Small-Angle Neutron Scattering Study on Aggregation of 1-Alkyl-3-methylimidazolium Based Ionic Liquids in Aqueous Solution

Aggregation structures of 1-alkyl-3-methylimidazolium based ionic liquids (ILs) in aqueous solution were investigated by small-angle neutron scattering (SANS) from the viewpoint of alkyl chain length, n, and anions (Cl^?, Br^? and trifluoromethanesulfonate, $ {\text{CF}}_{3} {\text{SO}}_{3}^{ - } $ ). In [C₄mIm⁺]-based IL systems, no noticeable SANS intensity was observed for all of the systems examined here, although aqueous [C₄mIm⁺][ $ {\text{BF}}_{4}^{ - } $ ] solutions show a significant SANS profile originating from concentration fluctuations in the solution (Almasy et al. J Phys Chem B 112:2382–2387, 2008). This suggests that [C₄mIm⁺][Cl^?], [C₄mIm⁺][Br^?] and [C₄mIm⁺][ $ {\text{CF}}_{3} {\text{SO}}_{3}^{ - } $ ] homogeneously mix with water, unlike the [C₄mIm⁺][ $ {\text{BF}}_{4}^{ - } $ ] system, due to preferential hydration of the ions. In the case of the C _n mIm cations with longer alkyl chain lengths (n = 8 and 12), SANS profiles were clearly observed in the aqueous solutions at IL concentrations of C _IL > 230 and 20.0 mmol·dm^?3, respectively. For aqueous [C₈mIm⁺][Br^?] solutions, the asymptotic behavior of the scattering function varied largely from I(q) ~ q ^?2 to ~q ^?4 with increasing C _IL, indicating that the solution changes from an inhomogeneous mixing state to a nano-scale micelle state. Aqueous [C₁₂mIm⁺][Br^?] solutions show a typical SANS profile for micelle formation in solution. It was found from a model-fitting analysis that the structure of the [C₁₂mIm⁺][Br^?] micelle is ellipsoidal, not spherical, in solutions over the C _IL range examined here.     

New Aspects of 1,3‐Diphosphacyclobutane‐2,4‐diyls

1,3‐Di(tert‐butyl)‐2,4‐bis[2,4,6‐tri(tert‐butyl)phenyl]‐1,3‐diphosphacyclobutane‐2,4‐diyl was formed from [2,4,6‐tri(tert‐butyl)phenyl]phosphaacetylene and t‐BuLi. In addition, the X‐ray diffraction analysis was carried out, together with theoretical calculations of the structure and NMR data.     

Photochemical Ionic-Conductivity Switching Systems of Photochromic Crown Ethers for Information Technology

Design of two types of ion-conducting systems using photochromic crown ethers as the photocontrol agents is described; one type is based on the phase transition of azobenzene derivatives induced by their photoisomerization and the other based on the molecular control of metal ion complexation by crowned spirobenzopyrans. The photoresponsive ion-conducting systems are applicable to electrostatic imaging and photorefractive materials.     

Ligand-ligand redox interaction through some metal-cluster units

The ligand-ligand redox interaction separated by di-, tri-, and hexanuclear cluster units is discussed in terms of the splitting of the redox waves (DeltaE(L)) and the comproportionation constants (Kcom(L)) of the ligand-based mixed valence state. Although two redox-active monodentate ligands in the mononuclear ruthenium(II) complexes (either cis or trans configurations) do not show appreciable splitting in their reduction waves, interestingly those separated by giant triruthenium and hexarhenium cluster units clearly show splitting. The molecular orbital considerations in the literature suggest that these units possess some pi-type molecular orbitals composed of metal dpi and possibly ligand ppi orbitals. Absence of the redox interactions in oxo-bridged diruthenium(II) and oxo-centered trirhodium(III) complexes where such pi molecular orbitals (including an antibonding one) are fully occupied, indicates the importance of empty pi* orbitals for the ligand redox communication.     

SYNTHESIS AND CHARACTERIZATION OF KINETICALLY STABILIZED 1,3-DIPHOSPHACYCLOBUTENE DERIVATIVES

1-(2,4,6-Tri-tert-butylphenyl)-2-phosphaethyne (1) was allowed to react with 0.5 equiv of an alkyllithium and subsequently with an alcohol to afford a bulky 1,3-diphosphacyclobutene, and its structure and coordination properties on transition metals were investigated. On the other hand, 1 was allowed to react with an alkyllithium and iodomethane to form a stable biradical, 1,3-diphosphacyclobutane-2,4-diyl.     

Fragmentation energetics of the phenol(+)···Ar(3) cation cluster

The various dissociation thresholds of phenol(+)···Ar(3) complexes for the consecutive loss of all three Ar ligands were measured in a molecular beam using resonant photoionization efficiency and mass analyzed threshold ionization spectroscopy via excitation of the first excited singlet state (S(1)). The adiabatic ionization energy is derived as 68077 ± 15 cm(-1). The analysis of the dissociation thresholds demonstrate that all three Ar ligands in the neutral phenol···Ar(3) tetramer are attached to the aromatic ring via π-bonding, denoted phenol···Ar(3)(3π). The value of the dissociation threshold for the loss of one Ar ligand from phenol(+)···Ar(3)(3π), ～190 cm(-1), is significantly lower than the binding energy measured for the π-bonded Ar ligand in the phenol(+)···Ar(π) dimer, D(0) = 535 ± 3 cm(-1). This difference is rationalized by an ionization-induced π → H isomerization process occurring prior to dissociation, that is, one Ar atom in phenol(+)···Ar(3)(3π) moves to the OH binding site, leading to a structure with one H-bonded and 2 π-bonded ligands, denoted phenol(+)···Ar(3)(H/2π). The dissociation thresholds for the loss of two and three Ar atoms are also reported as 860 and 1730 cm(-1). From these values, the binding energy of the H-bound Ar atom can be estimated as 870 cm(-1).     

Effect of industrial water components on thermal stability of nitrocellulose

In order to prevent the spontaneous ignition of nitrocellulose (NC), NC is stabilized by washing with industrial water in its synthesis process. However, there is a possibility that the components in industrial water contribute to the thermal stability of NC. In this way, the purpose of this study is to clarify the effect of industrial water components on the thermal stability of NC. In experiments, a heat flux calorimeter was used to observe the thermal behavior of NC with the residue of vaporized industrial water. The induction period of heat release of NC with 2-mass% residues was approximately 2–5 h shorter than that of NC alone whose induction period was observed at 7 h. Those results indicate that the residue destabilized NC. On the other hand, when the additive amount of the residue was increased, the induction period gradually increased as well. Based upon these results, we assume that inorganic salts contributing to stabilization and destabilization competitively coexist in the industrial water components. The same thermal analysis was performed on NC with CaCO₃, CaSO₄, CaCl, ZnSO₄, NaCl, and CuCl. Those salts are predicted to exist in the industrial water. In the results, the induction period of NC with 2-mass% CaCO₃ was approximately 15-h longer than that of NC alone, while the induction period with the inorganic salts CaSO₄, CaCl, ZnSO₄, NaCl, and CuCl was 4–5-h shorter. Therefore, when the industrial water components accumulate in NC, the destabilization by inorganic salts such as CaSO₄, CaCl, ZnSO₄, NaCl, and CuCl and the stabilization by compounds such as CaCO₃ are thought to countervail against each other.     

IR signature of the photoionization-induced hydrophobic-->hydrophilic site switching in phenol-Arn clusters

IR spectra of phenol-Arn (PhOH-Arn) clusters with n=1 and 2 were measured in the neutral and cationic electronic ground states in order to determine the preferential intermolecular ligand binding motifs, hydrogen bonding (hydrophilic interaction) versus pi bonding (hydrophobic interaction). Analysis of the vibrational frequencies of the OH stretching motion, nuOH, observed in nanosecond IR spectra demonstrates that neutral PhOH-Ar and PhOH-Ar2 as well as cationic PhOH+-Ar have a pi-bound structure, in which the Ar atoms bind to the aromatic ring. In contrast, the PhOH+-Ar2 cluster cation is concluded to have a H-bound structure, in which one Ar atom is hydrogen-bonded to the OH group. This pi-->H binding site switching induced by ionization was directly monitored in real time by picosecond time-resolved IR spectroscopy. The pi-bound nuOH band is observed just after the ionization and disappears simultaneously with the appearance of the H-bound nuOH band. The analysis of the picosecond IR spectra demonstrates that (i) the pi-->H site switching is an elementary reaction with a time constant of approximately 7 ps, which is roughly independent of the available internal vibrational energy, (ii) the barrier for the isomerization reaction is rather low(<100 cm(-1)), (iii) both the position and the width of the H-bound nuOH band change with the delay time, and the time evolution of these spectral changes can be rationalized by intracluster vibrational energy redistribution occurring after the site switching. The observation of the ionization-induced switch from pi bonding to H bonding in the PhOH+-Ar2 cation corresponds to the first manifestation of an intermolecular isomerization reaction in a charged aggregate.