Thermal Conductivity of Ionic Liquids: Recent Challenges Facing Theory and Experiment

Journal of Solution Chemistry - Recently ionic liquids have been considered as prospective substances for application as heat transfer fluids, which requires accurate knowledge of their thermal...     

Strength of Si–H ⋯ B charge-inverted hydrogen bonds in 1-silacyclopent-2-enes and 1-silacyclohex-2-enes

It is shown that the H ? B contacts in 1-silacyclohex-2-enes are clearly stabilizing and strong, whereas those in 1-silacyclopent-2-enes are much weaker. This result is supported by analysis of QTAIM-based parameters and appropriate structural changes taking place upon the open form → closed form transformation and is in full agreement with previous NMR spectroscopic data [Wrackmeyer et al. (2006) Appl Organometal Chem 20:99–105]. Also, the influence of electronic and steric effects originating from the presence of specific substituents on the strength of the H ? B contacts is discussed in detail. Some problems and ideas associated with the use of the so-called open-closed method utilized in assessing values of interaction energies are discussed in detail. Particular attention is paid to the correct choice of reference open systems. It is shown that their partial geometry optimization leads to reliable values of interaction energies.     

Catalytic Oxidative Cyclocondensation of o‐Aminophenols to 2‐Amino‐3H‐phenoxazin‐3‐ones

The catalytic oxidative cyclocondensation of the o‐aminophenols 1a–f was investigated. The oxidants used were air/laccase, H₂O₂/horseradish peroxidase, H₂O₂/ebselen (3), and TBHP/diphenyl diselenide 4. The products obtained were 2‐amino‐3H‐phenoxazin‐3‐one—questiomycin A, its derivative 2b, and cinnabarinic acid and actinocin (2c,d). Substrates with methyl groups at 4 and 5 positions of benzene ring were converted to different dihydrophenoxazinones 2g,h. Compounds having chlorine atoms at the same positions underwent oxidation to planar phenoxa-zinones 2e,f with elimination of one hydrochloride molecule.     

Catalytic Oxidative Domino Degradation of Alkyl Phenols Towards 2- and 3-Substituted Muconolactones

The catalytic oxidative domino degradation of phenols was investigated. Hydrogen peroxide (30% aq.) was used as an oxidant and 2,2′-dinitro-4,4′-ditrifluoromethyldiphenyl diselenide 4e as a catalyst. The products were muconic acid 5, and muconolactones muconolactones—5-carboxymethylfuran-2(5H)-ones 7 and 9. Phenols with alkyl groups at 2 or 4 positions of the benzene ring were converted regioselectively to corresponding muconolactones substituted at alkenylene ring carbon atoms. The reaction mechanism is proposed.     

Sulfur-linked cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

ABSTRACT

The synthesis and characterisation of two series of cyanobiphenyl-based liquid crystal dimers containing sulfur links between the spacer and mesogenic units, the 4?-[1,ω-alkanediylbis(thio)]bis-[1,1?-biphenyl]-4-carbonitriles (CBSnSCB), and 4?-({ω-[(4?-cyano[1,1?-biphenyl]-4-yl)oxy]alkyl}thio)[1,1?-biphenyl]-4-carbonitriles (CBSnOCB) are described. The odd members of both series show twist-bend nematic and nematic phases, whereas the even members exhibit only the nematic phase. An analogous cyanoterphenyl-based dimer, 3⁴-{6-[(4?-cyano[1,1?-biphenyl]-4-yl)thio]-hexyl}[1¹,2¹:2⁴,3¹-terphenyl]-1⁴-carbonitrile (CT6SCB), is also reported and shows enantiotropic N_TB and N phases. The transitional properties of these dimers are discussed in terms of molecular curvature, flexibility and biaxiality. The same molecular factors also influence the birefringence of nematic phases. Resonant X-ray scattering studies of the twist-bend nematic phase at both the carbon and sulfur absorption edges were performed, which allowed for the determination of critical behaviour of the helical pitch at the transition to the nematic phase, the behaviour was found to be independent of molecular structure. It was also observed that despite the different molecular bending angle and flexibility, in all compounds the helical pitch length far from the N-N_TB transition corresponds to 4 longitudinal molecular distances.     

Software package SIMPRE—Revisited

This article elucidates the pitfalls identified in the software package SIMPRE recently developed by Baldoví et al. (J. Comput. Chem. 2013, 34, 1961) for modeling the spectroscopic and magnetic properties of single ion magnets as well as single‐molecule magnets. Analysis of the methodology used therein reveals that the crystal field parameters (CFPs), expressed nominally in the Stevens formalism, exhibit features characteristic for the CFPs expressed in the Wybourne notation. The resemblance of the two types of CFPs introduces a serious confusion that may lead to wrong comparisons of the CFPs taken from various sources. To clarify this confusion, the properties of the CFPs ( , ) associated with the Stevens operators ( X = S , J , or L ), which belong to the class of the tesseral‐tensor operators, are contrasted with those of the CFPs B_kq associated with the Wybourne operators , which belong to the class of the spherical‐tensor operators. Importantly, the confused properties of Stevens and Wybourne operators may bear on reliability of SIMPRE calculations. To consider this question independent calculations are carried out using the complete approach and compared with those of the restricted approach utilized earlier. It appears that the numerical results of the package SIMPRE are formally acceptable, however, the meaning of the CFPs must be properly reformulated. Several other conceptual problems arising from misinterpretations of the crucial notions and the CFP notations identified therein are also discussed and clarified. © 2014 Wiley Periodicals, Inc.