Orientation polarization from faster motions in the ultraviscous and glassy diethyl phthalate and its entropy

Dielectric spectra of the beta relaxation in glassy and ultraviscous liquid diethyl phthalate show that its relaxation strength Delta epsilon(beta), the distribution of times, and the relaxation rate are more sensitive to temperature T in the ultraviscous liquid than in the glassy state. The Delta epsilon(beta) against temperature plot has an elbow-shaped break near T(g) of approximately 181 K, which is remarkably similar to that observed in the entropy, enthalpy, and volume against temperature plots, and in the plot of Delta epsilon(beta) against the liquid's entropy minus its 0 K value. The ratio of Delta epsilon(beta) to diethyl phthalate's entropy, after subtracting the 0 K value, is 1.08 x 10(-3) mol K/J in the glassy state at 120.4 K, which decreases slowly to 0.81 x 10(-3) mol K/J at 176 K near T(g) and thereafter rapidly increases to 1.57 x 10(-3) mol K/J at 190 K. Variation in Delta epsilon(beta) parallels the variation of the entropy. A change in the activation energy of the beta process at T>T(g) indicates that its rate is also determined by the structure of the ultraviscous liquid. Features of beta relaxation are consistent with localized motions of molecules and may not involve small-angle motions of all molecules.     

Synthesis and characterization of some α-naphthyl selenium/tellurium derivatives: X-ray crystal structure of benzyl-1-naphthyl selenide and diphenylmethyl-1-naphthyl selenide

A large number of α-naphthyl selenium and tellurium compounds (1-14) have been prepared through two different methods. The first method involves the alkylation of sodium 1-naphthylselenolate/tellurolate, generated in situ using hydrazine hydrate as reducing agent while the second method involves the reaction of in situ generated α-naphthylseleno/telluromagnesium bromide with an appropriate electrophile. The synthesized alkyl-1-naphthyl selenides/tellurides and some α,ω-bis(1-naphthylseleno)alkanes have been characterized with the help of elemental analysis and using various spectroscopic techniques viz., NMR (¹H, ¹³C, ⁷⁷Se and ¹²⁵Te), IR, UV/vis spectroscopy and mass spectrometry (only in few representative cases). Interpretation of ¹H, ¹³C NMR spectra and assignment of individual resonances for tris(1-naphthylseleno)methane have been done with the help of [¹H-¹H] and [¹H-¹³C] correlation spectroscopy (COSY). X-ray crystallographic results and molecular geometry of benzyl-1-naphthyl selenide, 2 and diphenylmethyl-1-naphthyl selenide, 3 have also been illustrated.     

Polynitrogen chemistry. Synthesis, characterization, and crystal structure of surprisingly stable fluoroantimonate salts of N5+.

The new N5+ salt, N5+ SbF(6)(-), was prepared from N(2)F(+)SbF(6)(-) and HN(3) in anhydrous HF solution. The white solid is surprisingly stable, decomposing only at 70 degrees C, and is relatively insensitive to impact. Its vibrational spectrum exhibits all nine fundamentals with frequencies that are in excellent agreement with the theoretical calculations for a five-atomic V-shaped ion of C(2)(v)symmetry. The N5+ Sb(2)F(11)(-) salt was also prepared, and its crystal structure was determined. The geometry previously predicted for free gaseous N5+ from theoretical calculations was confirmed within experimental error. The Sb(2)F(11)(-) anions exhibit an unusual geometry with eclipsed SbF(4) groups due to interionic bridging with the N5+ cations. The N5+ cation is a powerful one-electron oxidizer. It readily oxidizes NO, NO(2), and Br(2) but fails to oxidize Cl(2), Xe, or O(2).     

The role of hydrogen bonding in pseudo-macrocyclic ring formation in 2,6-dimethyl-1,3,5,7-cyclooctatetraene 1,3,5,7-tetracarboxylic acid monohydrate

2,6-Dimethyl-1,3,5,7-cyclooctatetraene-1,3,5,7-tetracarboxylic acid 3, C₁₄H₁₄O₉, was prepared by thermolysis of the corresponding semibullvalene and characterized by spectroscopic and single-crystal X-ray diffraction studies. The monohydrate of 3 crystallizes in the tetrahedral space group P-4n2, a = 11.0924(3) Å, c = 12.6799(5) Å, V = 1560.15(9) ų, Z = 4. The cyclooctatetraene ring adopts a tub-shaped conformation with a crystallograpically imposed twofold rotational symmetry, and is composed of localized C=C double bonds in the 1,3,5, and 7 positions with an average interatomic distance of 1.327 (5) Å and C–C single bonds with an average interatomic distance of 1.489(5) Å. The average C=C–C angle in the ring is 122.6(3)°. Each symmetry generated eight-membered ring contains four carboxyl groups, two of which are coplanar with the methyl groups across the C=C ring atoms. However, across the C–C bonds the carboxyl groups and the methyl groups show a torsion angle of 64.3(4)°. The presence of a water molecule in the crystal lattice generates a three-dimensional network of close hydrogen bondings between water and the carboxyl groups of multiple rings. This creates a network of orthogonal 10-membered rings between the 8-membered rings. Two given cyclooctatetraene rings are intermolecularly hydrogen bonded not only directly through their carboxyl groups but also via a bridging water molecule. This effect is rare in polycarboxylic acids and their monohydrates which bond only with water or among themselves.     

Perfluorovinyl Morpholine and Perfluorovinyl Pyrrolidine with Nucleophiles and Electrophiles

In this study, both monofunctional and bifunctional nucleophiles, as well as the electrophile FNO, are reacted with perfluorovinyl amines. The perfluorovinyl amines CF?CF₂ and CF?CF₂ have been reacted with dimethylamine and diethylamine in the presence of small amounts of water to give CHFC(O)N(CH₃)₂ ( 1 ), CHFC(O)N(CH₃)₂ ( 2 ), and CHFC(O)N(C₂H₅)₂ ( 3 ). With perfluorovinyl pyrrolidine and perfluorovinyl morpholine, ethanolamine gives the cyclized products CHF ( 4 ) and CHF ( 5 ), respectively. Reaction of the vinyl amines with (CH₃)₃SiOCH₂CF₃ in the presence of catalytic amounts of CsF results in the formation of cis- ( 6 ) and trans- ( 7 ) CF?CF(OCH₂CF₃) and cis- ( 8 ) and trans- ( 9 ) CF?CF(OCH₂CF₃). The electrophile FNO reacts slowly with perfluorovinyl pyrrolidine and perfluorovinyl morpholine, and more rapidly with (CF₃)₃CCF?CF₂ to give CF(NO)CF₃ ( 10 ), CF(NO)CF₃ ( 11 ) and (CF₃)₃CF(NO)CF₃ ( 12 ), respectively. Single crystal X-ray analysis is used to confirm the identity of the product obtained from the controlled hydrolysis of the sultone of perfluorovinyl pyrrolidine as the sulfonic acid anhydride C(O)CF₂OS(O)₂OCF₂C(O) ( 13 ). The X-ray crystal structure of perfluorosuccinic acid monohydrate ( 14 ), which is obtained when the perfluorovinyl pyrrolidine sultone is hydrolyzed in excess water, is also reported for the first time.     

Structures of the BrF(4)(+) and IF(4)(+) cations

The large discrepancies between the calculated and observed structures for BrF(4)(+) and IF(4)(+) (Christe, K. O.; Zhang, X.; Sheehy, J. A.; Bau, R. J. Am. Chem. Soc. 2001, 123, 6338) prompted a redetermination of the crystal structures of BrF(4)(+)Sb(2)F(11)(-) (monoclinic, P2(1)/c, a = 5.2289(6) A, b = 14.510(2) A, c = 14.194(2) A, beta = 90.280(1) degrees, Z = 4) and IF(4)(+)SbF(6)(-) (orthorhombic, Ibca, a = 8.2702(9) A, b = 8.3115(9) A, c = 20.607(2) A, Z = 8). It is shown that for BrF(4)(+), the large differences were mainly due to large errors in the original experimental data. For IF(4)(+)SbF(6)(-), the geometry previously reported for IF(4)(+) was reasonably close to that found in this study despite a very large R-factor of 0.15 and a refinement in an incorrect space group. The general agreement between the calculated and the redetermined geometries of BrF(4)(+) and IF(4)(+) is excellent, except for the preferential compression of one bond angle in each ion due to the influence of interionic fluorine bridges. In BrF(4)(+), the fluorine bridges are equatorial and compress this angle. In IF(4)(+), the nature of the fluorine bridges depends on the counterion, and either the axial (in IF(4)(+)SbF(6)(-)) or the equatorial (in IF(4)(+)Sb(2)F(11)(-)) bond angle is preferentially compressed. Therefore, the geometries of the free ions are best described by the theoretical calculations.     

Structure of the SO(2)F(-) anion, a problem case

Recently, room-temperature crystal structures of SO(2)F(-) in its K(+) and Rb(+) salts were published in Z. Anorg. Allg. Chem. 1999, 625, 385 and claimed to represent the first reliable geometries for SO(2)F(-). However, their almost identical S-O and S-F bond lengths and O-S-O and O-S-F bond angles are in sharp contrast to the results from theoretical calculations. To clarify this discrepancy, the new [(CH(3))(2)N](3)SO(+) and the known [N(CH(3))(4)(+)], [(CH(3))(2)N](3)S(+), and K(+) salts of SO(2)F(-) were prepared and their crystal structures studied at low temperatures. Furthermore, the results from previous RHF and MP2 calculations were confirmed at the RHF, B3LYP, and CCSD(T) levels of theory using different basis sets. It is shown that all the SO(2)F(-) salts studied so far exhibit varying degrees of oxygen/fluorine and, in some cases, oxygen-site disorders, with [(CH(3))(2)N](3)SO(+)SO(2)F(-) at 113 K showing the least disorder with r(S-F) - r(S-O) = 17 pm and angle(O-S-O) - angle(F-S-O) = 6 degrees. Refinement of the disorder occupancy factors and extrapolation of the observed bond distances for zero disorder resulted in a geometry very close to that predicted by theory. The correctness of the theoretical predictions for SO(2)F(-) is further supported by the good agreement between the calculated and the experimentally observed vibrational frequencies and their comparison with those of isoelectronic ClO(2)F. A normal coordinate analysis of SO(2)F(-) confirms the weakness of the S-F bond with a stretching force constant of only 1.63 mdyn/A and shows that there is no highly characteristic S-F stretching mode. The S-F stretch strongly couples with the SO(2) deformation modes and is concentrated in the two lowest a' frequencies.     

Fourier transform infrared study of poly (2-hydroxyethyl methacrylate) PHEMA

 Fourier transform infrared spectra in the wave number range 450–4500 cm^-1 of poly (2-hydroxy-ethyl methacrylate) PHEMA have been studied as functions of water content in the range 38–2.6 wt% and of temperature in the range 300–373 K. The results show changes in the intensities of the stretching frequencies of the carbonyl band, H–O–H bending vibration and O–H stretching vibration with a change in water content and temperature. The results confirm two types of water in the hydrogel polymer system, tightly bound water and loosely bound water. At low concentrations, water is mainly hydrogen-bonded to the polymer and is described as tightly bound water. However, at water concentrations greater than 18% by weight, part of the water exists in a different form and behaves as loosely bound water. For concentrations over 30%, there is some evidence that excess water behaves more loosely bound somewhat like bulk water. Infrared spectroscopic results supplement those obtained by means of NMR by Smyth et al. and by dielectric spectroscopy. Our results also show that some of the water continues to be hydrogen bonded to the polymer until at least a temperature of 373 K when the bulk water should have evaporated. FTIR is found to yield greater site-specific insight into the local behaviour of water in hydrated PHEMA. Received: 22 August 1996 Accepted: 11 November 1996