The crystal structure of [C(n)mim]NTf(2) (n = 2, 4, 6) was studied for the first time simultaneously by X-ray diffraction method and IR spectroscopy. The temperature-dependent IR spectrum for crystalline [C(4)mim]NTf(2) was demonstrated to correlate with both the X-ray data and the calorimetric results obtained earlier. Therefore, it was found that IR spectroscopy is able to establish the correspondence between the X-ray and the calorimetric data in this case. The joint use of X-ray diffraction, IR spectroscopy, and quantum-chemical calculations allowed us to determine the structure of all [C(2)mim]NTf(2) crystalline modifications obtained earlier by adiabatic calorimetry measurements. Thus, a new approach for the future identification of ionic liquid crystal structure by use of temperature-dependent infrared spectroscopy is suggested and justified.

Various 1,3‐dialkylimidazolium and tetraalkylphosphonium ionic liquids (ILs), including novel ones, have been studied as reaction media for free radical polymerization of methyl methacrylate (MMA), acrylonitrile (AN) and 1‐vinyl‐3‐ethylimidazolium salts (ViEtIm+)Y−. The influence of IL's nature upon the polymer formulation was investigated. The use of different ionic liquids allows not only to obtain the polymers with high molecular weight (PMMA, ${\bar M}_w$ up to 5,770,000 g/mol; PAN, ${\bar M}_v$ up to 735,000 g/mol and poly[(ViEtIm+)Y−], $\bar M_z$ up to 1,130,000 g/mol) in high yields, but also to control the polymerization rate and molecular mass. The physicochemical characteristics, including mechanical properties, thermal stability and heat‐resistance of the obtained polymers were studied in order to compare with those of polymers prepared in a traditional media. It was found that elongation, tensile modulus and strength of PAN, which was synthesized in ionic liquid, are reliatively higher. The influence of IL's nature upon their ionic conductivity and the formation of conductive polymers from molten‐salt‐type vinyl monomers was investigated. Molecular design of the polymers simultaneously with the influence of IL's nature in order to achieve higher ionic conductivity is discussed. Flexible, transparent polymer films, obtained in different ways, show relatively high ionic conductivity (of about 10−5 S cm−1 at 20°C). Copyright © 2006 John Wiley & Sons, Ltd.

Tetramethylcyclobutadiene(cyclopentadienyl)cobalt complexes Cb*Co(C 5 H 4 R) (Cb* ) η 4 -C 4 Me 4 ; R ) H (5a), Me (5b), SiMe 3 (5d), C(O)H (5f), and C(O)Me (5g)) were obtained by reaction of cyclopentadienide anions either with the (carbonyl)iodide complex Cb*Co(CO) 2 I (1) (method A) or with the more reactive acetonitrile complex [Cb*Co(MeCN) 3 ] + (2) (method B). Analogous compounds Cb*CoCp* (5c), Cb*Co(1,3-C 5 H 3 (SiMe 3 ) 2 ) (5e), and Cb*Co(η 5indenyl) (6) can be prepared only by method B. Treatment of 5f,g with NaBH 4 /AlCl 3 or LiAlH 4 affords the alkyl derivatives 5b and 5h (R ) Et) or the alcohols 5i (R ) CH 2 OH) and 5j (R ) CH(OH)Me), respectively. The reaction of 1 with fluorene/AlCl 3 yields complex [Cb*Co-(η 6 -fluorene)] + (8), which was deprotonated by KOBu t to give Cb*Co(η 6 -fluorenyl) (9). Visible light irradiation of 9 induces η 6 fη 5 haptotropic rearrangement to afford Cb*Co(η 5 -fluorenyl) (7). The pyrrolyl and phospholyl complexes Cb*Co(C 4 R 4 N) (R ) H (10a), Me (10c)) and Cb*Co-(C 4 R 4 P) (R ) H ( 11a), Me (11c); R 4 ) H 2 Me 2 (11b)) were obtained by reaction of 2 with the corresponding pyrrolide or phospholide anions. Improved procedures for the preparation of the starting materials 1 and 2 were developed. Using a one-pot procedure, the iodide 1 was obtained in high yield from 2-butyne and Co 2 (CO) 8 . Complex 2 was prepared by heating or irradiation of the toluene complex [Cb*Co(C 6 H 5 Me)] + (4b) in acetonitrile. Structures of 5g, 6, and 11c were investigated by X-ray diffraction. Electrochemistry and joint UV-visible and EPR spectroelectrochemistry of complexes prepared were studied. Scheme 3Scheme 4

A new monoclinic polymorph of triphenyl phosphite has been investigated by means of X-ray diffraction analysis; crystallization of the new polymorph was found to be a result of solvent polarity (in our case ionic liquid) and method of cooling.Triphenyl phosphite (TPP) is known to exhibit polyamorphic transitions (see ref. 1 and refs. therein). In general, in these transitions a one-component system can exist in at least two liquid or amorphous phases that undergo a first-order phase transition. Both phases are significantly different in density.The most wellknown example is transformation of the high-density amorphous ice into a low-density phase, which is accompanied by a change in density of about 23%. 2 It is known that TPP, according to a number of investigations undergoes a liquid-liquid first-order phase transition. 1a,b The first amorphous phase (aI) is a supercooled liquid that transforms to a second amorphous phase (aII) via a phase transition in the range 215-230 K. At higher temperatures the aII phase transforms into a crystalline state, and thus the aII phase is metastable with respect to the crystalline one (see ref. 3 and refs. therein).In spite of detailed analysis on the TPP aII phase there is still no clear decision about its nature. According to He ´doux et al. the aII phase is a mixture of nanocrystals in a supercooled liquid. 4a,b However, Senker et al. made a conclusion that the aII phase is homogeneous. 4c,d Crystals of TPP can be easily obtained by crystallization from the liquid upon rapid cooling, 5 from acetone solution 5 or by phase transition from the aII phase. 3 All of the crystals thus obtained had a needle-like shape and crystallized in the hexagonal space group R3 ¯(a 5 37.887(5), b 5 c 5 5.722(1) A ˚, V 5 7113(2) A ˚3, Z 5 18) with one independent molecule of TPP in the asymmetric unit. 5 Powder X-ray diffraction analysis and 31 P NMR investigations of the crystalline state have revealed no phase transition and dynamical disorder within the temperature range 150-290 K. 4d,5,6 In 1999 He ´doux et al. reported 1c that the aII phase is a mixture of supercooled liquid (aI phase) and monoclinic nanocrystals with unit cell dimensions: a 5 10.959(6), b 5 18.75(1), c 5 5.686(3) A ˚,