Crystal NMR study

Recent solid state NMR studies of liquid crystalline materials are surveyed. The review deals first with some background information in order to facilitate discussions on various NMR (13C, ll, 21 , I9F etc.) works to be followed. This includes the following spin Hamiltonians, spin relaxation theory, and a survey of recent solid state NMR methods (mainly 13C) for liquid crystals on the one hand, while on the other hand molecular ordering of mesogens and motional models for liquid crystals. NMR studies done since 1997 on both solutes and solvent molecules are discussed. For the latter, thermotropic and lyotropic liquid crystals are included with an emphasis on newly discovered liquid crystalline materials. For the solute studies, both small molecules and weakly ordered biomolecules are briefly surveyed. 

A number of detailed 1H NMR studies of thietane and thiete derivatives have appeared in which all of the coupling constants have been determined and some of these data are summarized in Table 2. Liquid crystal NMR studies of thietane (75MI51400) and thietane... 

Cho H. and Rossman (1993) Single-crystal NMR studies of low-concentration hydrous species in minerals grossular garnet. Am. Mineral. 78, 1149-1164. 

Supercooled liquid solutions can also give meaningful ENDOR results,12 but most ENDOR has been done on single crystals. NMR studies can also be done, but there are few reports in the literature where any analysis has been done on an asymmetric NMR line. 

Despite the wealth of information offered by single-crystal NMR experiments, growing single crystal biomolecules of suitable size (millimetre) and quahty is a great challenge. For this reason, there are only a few single-crystal NMR studies benzophenone [10], a-glycine [11], dimethylmalonic acid [51], a-oxalic acid [52], and model peptides [28]. In the latter study. 

Andersen, M. D., H. J. Jakobsen and J. Skibsted. 2005. Effects of Ti relaxation in MAS NMR spectra of the satellite transitions for quadrupolar nuclei A Al MAS and single-crystal NMR study of alum KAI(S04)2T2H20./. Magn. Reson. 173, 209-217. 

The entropy value of gaseous HCl is a sum of contributions from the various transitions summarized in Table 4. Independent calculations based on the spectroscopic data of H Cl and H Cl separately, show the entropy of HCl at 298 K to be 186.686 and 187.372 J/(mol K) (44.619 and 44.783 cal/(mol K), respectively. The low temperature (rhombic) phase is ferroelectric (6). SoHd hydrogen chloride consists of hydrogen-bonded molecular crystals consisting of zigzag chains having an angle of 93.5° (6). Proton nmr studies at low temperatures have also shown the existence of a dimer (HC1)2 (7). 

In the case of phenyllithium, it has been possible to demonstrate by NMR studies that the compound is tetrameric in 1 2 ether-cyclohexane but dimeric in 1 9 TMEDA-cyclohexane. X-ray crystal structure determinations have been done on both dimeric and tetrameric structures. A dimeric structure crystallizes from hexane containing TMEDA. This structure is shown in Fig. 7.1 A. A tetrameric structure incorporating four ether molecules forms from ether-hexane solution. This structure is shown in Fig. 7.IB. There is a good correspondence between the structures that crystallize and those indicated by the NMR studies. 

Characterization439 Inherent viscosity before and after solid-sate polymerization is 0.46 and 3.20 dL/g, respectively (0.5 g/dL in pentafluorophenol at 25°C). DSC Tg = 135°C, Tm = 317°C. A copolyester of similar composition440 exhibited a liquid crystalline behavior with crystal-nematic and nematic-isotropic transition temperatures at 307 and 410°C, respectively (measured by DSC and hot-stage polarizing microscopy). The high-resolution solid-state 13C NMR study of a copolyester with a composition corresponding to z2/zi = 1-35 has been reported.441... 

The two -OH groups in l,2 5,6-di-0-cyclohexylidene-wii/o-inositol and its di-O-isopropylidene analog are trans. The X-ray crystal structure of the latter compound suggests that the ring is in a skew conformation with the 0-3 and 0-4 -OH groups both in ax positions, but NMR studies and ab initio calculations indicate that a mixture of the skew and chair conformations, with 0-3 and 0-4 both in eq positions, is present. Formation of a dibutylstannylene acetal presumably locks these two compounds in the latter conformation. 

Reliable information on the thermodynamic stability of group 13/15 adducts is usually obtained by gas phase measurements. However, due to the lability of stibine and bismuthine adducts in the gas phase toward dissociation, temperature-dependent H-NMR studies are also useful for the determination of their dissociation enthalpies in solution [41b], We focussed on analogously substituted adducts t-BusAl—E(f-Pr)3 (E = P 9, As 10, Sb 11, Bi 12) since they have been fully characterized by single crystal X-ray diffraction, allowing comparisons of their thermodynamic stability in solution with structural trends as found in their solid state structures. 

We reacted 2 first with bromine in chloroform at 10 C. iH NMR studies have revealed that the reaction mixture was very complex and consisted of six products. This mixture was submitted to silica gel column chromatography. Careful repeated chromatography followed by fractional crystallization allowed us to isolate ten products (Scheme 3). IR analysis indicated that a hydroxyl group was incorporated in compounds lfi-19. Therefore, we assume that these products have been formed by partial hydrolysis of compounds lfl-14. Structural determination of compounds lfl-19 revealed that the barrelene skeleton was rearranged completely. 

For example, the difference between the monoclinic CaC2 phases is the presence of only one type of acetylide ion in phase II and two distinct C2 species in phase III, as concluded from their crystal structures and from C-NMR studies (Fig. 8.3) [8]. The transformation between phases II and III is induced by heating phase II above 150°C until the metastable phase. III, is formed. Phase III remains stable even when being cooled down to room temperature. However, when the metastable phase III is ground in a mortar at room temperature, it transforms back into phase II. 

The free t-butyl cation [7" ] in the gas phase is nothing more than a species detectable by the electron impact method (Yeo and Williams, 1970). However, it is not only an observable species by nmr studies in SbFs/FSOsH (Olah et al., 1964), but can be isolated from the solution in the form of its SbF or Sb2Ffi salt (Olah and Lukas, 1967a,b Olah et al., 1973 Yannoni et al., 1989). The crystal structure shows that this ion is planar and its carbon-carbon bonds are shortened to 144.2 pm (Hollenstein and Laube, 1993). Its particular electronic stabilization among aliphatic carbocations is attributed by physical organic chemists to the operation of both inductive and hyperconjugative effects in the cr bond system. 

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