments, which should be distinguished from their entirely statistical counterpairs. Non-classicality of the network dynamics is shown to reflect itself in the luminescence-photonstatistics. 相似文献
10.