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1.
Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co+2FeII) and ferricyanides (Co+2FeIII) in an ozone flow. The CN stretching bands occur at 2085 cm–1 for Co+2FeII and at 2160 cm–1 for Co+2FeIII. After the ozonization process of Co+2FeII, an intense band approximately at 2125 cm–1 is detected. This intermediate band must correspond to a mixed valence state of the type: FeII–CN–Co2+–NC–FeIII Mössbauer spectra recorded in situ during the ozonization of Co+2FeII show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co+2FeII after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable. 相似文献
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Jean-Franois Nierengarten Tilo Habicher Roland Kessinger Francesca Cardullo Franois Diederich Volker Gramlich Jean-Paul Gisselbrecht Corinne Boudon Maurice Gross 《Helvetica chimica acta》1997,80(7):2238-2276
The macrocyclization between buckminsterfullerene, C60, and bis-malonate derivatives in double Bingel reaction provides a versatile and simple method for the preparation of covalent bis-adducts of C60 with high regio- and diastereoselectivity. A combination of spectral analysis, stereochemical considerations, and X-ray crystallography (Fig. 2) revealed that out of the possible in-in, in-out, and out-out stereoisomers, the reaction of bis-malonates linked by o-, m-, or p-xylylene tethers afforded only the out-out ones (Scheme 1). In contrast, the use of larger tethers derived from 1,10-phenanthroline also provided a first example, (±)- 19 (Scheme 2), of an in-out product. Starting from optically pure bis-malonate derivatives, the new bis-functionalization method permitted the diastereoselective preparation of optically active fullerene derivatives (Schemes 4 and 5) and, ultimately, the enantioselective preparation (enantiomeric excess ee > 97%) of optically active cis-3 bis-adducts whose chirality results exclusively from the addition pattern (Fig. 6). The macrocyclic fixation of a bis-malonate with an optically active, 9,9′-spirobi[9H-fluorene]-derived tether to C60 under generation of 24 and ent- 24 with an achiral addition pattern (Scheme 4) was found to induce dramatic changes in the chiroptical properties of the tether chromophore such as strong enhancement and reversal of sign of the Cotton effects in the circular dichroism (CD) spectra (Figs. 4 and 5). By the same method, the functionafized bis-adducts 50 and 51 (Schemes 10 and 11) were prepared as initiator cores for the synthesis of the fullerene dendrimers 62 , 63 , and 66 (Schemes 12 and 13) by convergent growth. Finally, the new methodology was extended, to the regio- and diastereoselective construction of higher cyclopropanated adducts. Starting from mono-adduct 71 , a clipping reaction provided exclusively the all-cis-2 tris-adduct (±)- 72 (Scheme 14), whereas the similar reaction of bis-adduct 76 afforded the all-cis-2 tetrakis-adduct 77 (Scheme 15). Electrochemical investigations by steady-state voltammetry (Table 2) in CH2Cl2 (+0.1M Bu4NPF6) showed that all macroeyciic bis(methano)fullerenes underwent multiple reduction steps, and that regioisomerism was not much influencing the redox potentials, All cis-2 bis-adducts gave an instable dianion which decomposed during the electrochemical reduction. In CH2Cl2, the redox potential of the fullerene core in dendrimers 62, 63 , and 66 is not affected by differences in size and density of the surrounding poly(ether-amide) dendrons. The all-cis-2 tris- and tetrakis(meihano)fullercnes (±) -72 and 77 , respectively, are reduced at more negative potential than previously reported all-e tris- and tetrakis-adducts with methane bridges that are also located along an equatorial belt. This indicates a larger perturbation of the original fullerene π-chromophore and a larger raise in LUMO energy in the former derivatives. 相似文献
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van den Brand JF Ent R Anthony PL Arnold RG Arrington J Beise EJ Belz JE Bosted PE Bulten H Chapman MS Coulter KP Dietrich FS Epstein M Filippone BW Gao H Gearhart RA Geesaman DF Hansen J Holt RJ Jackson HE Jones CE Keppel CE Kinney ER Kuhn S Lee K Lorenzon W Lung A Makins NC Margaziotis DJ McKeown RD Milner RG Mueller B Napolitano J Nelson J O'Neill TG Papavassiliou V Petratos GG Potterveld DH Rock SE Spengos M Szalata ZM Tao LH van Bibber K Wasson DA White JL Zeidman B 《Physical review D: Particles and fields》1995,52(9):4868-4871
6.
Makins NC Ent R Chapman MS Hansen J Lee K Milner RG Nelson J Arnold RG Bosted PE Keppel CE Lung A Rock SE Spengos M Szalata ZM Tao LH White JL Coulter KP Geesaman DF Holt RJ Jackson HE Papavassiliou V Potterveld DH Zeidman B Arrington J Beise EJ Belz E Filippone BW Gao H Lorenzon W Mueller B McKeown RD O'Neill TG Epstein M Margaziotis DJ Napolitano J Kinney E Anthony PL van Bibber K Dietrich FS Gearhart RA Patratos GG Kuhn SE van den Brand JF Bulten H Jones CE 《Physical review letters》1994,72(13):1986-1989
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Cardinali F Mamlouk H Rio Y Armaroli N Nierengarten JF 《Chemical communications (Cambridge, England)》2004,(14):1582-1583
A multicomponent array made of a bis-copper(I) helicate core and two peripheral fullerene subunits has been prepared and electron transfer from the photoexcited Cu(I)-complexed unit to C60 occurs. 相似文献
9.
Nicola Armaroli Gianluca Accorsi JohnN. Clifford Jean‐Franois Eckert Jean‐Franois Nierengarten 《化学:亚洲杂志》2006,1(4):564-574
Oligophenylenevinylene (OPV)‐terminated phenylenevinylene dendrons G1 – G4 with one, two, four, and eight “side‐arms”, respectively, were prepared and attached to C60 by a 1,3‐dipolar cycloaddition of azomethine ylides generated in situ from dendritic aldehydes and N‐methylglycine. The relative electronic absorption of the OPV moiety increases progressively along the fullerodendrimer family C60G1 – C60G4 , reaching a 99:1 ratio for C60G4 (antenna effect). UV/Vis and near‐IR luminescence and transient absorption spectroscopy was used to elucidate photoinduced energy and electron transfer in C60G1 – C60G4 as a function of OPV moiety size and solvent polarity (toluene, dichloromethane, benzonitrile), taking into account the fact that the free‐energy change for electron transfer is the same along the series owing to the invariability of the donor–acceptor couple. Regardless of solvent, all the fullerodendrimers exhibit ultrafast OPV→C60 singlet energy transfer. In CH2Cl2, the OPV→C60 electron transfer from the lowest fullerene singlet level (1C60*) is slightly exergonic (ΔGCS≈0.07 eV), but is observed, to an increasing extent, only in the largest systems C60G2 – C60G4 with lower activation barriers for electron transfer. This effect has been related to a decrease of the reorganization energy upon enlargement of the molecular architecture. Structural factors are also at the origin of an unprecedented OPV→C60 electron transfer observed for C60G3 and C60G4 in apolar toluene, whereas in benzonitrile, electron transfer occurs in all cases. Monitoring of the lowest fullerene triplet state by sensitized singlet oxygen luminescence and transient absorption spectroscopy shows that this level is populated through intersystem crossing and is not involved in photoinduced electron transfer. 相似文献
10.
Schell J. Felder D. Nierengarten J.-F. Rehspringer J.-L. Lévy R. Hönerlage B. 《Journal of Sol-Gel Science and Technology》2001,22(3):225-236
Porous sol-gel glasses, either impregnated with pure C60 or doped with a methanofullerene derivative, have been studied and induced absorption or reverse saturable absorption (RSA) has been observed in both types of solid materials. The samples impregnated by pure C60 mainly contain well-dispersed fullerene molecules. Unlike crystalline films of C60, their absorption dynamics can be well described by a 5-level model, developed for non-interacting C60-molecules in solutions. Methanofullerene samples, on the other hand, show signs of micellar aggregation and therefore RSA dynamics that are influenced by solid state effects. We observe an important decrease of transmission at high fluences for both kinds of samples, a shortened singlet-state lifetime to that observed in solution, but nonetheless, a triplet yield, that cannot be considered as negligible. In the case of pure C60 in a sol-gel matrix, we can explain the faster de-excitation dynamics, relative to behavior in solution, mainly by the absence of stabilizing aromatic solvents and also by the interaction of the amorphous environment with the molecules. Concerning the methanofullerene samples, the acceleration of the de-excitation dynamics can be principally attributed to solid-state effects due to the micellar aggregation. 相似文献