Search results for "RIP"
showing 10 items of 9780 documents
One-Pot Synthesis to Quinone-Based Diaza[3.3]cyclophanes
2017
A simple one-pot synthesis to [3.3]cyclophanes that involves quinone moieties was found. The protocol tolerates a variety of amines that include aliphatic and aromatic structures with different functional groups, such as hydroxy groups, amides, and terminal double and triple bonds. The straightforward synthesis can be performed by a twofold N-alkylation reaction with 2,5-bis(bromomethyl)-3,6-dimethyl-1,4-benzoquinone (1). Neither anhydrous nor inert conditions are required. Various amines can be employed without any activating groups, several functionalities at end groups are tolerated, and the cyclophanes generated can be easily modified or embedded into larger molecular architectures. The…
Role of the Open-Shell Character on the Pressure-Induced Conductivity of an Organic Donor-Acceptor Radical Dyad
2018
Single‐component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF‐Ph‐PTM derivative (1) are reported and implications of its crystal…
Theoretical Investigation of the Low-Energy States of CpMoCl(PMe 3 ) 2 and Their Role in the Spin-Forbidden Addition of N 2 and CO
2003
International audience; A recent computational investigation of Jahn−Teller effects in unsaturated 16-electron d4d6 [CpMLn] complexes (Abu-Hasanayn, F.; Cheong, P.; Oliff, M. Angew. Chem.2002, 41, 2120) highlighted the typical presence of two spin-triplet and two singlet states of competing stability in these complexes and pointed out the necessity to account for more than one electronic state in studies thereof. Consequently, we have reinvestigated the addition of N2 to all the four low-energy states of CpMoCl(PH3)2, a reaction for which previously only one singlet and one triplet state have been considered (Keogh, D. W.; Poli, R. J. Am. Chem. Soc.1997, 119, 2516). The present study was pe…
Cis- and trans molybdenum oxo complexes of a prochiral tetradentate aminophenolate ligand : Synthesis, characterization and oxotransfer activity
2020
Abstract Reaction of [MoO2Cl2(dmso)2] with the tetradentate O2N2 donor ligand papy [H2papy = N-(2-hydroxybenzyl)-N-(2-picolyl)glycine] leads to formation of the dioxomolybdenum(VI) complex [MoO2(papy)] (1) as a mixture of cis and trans isomers. Recrystallization from methanol furnishes solid cis-1, whereas the use of a dichloromethane-hexane mixture allows for the isolation of the trans-1 isomer. Both isomers have been structurally characterized by X-ray crystallography and the energy difference between the isomeric pair has been investigated by electronic structure calculations. Optimization of two configurational isomers in the gas phase predicts the trans isomer to lie 2.5 kcal/mol lower…
Versatile behavior of conjugated diynes with zirconocene reactive species
2008
Thermal decomposition of Cp2ZrPh2 in the presence of the buta-1,3-diynes RC≡CC≡CR (R = Ph, SiMe3) can lead to seven- or five-membered metallacycles. In both cases a stable benzo-fused seven-membered zirconacyclocumulene arising from a 2-fold insertion of the triple bonds of the dialkyne in the in situ generated zirconocene benzyne is formed. In the case of Me3SiC≡CC≡CSiMe3 a second minor complex is isolated: a 3-alkynyl-substituted zirconaindene arising from a β monoinsertion of one acetylenic function of the conjugated diyne in the zirconocene benzyne. No stable 2-alkynyl-substituted zirconacycle was isolated. This α monoinsertion complex is an intermediate in the exchange of the metalated…
Design of bimetallic magnetic chains based on oxalate complexes: towards single chain magnets
2009
We describe the synthesis, structure and magnetic characterization of several oxalate-based bimetallic 1D systems. We will exemplify how by suitable choice of the molecular building blocks and strict control of their arrangement in the solid state, the magnetic properties of these low-dimensional materials can be tuned to finally obtain bimetallic oxalate chains behaving as single-chain magnets (SCM). First, we will focus on compounds [K(18-crown-6)][MII(bpy)Cr(ox)3] (1, 2; MII = Mn, Co; bpy = C10N2H8). The MnCr derivative behaves as a 1D ferromagnet down to 2 K, the lowest investigated temperature. The lack of magnetic ordering in this chain prompted us to prepare the more anisotropic MnCo…
Photomagnetic properties of an Fe(ii) spin-crossover complex of 6-(3,5-diamino-2,4,6-triazinyl)-2,2'-bipyridine and its insertion into 2D and 3D bime…
2017
International audience; The Fe(ii) complex of the L1 ligand (L1 = 6-(3,5-diamino-2,4,6-triazinyl)-2,2'-bipyridine) has been used as a templating cation for the growth of oxalate-based networks. The magnetic characterization of the [Fe(II)(L1)2](ClO4)2·CH3CN (1) precursor in the solid state has been performed for the first time showing that the low-spin (LS) state is predominating from 2 to 400 K with 10% of Fe(ii), which undergoes a gradual and irreversible spin-crossover above 350 K. 1 presents the LIESST effect with a photo-conversion close to 25% and a T(LIESST) of 49 K. During the preparation of 1, a secondary product of the formula [Fe(II)(L1)(CH3CN)2(H2O)](ClO4)2·CH3CN (2) has been ob…
Electrochemical meso-functionalization of magnesium(II) porphine
2010
International audience; Regioselective meso-functionalization of the totally unsubstituted magnesium(II) porphine was performed by controlled potential electrolysis with pyridine and triphenylphosphine as nucleophiles leading to the original pyridinium and phosphonium substituted derivatives, respectively. The crystallographic structure of the latter is described as the only meso-phosphonium porphyrin reported to date.
Cobaltocenium substituents as electron acceptors in photosynthetic model dyads
2017
Abstract Cobaltocenium carboxylic acid hexafluorophosphate has been attached to a zinc(II) meso-tetraphenyl porphyrin chromophore via an amide linkage. Optical and electrochemical studies reveal that the metallocene and the porphyrin interact only negligibly in the ground state of the dyad. Photoinduced charge-shift from the zinc porphyrin to the cobaltocenium substituent to give the zinc porphyrin radical cation and the cobaltocene occurs upon exciting the porphyrin with light. Steady state emission, time-resolved fluorescence and transient absorption pump–probe spectroscopy in addition to density functional theory calculations suggest that the charge shift to the cobaltocenium substituent…
The [Pd(bipy)]2+ “merry-go-round”: Insights into the lability of the Pd–N bond
2009
Abstract Two tripods (1 and 2) featuring pyrimidinyl pendant arms have been synthesized from 5-(1H-pyrazol-3-yl)-pyrimidine (5) and 1,3,5-tribromomethylbenzene derivatives. Reaction with three equivalents of [Pd(bipy)](NO3)2 to form a macrotricycle closed by palladium coordination unexpectedly afforded the mononuclear species [Pd(1)(bipy)]2+ and [Pd(2)(bipy)]2+. These complexes show fluxional behavior on the 1H NMR timescale, the [Pd(bipy)]2+ fragment hopping between the pyrimidinyl coordinating moieties. The ΔGc‡’s estimated by the coalescence method are temperature independent, which means that ΔSc‡ = 0. This indicates that the “merry-go-round” process of [Pd(bipy)]2+ occurs intramolecula…