排序方式: 共有50条查询结果,搜索用时 15 毫秒
21.
Grée D Vallerie L Grée R Toupet L Washington I Pelicier JP Villacampa M Pérez JM Houk KN 《The Journal of organic chemistry》2001,66(7):2374-2381
The preparations of new allylic fluorides from the corresponding alcohols are reported. Conformational analysis is achieved by comparison of experimental NMR measurements with theoretical (B3LYP) calculations of relative energies of conformers and J(H,H) and J(H,F) coupling constants. The Diels-Alder reactions of allylic fluorides are investigated experimentally and theoretically. The stereoselectivities of the reactions were determined by NMR analysis and, in one case, by X-ray crystallography. Theoretical predictions of stereoselectivity based upon transition state modeling provided good agreement with experiment. Theoretical models for allylic fluorides and transition state conformations are reported. 相似文献
22.
M González J L Segura C Seoane N Martín J Garín J Orduna R Alcalá B Villacampa V Hernández J T López Navarrete 《The Journal of organic chemistry》2001,66(26):8872-8882
Novel pi-conjugated donor-acceptor chromophores, based on the strong electron-donating tetrathiafulvalene moiety and different electron-withdrawing acceptors, exhibit large second-order optical nonlinearities. The effect of increasing the length of the polyenic spacer and the influence of the nature of the acceptor moiety on the NLO properties have been studied by using the electric field-induced second-harmonic generation (EFISH) technique as well as by semiempirical and ab initio theoretical calculations. A charge-transfer band has been observed in the absorption spectra of these D-pi-A compounds that undergoes an hypsochromic shift when increasing the number of vinylenic spacer units connecting both donor and acceptor moieties. The degree of the intramolecular charge transfer from the donor to the acceptor has also been analyzed by means of Raman spectroscopy. 相似文献
23.
We study the Dirichlet problem defined by u = f in and u =g in when is the half-space or the unitary rectangle, obtainingan a priori estimate of the solution. Furthermore, in both casesa concrete numerical estimation is arrived at. First we getthe a priori estimate in the case of the half-space. The problemis resolved for the rectangle by initially translating it intothe half-space and using the results we had obtained for it,so that the problem can then be reduced back to the rectangle.Because of this we first establish an extension of the Sobolevspace of second order in the rectangle to the one defined inthe half-space. 相似文献
24.
25.
Abstract The optical properties of RbCdF3 crystals doped with Cr3+, Mn2+ and Ni2+ have been studied. Absorption and photoluminescence spectra correspond to these ions in an octahedral environment. The lifetimes of the emitting levels have been measured at different temperatures. Single exponential decays are obtained for Mn2+ and Ni2+ while a non-exponential decay is found in the case of Cr3+. Radiation effects have also been studied. A new absorption band is produced in the 305 nm region by RT X-irradiation. Exciting with light in this band the 3d-ions emissions are observed. 相似文献
26.
Insuasty B Atienza C Seoane C Martín N Garín J Orduna J Alcalá R Villacampa B 《The Journal of organic chemistry》2004,69(21):6986-6995
A novel D-pi-A system in which tetrathiafulvalene (TTF) and pi-extended TTFs as strong electron donors are covalently connected to a tricarbonyl (eta(6)-arene)chromium complex as the acceptor moiety through a systematically increased conjugated bridge of vinylene units (12a-c, 16a-c) have been synthesized by Wittig-Horner olefination reaction. The electronic spectra as well as the electrochemical data reveal a different behavior of TTF derivatives (12a-c) and of exTTF derivatives (16a-c). Cyclic voltammetry shows the influence of the tricarbonylchromium arene on the oxidation potentials in compounds 12a-c, and no remarkable effect is observed for exTTFs (16a-c). The nonlinear optical properties of 12a-c and 16a-c have been calculated by using the ab initio CPHF/6-31G//B3P86/6-31G model, and the time-dependent density functional theory (TD-DFT) method has been used for the calculation of the electronic transitions. The calculations reveal that an intraligand charge-transfer transition (ILCT) and the metal to ligand charge-transfer transition (MLCT) are responsible for the nonlinear response. In addition, the large angles formed by the ground-state dipole moment and the vectorial hyperpolarizability are responsible for the mubeta values determined experimentally by the EFISH technique. 相似文献
27.
Structural and Photophysical Study on Heterobimetallic Complexes with d8–d10 Interactions Supported by Carborane Ligands: Theoretical Analysis of the Emissive Behaviour 下载免费PDF全文
Dr. Olga Crespo Prof. M. Concepción Gimeno Prof. Antonio Laguna Dr. Olli Lehtonen Dr. Isaura Ospino Prof. Pekka Pyykkö Dr. M. Dolores Villacampa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(11):3120-3127
Heterobimetallic complexes of formula [M{(PPh2)2C2B9H10}(S2C2B10H10)M′(PPh3)] (M=Pd, Pt; M′=Au, Ag, Cu) and [Ni{(PPh2)2C2B9H10}(S2C2B10H10)Au(PPh3)] were obtained from the reaction of [M{(PPh2)2C2B10H10}(S2C2B10H10)] (M=Pd, Pt) with [M′(PPh3)]+ (M′=Au, Ag, Cu) or by one‐pot synthesis from [(SH)2C2B10H10], (PPh2)2C2B10H10, NiCl2 ? 6 H2O, and [Au(PPh3)]+. They display d8–d10 intermetallic interactions and emit red light in the solid state at 77 K. Theoretical studies on [M{(PPh2)2C2B9H10}(S2C2B10H10)Au(PPh3)] (M=Pd, Pt, Ni) attribute the luminescence to ligand (thiolate, L)‐to‐“P2‐M‐S2” (ML′) charge‐transfer (LML′CT) transitions for M=Pt and to metal (M)‐to‐“P2‐M‐S2” (ML′) charge‐transfer (MML′CT) transitions for M=Ni, Pd. 相似文献
28.
Rodríguez C. A. Delgadillo A. Núñez J. Cabello-Guzmán G. Mera Adriana C. Delplancke M. P. Villacampa B. Carrasco C. 《Journal of Solid State Electrochemistry》2020,24(6):1405-1414
Journal of Solid State Electrochemistry - A one-step electrodeposition process was used to obtain CuInS2 (CIS) films on a molybdenum substrate by varying the supporting electrolyte (lithium... 相似文献
29.
Andreu R Galán E Orduna J Villacampa B Alicante R Navarrete JT Casado J Garín J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(3):826-838
Push–pull compounds, in which a proaromatic electron donor is conjugated to a 2‐dicyanomethylenethiazole acceptor, have been prepared, and their properties compared to those of model compounds featuring an aromatic donor. A combined experimental (X‐ray diffraction, 1H NMR, IR, Raman, UV/Vis, nonlinear optical (NLO) measurements) and theoretical study reveals that structural and solvent effects determine the ground‐state polarisation of these merocyanines: whereas 4H‐pyran‐4‐ylidene‐ and 4‐pyridylidene‐containing compounds are zwitterionic and 1,3‐dithiol‐2‐ylidene derivatives are close to the cyanine limit, anilino‐derived merocyanines are essentially neutral. This very large range of intramolecular charge transfer (ICT) gives rise to efficient second‐order NLO chromophores with μβ values ranging from strongly negative to strongly positive. In particular, pyranylidene derivatives are unusual in that they show an increase in the degree of ICT on lengthening the π‐spacer, a feature that lies behind the very large negative μβ values they display. The linking of the formally quinoidal 2‐dicyanomethylenethiazole moiety to proaromatic donors seems a promising approach towards the optimisation of zwitterionic NLO chromophores. 相似文献
30.
Bumbu O Ceamanos C Crespo O Gimeno MC Laguna A Silvestru C Villacampa MD 《Inorganic chemistry》2007,46(26):11457-11460
The reaction of [AuCl(PR'3)] with KTeR, prepared from RTeTeR and K-selectride, gives the gold-tellurolate clusters [Au8(mu-TeR)8(PR'3)4] (R = Ph, Tol; PR'3 = PPh3, PPh2py) in high yield. This result contrasts with the one obtained from the reaction with thiolates or selenolates, from which mononuclear complexes are synthesized. The structures of these species have been determined and consist on three layers of gold and tellurium atoms in the ratio Au3Te2:Au2Te4:Au3Te2. There are short gold...gold interactions ranging from 2.9463(7) to 3.31132(7) A, and the clusters are composed of di- and tri-coordinated gold centers. The result is unprecedented in gold-chalcogenolate chemistry from which mononuclear species are expected and represents one of the few examples of gold-tellurolate derivatives. These species show an interesting luminescent behavior in the solid state (at 77 K) and in solution (both at 298 and 77 K). 相似文献