Search results for " coupling"

Thermal Behavior of dry and hydrated MbCO crowded systems

2009

Coexistence of spin-crossover and antiferromagnetic coupling phenomena in the novel dinuclear Fe(II) complex [Fe(dpa)(NCS)2]2bpym

2003

Abstract The iron(II) spin crossover dinuclear compound [Fe(dpa)(NCS) 2 ] 2 bpym where dpa = 2,2 ′ -dipyridylamine and bpym = 2,2 ′ -bipyrimidine has been synthesized and characterized. Variable-temperature magnetic susceptibility and 57 Fe Mossbauer spectroscopy data provide evidence for a rather complete and continuous S=2 ( HS )↔S=0 (LS) spin-crossover behavior taking place in the temperature range 400–50 K (T 1/2 =245 K ) without the presence of a plateau at 50% of conversion. The absence of such plateau, which is characteristic of all dinuclear compounds so far studied, is interpreted in terms of synergetic effect between intramolecular and intermolecular interactions.

Selective Photoswitching of the Binuclear Spin Crossover Compound{[Fe(bt)(NCS)2]2(bpm)}into Two Distinct Macroscopic Phases

2005

The low-spin (LS-LS, $S=0$) diamagnetic form of the binuclear spin crossover complex ${[\mathrm{Fe}(\mathrm{bt})(\mathrm{NCS}{)}_{2}{]}_{2}(\mathrm{bpm})}$ was selectively photoconverted into two distinct macroscopic phases at different excitation wavelengths (1342 or 647.1 nm). These long-lived metastable phases have been identified, respectively, as the symmetry-broken paramagnetic form (HS-LS, $\mathrm{S}=2$) and the antiferromagnetically coupled (HS-HS, $S=0$) high-spin form of the compound. The selectivity may be explained by the strong coupling of the primary excited states to the paramagnetic state.

Interplay of Antiferromagnetic Coupling and Spin Crossover in Dinuclear Iron(II) Complexes

2003

This article reports on the study of the interplay between magnetic coupling and spin transition in 2,2′-bipyrimidine (bpym)-bridged iron(II) dinuclear compounds. Coexistence of both phenomena has been observed in [Fe(bpym)(NCS)2]2bpym, [Fe(bpym)(NCSe)2]2bpym and [Fe(bt)(NCS)2]2bpym (bpym = 2,2′-bipyrimidine, bt = 2,2′-bithiazoline) by the action of external physical factors namely pressure or electromagnetic radiation. Competition between magnetic exchange and spin crossover has been studied in [Fe(bpym)(NCS)2]2bpym at 6.3 kbar. LIESST experiments carried out in [Fe(bpym)(NCSe)2]2bpym and [Fe(bt)(NCS)2]2bpym at 4.2 K have shown that is possible to achieve dinuclear molecules with different…

Numerical simulation of fatigue-driven delamination using interface elements

2005

This paper presents a computational technique for the prediction of fatigue-driven delamination growth in composite materials. The interface element, which has been extensively applied to predict delamination growth due to static loading, has been modified to incorporate the effects of cyclic loading. Using a damage mechanics formulation, the constitutive law for the interface element has been extended by incorporating a modified version of a continuum fatigue damage model. The paper presents details of the fatigue degradation strategy and examples of the predicted fatigue delamination growth in mode I, mode II and mixed mode I/II are presented to demonstrate that the numerical model mimics…

General restrictions for the relaxation constants of the polarization moments of the density matrix

1992

General inequalities for the relaxation constants of polarization moments are examined. Concrete numerical limitations for the values of these constants are obtained. In recent years it has been generally accepted to characterize the distribution of the angular momentum j of atomic as well as molecular states in the framework of the irreducible tensorial operators PG. The state is described by means of polarization moments p& which are the expansion coefficients of the angular momentum density matrix pm,,,, on the tensorial operators pz:

Catalytic Efficiency of a New Tridentate Ferrocenyl Phosphine Auxiliary: Sonogashira Cross-Coupling Reactions of Alkynes with Aryl Bromides and Chlor…

2005

[structure: see text] The catalytic activity in Sonogashira cross-coupling reactions of alkynes with a variety of aryl halides (including chlorides) using a multidentate ferrocenyl phosphine is presented. The novel mixed ferrocenyl aryl/alkyl triphosphine is thermally stable and insensitive to air or moisture, and its robustness allows aryl alkynylation at 10(-1) to 10(-4) mol % catalyst loadings with TONs up to 250,000. Copper-free coupling using phenylacetylene is also accessible in good yield.

Copper(I) Iodide Polyphosphine Adducts at Low Loading for Sonogashira Alkynylation of Demanding Halide Substrates: Ligand Exchange Study between Copp…

2010

The prestabilization of copper iodide with a multidentate ferrocenyl phosphine ligand promotes the palladium-catalyzed cross-coupling of demanding halides with phenylacetylene in a selective way. Novel CuI-triphosphine adducts are described in the solid state and in solution. Their use allowed the introduction of the copper iodide cocatalyst in unprecedented low amounts (0.4 to 0.1 mol %) in systems also employing low amounts of “ligand-free” [PdII(η3-allyl)Cl]2 precursor (0.2 to 0.05 mol %). The scope of substrates is reported, and electronically or sterically deactivated bromides were efficiently coupled. Concerning aryl chlorides, electron-poor activated substrates were also coupled usin…

Dehydrogenative Anodic C−C Coupling of Phenols Bearing Electron‐Withdrawing Groups

2019

Abstract We herein present a metal‐free, electrosynthetic method that enables the direct dehydrogenative coupling reactions of phenols carrying electron‐withdrawing groups for the first time. The reactions are easy to conduct and scalable, as they are carried out in undivided cells and obviate the necessity for additional supporting electrolyte. As such, this conversion is efficient, practical, and thereby environmentally friendly, as production of waste is minimized. The method features a broad substrate scope, and a variety of functional groups are tolerated, providing easy access to precursors for novel polydentate ligands and even heterocycles such as dibenzofurans.

A conjugated polymer with ethyl 2-(2-(pyridin-2-yl)-1H-benzo[d]imidazol-1-yl) acetate units as a novel fluorescent chemosensor for silver(I) detection

2013

Abstract A novel conjugated polymer ( P1 ) containing fluorene and ethyl 2-(2-(pyridin-2-yl)-1 H -benzo[ d ]imidazol-1-yl)acetate (PBMA) was designed and successfully synthesized through the Sonogashira coupling reaction. P1 shows high sensitivity and selectivity for Ag + detection in comparison to other metal cations. Upon addition of Ag + , the fluorescent emission of the polymer solution in THF was quenched dramatically, accompanying the color changed from blue to green. The detection limit for Ag + was 5 × 10 −8  mol L −1 . However, the similar copolymers P2 and P3 containing 2-(pyridin-2-yl)-1 H -benzo[ d ]imidazole and 2-(thiophen-2-yl)-1 H -benzo[ d ]imidazole, respectively, did not …