Search results for "ion chemistry"
showing 10 items of 254 documents
NHC-Based Iron Sensitizers for DSSCs
2018
International audience; Nanostructured dye-sensitized solar cells (DSSCs) are promising photovoltaic devices because of their low cost and transparency. Ruthenium polypyridine complexes have long been considered as lead sensitizers for DSSCs, allowing them to reach up to 11% conversion efficiency. However, ruthenium suffers from serious drawbacks potentially limiting its widespread applicability, mainly related to its potential toxicity and scarcity. This has motivated continuous research efforts to develop valuable alternatives from cheap earth-abundant metals, and among them, iron is particularly attractive. Making iron complexes applicable in DSSCs is highly challenging due to an ultrafa…
Polynitrile anions as ligands: From magnetic polymeric architectures to spin crossover materials
2010
International audience; The use of polynitrile anions as ligands (L) either alone or in combination with neutral co-ligands (L′) is a very promising and appealing strategy to get molecular architectures with different topologies and dimensionalities thanks to their ability to coordinate and bridge metal ions in many different ways. The presence of several potentially coordinating nitrile groups (or even other donor groups as –OH, –SH or –NH2), their rigidity and their electronic delocalization allow the synthesis of original magnetic high dimensional coordination polymers with transition metals ions. Furthermore, these ligands have shown coordinating and bridging capabilities in novel discr…
Radical Polymerization of Styrene Controlled by Half-Sandwich Mo(III)/Mo(IV) Couples: All Basic Mechanisms Are Possible
2001
Density functional calculations of bond dissociation energies (BDEs) have been used as a guide to the choice of metal system suitable for controlling styrene polymerization by either the stable free radical polymerization (SFRP) or the atom transfer radical polymerization (ATRP) mechanism. In accord with the theoretical prediction, CpMo(eta(4)-C(4)H(6))(CH(2)SiMe(3))(2), 2, is not capable of yielding SFRP of styrene. Still in accord with theoretical prediction, CpMo(eta(4)-C(4)H(6))Cl(2), 1, CpMo(PMe(3))(2)Cl(2), 3, and CpMo(dppe)Cl(2) (dppe = 1,2-bis(diphenylphosphino)ethane), 4, yield controlled styrene polymerization by the SFRP mechanism in the presence of 2,2'-azobisisobutyronitrile (A…
Controlled radical polymerization of alkyl acrylates and styrene using a half-sandwich molybdenum(III) complex containing diazadiene ligands
2003
Abstract The half-sandwich molybdenum(III) complex CpMoCl 2 ( i Pr 2 -dad) ( i Pr 2 -dad= i Pr–NCH–CHN– i Pr) proved to be an effective metal catalyst for the controlled radical polymerization of methyl acrylate, butyl acrylate, and styrene. In conjunction with an alkyl iodide [R–I: CH 3 CH(COOEt)I] as an initiator and in the presence or absence of Al(O– i -Pr) 3 as a co-catalyst, the molybdenum-based system gave polymers with narrow molecular weight distributions. The in situ addition of styrene to a macroinitiator of poly(methylacrylate) afforded an AB-type block copolymer.
Half-sandwich molybdenum(III) compounds containing diazadiene ligands and their use in the controlled radical polymerization of styrene
2002
Abstract The reaction of CpMoCl2 with diazadiene ligands RNCHCHNR (R2dad) affords the corresponding paramagnetic complexes CpMoCl2(R2dad) (R=Ph, 1; p-Tol, 2; C6H3Pr2i-2,6, 3; and Pri, 4). All compounds have been characterized by EPR spectroscopy and have been investigated by cyclic voltammetry. They display one-electron oxidation and reduction processes, these being reversible or irreversible depending on the nature of R. The irreversibility of the reduction wave is due to a chemical follow-up process which consists of chloride loss from the reduced product. This phenomenon is suppressed in the presence of excess chloride in solution. An X-ray structure of 3 verifies the mononuclear na…
How the interplay of different control mechanisms affects the initiator efficiency factor in controlled radical polymerization: An investigation usin…
2007
International audience; Compound CpMoI2(iPr2dad) (iPr2dad = iPrNdouble bondCHsingle bondCHdouble bondNiPr), obtained by halide exchange from CpMoCl2(iPr2dad) and NaI, has been isolated and characterized by EPR spectroscopy, cyclic voltammetry, and X-ray crystallography. Its action as a catalyst in atom transfer radical polymerization (ATRP) and as a spin trap in organometallic radical polymerization (OMRP) of styrene and methyl acrylate (MA) monomers has been investigated and compared with that of the dichloro analogue. Compound CpMoCl2(iPr2dad) catalyzes the ATRP of styrene and MA with low efficiency factors f (as low as 0.37 for MA and ethyl 2-chloropropionate as initiator), while it irre…
Half-sandwich Mo(III) complexes with asymmetric diazadiene ligands
2006
The asymmetric 1,4-diazadiene ligands R ∗ N CHCH NR ∗ [R ∗ = ( S )-CH(CH 3 )Ph], R 2 ∗ dad , and 2,2′-bis(4-ethyloxazoline), as-ox, have been used to generate half-sandwich Mo III derivatives by addition to Cp 2 Mo 2 Cl 4 . Ligand R 2 ∗ dad affords a mononuclear, paramagnetic 17-electron product, CpMoCl 2 ( R 2 ∗ dad ) , whereas as-ox leads to the isolation of a dinuclear compound where only one molecule of ligand has been added per two Mo atoms, Cp 2 Mo 2 Cl 4 (as-ox). In the presence of free as-ox, this compound coexists with the paramagnetic mononuclear complex in solution. Both products are capable of controlling the radical polymerization of styrene under typical atom transfer radical…
The Grignard Reaction − Unraveling a Chemical Puzzle
2020
More than 100 years since its discovery, the mechanism of the Grignard reaction remains unresolved. Ambiguities arise from the concomitant presence of multiple organomagnesium species and the competing mechanisms involving either nucleophilic addition or the formation of radical intermediates. To shed light on this topic, quantum-chemical calculations and ab initio molecular dynamics simulations are used to study the reaction of CH3MgCl in tetrahydrofuran with acetaldehyde and fluorenone as prototypical reagents. All organomagnesium species coexisting in solution due to the Schlenk equilibrium are found to be competent reagents for the nucleophilic pathway. The range of activation energies …
Slow Dynamics of the Magnetization in One-Dimensional Coordination Polymers: Single-Chain Magnets
2009
18 pages; International audience; Slow relaxation of the magnetization (i.e., "magnet-like" behavior) in materials composed of magnetically isolated chains was observed for the first time in 2001. This type of behavior was predicted in the 1960s by Glauber in a chain of ferromagnetically coupled Ising spins (the so-called Glauber dynamics). In 2002, this new class of nanomagnets was named single-chain magnets (SCMs) by analogy to single-molecule magnets that are isolated molecules displaying related superparamagnetic properties. A long-range order occurs only at T = 0 K in any pure one-dimensional (1D) system, and thus such systems remain in their paramagnetic state at any finite temperatur…
Binding of fluoride and carbonate by open chain polyammonium cations
2004
The formation of open chain polyammonium cation-fluoride and -carbonate complexes was studied by potentiometric and calorimetric techniques at t=25 degrees C. Several species of H(i)AL (A=amine; L=F(-), CO(3)(2-)) are formed in both systems with a mean stability log K=1.0zeta (zeta=|z(anion)xz(cation)|) and log K=2.0zeta for fluoride and carbonate, respectively. The comparison with analogous systems (chloride and acetate for fluoride and hydrogenphosphate, sulfate and malonate for carbonate) showed that fluoride and carbonate form the most stable species with open chain polyammonium cations, among low molecular weight anions. The N-alkyl substitution does not play negligible role in the sta…