Search results for "ionic"
showing 10 items of 2016 documents
Doubly charged ions of bridged [4n] annulenes. An evaluation of diatropic ring current effects.
1985
Abstract [4n]Annulenes are transformed into doubly charged ions (dianion, dication) and characterized NMR spectroscopically. The diatropic character of the ionic (4n+2)π-systems is studied as a function of the number of π-electrons.
Indication of an order-order-transition by a partial disordering in ABC-triblock copolymers
1996
Poly(ethylene-alt-propylene)-block-polyethylethylene-block-polystyrene (PEP-b-PEE-b-PS) triblock copolymers were synthesized by anionic polymerization and subsequent hydrogenation of poly-1,4-isoprene-block-poly-1,2-butadiene-block-polystyrene triblock copolymers (1,4PI-b-1,2PB-b-PS). Differential scanning calorimetry and dynamic mechanical spectroscopy reveal an order-order transition which is induced by the mixing of PEP and PEE above their respective order-disorder transition (ODT).
A correlative IR, MS, 1H, 13C and 15N NMR and theoretical study of 4-arylthiazol-2(3H)-onesElectronic supplementary information (ESI) available: NMR …
2002
Sixteen 4-arylthiazol-2(3H)-ones (3) were synthesised by cyclisation of α-thiocyanatoacetophenones (1) in acid solution. They appear to prefer greatly the oxo tautomeric forms. In CCl4 solution an equilibrium between the free CO bond and a “dimeric” hydrogen-bonded form exists in which the latter predominates. Several IR and NMR (1H, 13C and 15N) spectral properties are shown to correlate with Hammett σ-values and/or atomic Mulliken charges and bond orders, the latter being estimated by PM3 or AM1 semiempirical methods. The electron-impact mass spectra were also recorded and the fragmentation mechanisms interpreted in terms of the energetics of the ionic species. In addition, the geometric …
Structural effects of Co and Cr substitution in LaMnO3 + δ
2000
Series of perovskite oxides with the composition LaMn1 − xMxO3 + δ (M = Cr, Co; 0 ≤ x ≤ 1) have been synthesized by thermal treatment of precursors obtained by freeze-drying of acetic acid solutions. The oxides have been characterized by X-ray diffraction, and the Mn4+ content and, thus, the oxygen excess, δ, has been determined by redox back-titration. LaMnO3.14 and LaCrO3 phases have the rhombohedral-LaAlO3 and the orthorhombic-GdFeO3 structures, respectively. The LaMn1 − xCrxO3 + δ phases have the rhombohedral structure for x ≤ 0.3, and the orthorhombic structure for x ≥ 0.5. LaCoO3 has, as LaMnO3.14, the rhombohedral structure. However, the LaMn1 − xCoxO3 + δ phases have orthorhombic st…
Competitive gold-activation modes in terminal alkynes: an experimental and mechanistic study.
2013
The competition between π- and dual σ,π-gold-activation modes is revealed in the gold(I)-catalyzed heterocyclization of 1-(o-ethynylaryl)urea. A noticeable effect of various ligands in gold complexes on the choice of these activation modes is described. The cationic [Au(IPr)](+) (IPr=2,6-bis(diisopropylphenyl)imidazol-2-ylidene) complex cleanly promotes the π activation of terminal alkynes, whereas [Au(PtBu3 )](+) favors intermediate σ,π species. In this experimental and mechanistic study, which includes kinetic and cross-over experiments, several σ-gold, σ,π-gold, and other gold polynuclear reaction intermediates have been isolated and identified by NMR spectroscopy, X-ray diffraction, or …
Properties of small clusters at ionic surfaces: (NaCl)nclusters (n=1–48) at the (100) MgO surface
1995
We have studied the geometry, binding energy, interaction with the surface, barriers for diffusion, optical absorption, and the possibility for their observation using atomic force microscopy of (NaCl${)}_{\mathit{n}}$ clusters (n=1--48) on the (100) MgO surface. We address the questions at which cluster size do the adsorbed molecules lose their identity and how do strained clusters accommodate the strain. The relation between the structure of initial molecular fragments adsorbed at the surface and the structure of the corresponding thick film is discussed. The results are compared with the calculated structures of the free clusters and the experimental data on the molecular-beam epitaxy of…
Dynamic segregation during ferrite oxidation revealed by XPS
2002
Dynamic segregation phenomena were revealed by XPS during the oxidation of some ferrites (Fe 2.5 Ti 0.5 O 4 , Fe 2.5 Ni 0.5 O 4 , Fe 2 CrO 4 and FeCr 2 O 4 ). This kind of phenomenon induces, at a low temperature (below room temperature), drastic changes in the cationic composition of the most external layers. Dynamic segregation is a function of the cationic composition, the oxidation capability and the morphology of these ferrites. Although dynamic segregation seems to be a quite frequent phenomenon that often can be observed during ferrite oxidation, there are materials in existence where it does not appear, such as molybdenum ferrite.
An Open-Shell Coronoid with Hybrid Chichibabin-Schlenk Conjugation.
2021
A hexaradicaloid molecule with alternating Kekule and non-Kekule connectivities between adjacent spin centers was obtained by fusing two conjugation motifs in Chichibabin and Schlenk hydrocarbons into a coronoid structure. 1 H NMR, ESR, and SQUID experiments and computational analyses show that the system has a singlet ground state with a significant hexaradicaloid character (γ0 =0.826, γ1 =γ2 =0.773). It has multiple thermally accessible high-spin states (up to the septet), with uniform energy gaps of ca 1.0 kcal mol-1 between consecutive multiplicities. In line with its open-shell character, the coronoid has a small electronic band gap (ca. 0.8 eV) and undergoes two consecutive one-electr…
New tubular transition metal oxoanionic derivatives: a systematic approach to condensed phases of the dumortierite family
1993
Abstract An unified synthetic approach has allowed us to isolate a wide set of highly condensed oxoanionic derivatives of transition metals by using solution chemistry procedures. New phases are described [Ni 12+ x H 6−2 x (AsO 4 ) 8 (OH) 6 . Ni 6 (SeO 3 ) 4 (OH) 4 ], and the preparation of other already known [Ni 12+ x H 6−2 x (PO 4 ) 8 (OH) 6 , Ni 3 Te 2 O 6 (OH) 2 ] is significantly simplifi ed. The structure of these derivatives, as well as that of other phases such as M 11 (HPO 3 ) 8 (OH) 6 (M=Zn, Co, Ni), previously characterized by us, can be related to that of the dumortierite mineral. The main features of the tubular channels that characterize this structure and the possibility to …
Unprecedented Hexa- and Undecanuclear Frameworks of Two New Tin(IV) Oxo Clusters Resulting from Partial Debenzylation Reactions
2010
A new and facile synthetic route to the known neutral cluster ((PhCH2)2SnO)6[((PhCH2)2SnOH)2- (CO3)]2 (2) as well as its reactivity toward trifluoromethanesulfonic acid (HO3SCF3, TfOH) are reported. The solid-state structure of the new solvate 2·6C7H8 has been determined by single-crystal X-ray diffraction. The core of 2 can be described as a pair of coplanar pentanuclear [(PhCH2)2SnO]5 ladders bridged at their ends by two carbonate groups. Successive additions of TfOH to a suspension of 2 in CD3CN were monitored by 119Sn{1H} NMR spectroscopy showing the transformation of the fingerprint of 2 (δ = −244, −246, −306 ppm), via new upfield signals, to a final broad resonance located at δ = −474…