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961.
962.
Dr. Benjamin J. Coe Dr. Aggelos Avramopoulos Dr. Manthos G. Papadopoulos Prof. Dr. Kristine Pierloot Dr. Steven Vancoillie Dr. Heribert Reis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(47):15955-15963
Static excited‐state polarisabilities and hyperpolarisabilities of three RuII ammine complexes are computed at the density functional theory (DFT) and several correlated ab initio levels. Most accurate modelling of the low energy electronic absorption spectrum is obtained with the hybrid functionals B3LYP, B3P86 or M06 for the complex [RuII(NH3)5(MeQ+)]3+ (MeQ+=N‐methyl‐4,4′‐bipyridinium, 3 ) in acetonitrile. The match with experimental data is less good for [RuII(NH3)5L]3+ (L=N‐methylpyrazinium, 2 ; N‐methyl‐4‐{E,E‐4‐(4‐pyridyl)buta‐1,3‐dienyl}pyridinium, 4 ). These calculations confirm that the first dipole‐ allowed excited state (FDAES) has metal‐to‐ligand charge‐transfer (MLCT) character. Both the solution and gas‐phase results obtained for 3 by using B3LYP, B3P86 or M06 are very similar to those from restricted active‐space SCF second‐order perturbation theory (RASPT2) with a very large basis set and large active space. However, the time‐dependent DFT λmax predictions from the long‐range corrected functionals CAM‐B3LYP, LC‐ωPBE and wB97XB and also the fully ab initio resolution of identity approximate coupled‐cluster method (gas‐phase only) are less accurate for all three complexes. The ground state (GS) two‐state approximation first hyperpolarisability β2SA for 3 from RASPT2 is very close to that derived experimentally via hyper‐Rayleigh scattering, whereas the corresponding DFT‐based values are considerably larger. The β responses calculated by using B3LYP, B3P86 or M06 increase markedly as the π‐conjugation extends on moving along the series 2 → 4 , for both the GS and FDAES species. All three functionals predict substantial FDAES β enhancements for each complex, increasing with the π‐conjugation, up to about sevenfold for 4 . Also, the computed second hyperpolarisabilities γ generally increase in the FDAES, but the results vary between the different functionals. 相似文献
963.
964.
965.
Benjamin M. Gridley Dr. Graeme J. Moxey Dr. William Lewis Prof. Alexander J. Blake Dr. Deborah L. Kays 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11446-11453
The synthesis and characterization of the first series of low‐coordinate bis(terphenyl) complexes of the Group 12 metals, [Zn(2,6‐Naph2C6H3)2] ( 1 ), [Cd(OEt2)(2,6‐Naph2C6H3)2] ( 2 ) and [Hg(OEt2)(2,6‐Naph2C6H3)2] ( 3 ) (Naph=1‐C10H7) are described. The naphthyl substituents of the terphenyl ligands confer considerable steric bulk, and as a result of limited flexibility introduce multiple conformations to these unusual systems. In the solid state, complex 1 features a two‐coordinate Zn centre with the ligands oriented in a syn/anti conformation, whereas the three‐coordinate distorted T‐shaped complexes 2 and 3 feature the ligands in the syn/syn configurations. The results of DFT calculations are in good agreement with the solid‐state configurations for these complexes and support the spectroscopic measurements, which indicate several conformers in solution. 相似文献
966.
Philipp Bissinger Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Rian D. Dewhurst Dr. Katharina Kraft Thomas Kramer Dr. Krzysztof Radacki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13402-13407
The synthesis of base‐stabilized boryl and borylene complexes is reported. An N‐heterocyclic carbene (NHC)‐stabilized iron–dihydroboryl complex was prepared by two different routes including methane liberation and salt elimination. A range of base‐stabilized iron–dichloroboryl complexes was prepared by addition of Lewis bases to boryl complexes. Base‐stabilized, cationic monochloroborylene complexes were synthesized from these boryl complexes by halide abstraction by using weakly coordinating anions. 相似文献
967.
Dipl.‐Chem. Steffen Styra Dr. Sandra González‐Gallardo Dr. Felix Armbruster Dr. Pascual Oña‐Burgos Dipl.‐Chem. Eric Moos Dr. Matthias Vonderach Priv.‐Doz. Dr. Patrick Weis Priv.‐Doz. Dr. Oliver Hampe Dipl.‐Chem. Anneken Grün Dipl.‐Chem. Yvonne Schmitt Prof. Dr. Markus Gerhards Dipl.‐Chem. Fabian Menges Dipl.‐Chem. Maximilian Gaffga Prof. Dr. Gereon Niedner‐Schatteburg Prof. Dr. Frank Breher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8436-8446
A series of bimetallic silyl halido cuprates consisting of the new tripodal silicon‐based metalloligand [κ3N‐Si(3,5‐Me2pz)3Mo(CO)3]? is presented (pz=pyrazolyl). This metalloligand is straightforwardly accessible by reacting the ambidentate ligand tris(3,5‐dimethylpyrazolyl)silanide ({Si(3,5‐Me2pz)3}?) with [Mo(CO)3(η6‐toluene)]. The compound features a fac‐coordinated tripodal chelating ligand and an outward pointing, “free” pyramidal silyl donor, which is easily accessible for a secondary coordination to other metal centers. Several bimetallic silyl halido cuprates of the general formula [CuX{μ‐κ1Si:κ3N‐Si(3,5‐Me2pz)3Mo(CO)3}]? (X=Cl, Br, I) have been synthesized. The electronic and structural properties of these complexes were probed in detail by X‐ray diffraction analysis, electrospray mass spectrometry, infrared‐induced multiphoton dissociation studies, cyclic voltammetry, spectroelectrochemistry, gas‐phase photoelectron spectroscopy, as well as UV/Vis and fluorescence spectroscopy. The heterobimetallic complexes contain linear two‐coordinate copper(I) entities with the shortest silicon–copper distances reported so far. Oxidation of the anionic complexes in methylene chloride and acetonitrile solutions at ${E{{0\hfill \atop 1/2\hfill}}}$ =?0.60 and ?0.44 V (vs. ferrocene/ferrocenium (Fc/Fc+)), respectively, shows substantial reversibility. Based on various results obtained from different characterization methods, as well as density functional theory calculations, these oxidation events were attributed to the Mo0/MoI redox couple. 相似文献
968.
Dr. Stéphane Le Gac Dr. Btissam Najjari Dr. Vincent Dorcet Dr. Thierry Roisnel Dr. Luca Fusaro Prof. Dr. Michel Luhmer Dr. Eric Furet Dr. Jean‐François Halet Dr. Bernard Boitrel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):11021-11038
Overhanging carboxylic acid porphyrins have revealed promising ditopic ligands offering a new entry in the field of supramolecular coordination chemistry of porphyrinoids. Notably, the adjunction of a so‐called hanging‐atop (HAT) PbII cation to regular PbII porphyrin complexes allowed a stereoselective incorporation of the N‐core bound cation, and an allosterically controlled Newton’s cradle‐like motion of the two PbII ions also emerged from such bimetallic complexes. In this contribution, we have extended this work to other ligands and metal ions, aiming at understanding the parameters that control the HAT PbII coordination. The nature of the N‐core bound metal ion (ZnII, CdII), the influence of the deprotonation state of the overhanging COOH group and the presence of a neutral ligand on the opposite side (exogenous or intramolecular), have been examined through 1H NMR spectroscopic experiments with the help of radiocrystallographic structures and DFT calculations. Single and bis‐strap ligands have been considered. They all incorporate a COOH group hung over the N‐core on one side. For the bis‐strap ligands, either an ester or an amide group has been introduced on the other side. In the presence of a base, the mononuclear ZnII or CdII complexes incorporate the carbonyl of the overhanging carboxylate as apical ligand, decreasing its availability for the binding of a HAT PbII. An allosteric effector (e.g., 4‐dimethylaminopyridine (DMAP), in the case of a single‐strap ligand) or an intramolecular ligand (e.g., an amide group), strong enough to compete with the carbonyl of the hung COO?, is required to switch the N‐core bound cation to the opposite side with concomitant release of the COO?, thereby allowing HAT PbII complexation. In the absence of a base, ZnII or CdII binds preferentially the carbonyl of the intramolecular ester or amide groups in apical position rather than that of the COOH. This better preorganization, with the overhanging COOH fully available, is responsible for a stronger binding of the HAT PbII. Thus, either allosteric or acid–base control is achieved through stereoselective metalation of ZnII or CdII. In the latter case, according to the deprotonation state of the COOH group, the best electron‐donating ligand is located on one or the other side of the porphyrin (COO?>CONHR>COOR>COOH): the lower affinity of COOH for ZnII and CdII, the higher for a HAT PbII. These insights provide new opportunities for the elaboration of innovative bimetallic molecular switches. 相似文献
969.
Rinta Sato Dr. Kosuke Suzuki Midori Sugawa Prof. Dr. Noritaka Mizuno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(39):12982-12990
Polyoxometalates (POMs) with heterodinuclear lanthanoid cores, TBA8H4[{Ln(μ2‐OH)2Ln′}(γ‐SiW10O36)2] ( LnLn′ ; Ln=Gd, Dy; Ln′=Eu, Yb, Lu; TBA=tetra‐n‐butylammonium), were successfully synthesized through the stepwise incorporation of two types of lanthanoid cations into the vacant sites of lacunary [γ‐SiW10O36]8? units without the use of templating cations. The incorporation of a Ln3+ ion into the vacant site between two [γ‐SiW10O36]8? units afforded mononuclear Ln3+‐containing sandwich‐type POMs with vacant sites ( Ln1 ; TBA8H5[{Ln(H2O)4}(γ‐SiW10O36)2]; Ln=Dy, Gd, La). The vacant sites in Ln1 were surrounded by coordinating W? O and Ln? O oxygen atoms. On the addition of one equivalent of [Ln′(acac)3] to solutions of Dy1 or Gd1 in 1,2‐dichloroethane (DCE), heterodinuclear lanthanoid cores with bis(μ2‐OH) bridging ligands, [Dy(μ2‐OH)2Ln′]4+, were selectively synthesized ( LnLn′ ; Ln=Dy, Gd; Ln′=Eu, Yb, Lu). On the other hand, La1 , which contained the largest lanthanoid cation, could not accommodate a second Ln′3+ ion. DyLn′ showed single‐molecule magnet behavior and their energy barriers for magnetization reversal (ΔE/kB) could be manipulated by adjusting the coordination geometry and anisotropy of the Dy3+ ion by tuning the adjacent Ln′3+ ion in the heterodinuclear [Dy(μ2‐OH)2Ln′]4+ cores. The energy barriers increased in the order: DyLu (ΔE/kB=48 K)< DyYb (53 K)< DyDy (66 K)< DyEu (73 K), with an increase in the ionic radii of Ln′3+; DyEu showed the highest energy barrier. 相似文献