Pressure-induced Phase Transition and Compressive Behavior of Substituted Adamantanes

Hara, Kimihiko; Katou, Yoshikazu; Osugi, Jiro

doi:10.1246/bcsj.54.687

Cited by 17 publications

(29 citation statements)

References 10 publications

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“…, are close to the volume change at the ordered to orientationally disordered transition for some adamantane derivatives, [46][47][48] thus reinforcing the orientationally ordered character of phase I for the case here studied. Moreover, the changes of the thermodynamic properties at the melting process do not correlate with the relationships established for orientationally disordered phases.…”

Section: Resultssupporting

confidence: 77%

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Phase Transition in Hydrogen-Bonded 1-Adamantane-methanol

Hassine

Négrier

Barrio

et al. 2015

Crystal Growth & Design

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The polymorphism of 1-adamantane-methanol C 11 H 18 O has been investigated by differential thermal analysis and single-crystal and powder X-ray diffraction. Below the melting temperature (389.5 ± 0.4 K), this compound exhibits an orthorhombic phase (Phase I, Pnnm, Z=12, Z'=1.5). The melting enthalpy was determined to be 20.5 ± 0.4 kJ mol −1 , i.e.,with an entropy change of (6.34 ± 0.13)R, which is much higher than the quoted value fromTimmermans for the melting orientationally disordered phases (2.5R), thus supporting the orientationelly ordered character of phase I. This orthorhombic phase I exhibits a statistical disorder of the hydrogen atom related to the oxygen atom, due to the position of one independent molecule on the mirror. At ca. 272 K, phase I transforms continuously through an order-disorder transition to a low-temperature monoclinic phase II (P2 1 /n, Z=12, Z'=3). The monoclinic and orthorhombic phases are related by a group-subgroup relationship, which perfectly agrees with the continuous character of the II to I transition. Moreover, by a convenient choice of an order parameter related to the continuous tilt of the c-axis, the critical exponent for this transition is found to be close to the theoretical prediction of 3D-Ising model (with a critical exponent is of ca. 0.27).

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Section: Resultssupporting

confidence: 77%

“…Although the number of studies concerning 2-X-adamantane derivatives is less extensive, detailed polymorphic studies have also been reported. [15][16][17][18][19][20][21][22] The phase behavior of the 1-X adamantane compounds varies according to the substituent.…”

Section: Introductionmentioning

confidence: 99%

Phase Transition in Hydrogen-Bonded 1-Adamantane-methanol

Hassine

Négrier

Barrio

et al. 2015

Crystal Growth & Design

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“…[12][13][14][15][16][17][18] As for the latter, with C 2v symmetry, the literature studies are scarce and, concerning the polymorphic behavior as a function of temperature and pressure, there are some hints but sometimes contradictory. [19][20][21][22][23][24][25][26][27][28][29][30][31] Among the 2-X-adamantane derivatives, 2-O-adamantane (2-adamantanone, C 10 H 14 O, hereinafter called 2O-A) has probably been the most studied in the OD phase. The polymorphic behavior of this compound has been described as follows.…”

Section: Introductionmentioning

confidence: 99%

“…205 K. 19,20,30,31 A large number of works has been published concerning the orientational disorder of the OD phase, whereas the low-temperature phase was found to be perfectly ordered through NMR studies. [19][20][21][22][23][24][25][26][27][28][29][30][31] Nevertheless, recent dielectric spectroscopy analyses and X-ray diffraction have shown that a statistical intrinsic disorder concerning the site occupancy of the oxygen atom along different sites giving rise to large-angle molecular rotations associated to time-average fluctuations of the molecular dipole exist. 24 As a consequence of such a disorder the dielectric spectra showed the universal features of glass-like materials in which αand β-relaxation processes appear.…”

Section: Introductionmentioning

confidence: 99%

Polymorphism of 2-Adamantanone

Négrier

Barrio

Romanini

et al. 2014

Crystal Growth & Design

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The polymorphism of 2-adamantanone (C10H14O) has been investigated by means of X-ray diffraction and high-pressure thermal analysis. The intricate behavior of the low-temperature crystalline phases has been disentangled. The stable phase has been found to be orthorhombic (Cmc2 1, Z = 4), fully ordered, with lattice parameters a = 6.8884(18) Å, b = 10.830(3) Å, c = 10.658(3) Å, and V/Z = 198.8(1) Å3. The metastable phase was determined to be monoclinic (P21/c, Z = 4) with lattice parameters a = 6.5920(17) Å, b = 11.118(3) Å, c = 12.589(3) Å, ß= 118.869(11) o, and V/Z = 202.0(1) Å3. The pressure-temperature phase diagram irrefutably shows the stability relation between both phases and, accordingly, the long-time unknown polymorphic behavior is now revealed and gives coherent physical explanation of the literature published so far.Postprint (published version

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“…The order-disorder transitions in 1-substituted adamantanes (C10H15R; R = 1-COOH ( l o ) , 1-NH3+Cl-(1 l ) , 1-CN (12), 1-C1 (16), 1-Br (16)) have been examined. Little work has been done on 2-substituted derivatives (13,17,18), and as part of a study of the phase-transition behaviour of adamantane derivatives, we report here the results of an investigation of the order-disorder transitions in 2-chloroadamantane, 2-CloH15C1, by differential scanning calorimetry (DSC), and variable-temperature FT-IR and Raman spectros-COPY.…”

Section: Introductionmentioning

confidence: 99%

Phase transitions in adamantane derivatives: 2-chloroadamantane

Paroli¹,

Kawai²,

Butler³

et al. 1988

Can. J. Chem.

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Thispaper is dedicated to Professor Charles A. McDowell on the occasion of his seventieth birthdayRALPH M. PAROLI, NANCY T. KAWAI, IAN S. BUTLER, and DENIS F. R. GILSON. Can. J. Chem. 66, 1973 (1988. The phase transition behaviour of 2-chloroadamantane, 2-CloHlsC1, has been investigated by differential scanning calorimetry (DSC), and FT-IR and Raman spectroscopy. Two transitions were detected by both DSC and vibrational spectroscopy at 23 1 and 178 K, on cooling, and at 242 and 227 K, on heating. The measuredenthalpies were 8.3 kJ mol-' for the first transition (phase I + phase 11), and 0.47 kJ mol-' for the second (phase I1 + phase 111). The entropies were 35 and 2.3 J K-' mol-I, respectively. These are similar to those observed for other 2-substituted adamantanes, but significantly different from those for 1 -substituted derivatives. The large hystereses observed for the two transitions are independent of the DSC scanning rate and are characteristic of first-order phase transitions. The dramatic differences observed in the vibrational spectra of phases I and I1 provide clear evidence of an order-disorder transition at about 235 K.

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Pressure-induced Phase Transition and Compressive Behavior of Substituted Adamantanes

Cited by 17 publications

References 10 publications

Phase Transition in Hydrogen-Bonded 1-Adamantane-methanol

Phase Transition in Hydrogen-Bonded 1-Adamantane-methanol

Polymorphism of 2-Adamantanone

Phase transitions in adamantane derivatives: 2-chloroadamantane

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