Systematic study of aggregation structure and thermal behavior of a series of unique H-shape alkane molecules

Hiroko Yamamoto, Kohji Tashiro, Norio Nemoto, Yukihiro Motoyama, Yoshiaki Takahashi

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The H-shape alkanes of various arm lengths have been synthesized successfully through the Grignard reaction. The detailed investigation of these novel compounds may allow us to widen the topological chemistry field furthermore. The molecular form and molecular packing structure in the crystal lattice have been revealed successfully on the basis of X-ray structure analysis as well as the analysis of Raman longitudinal acoustic modes (LAM) sensitive to the alkyl zigzag chain segments. The molecular conformation in the crystal lattice is deformed markedly from the originally imagined H-shape. In the cases of C3HOH to C6HOH, for example, the molecules are packed in a complicated manner and the OH⋯O hydrogen bonds govern the whole intermolecular interactions mainly. Since the alkyl segmental length is not very long, the conformational change is not very drastic, i.e., the small configurational entropy. Synergic effect of the hydrogen bonds and the small configurational entropy gives the higher melting point as known from the thermal data. On the other hand, in the cases of C10HOH and C12HOH, one of the long alkyl chain arms is found to be bent by 90° so that all of the alky chain segments of planar-zigzag conformation can be packed as closely as possible, and the intermolecular OH⋯O hydrogen bonds are also formed effectively without any mistake. As a result, the contribution of nonbonded intra- and intermolecular van der Waals interactions between the trans-zigzag alkyl chain segments become major, and the coupling of this enthalpy effect with the larger configurational entropy effect of the molecular shape results in the decrement of the melting point which approaches gradually that of longer n-alkane compound. In this way a sensitive balance between the nonbonded van der Waals interact ons, the OH⋯O hydrogen bonds, as well as the configurational entropy effect gives the characteristic thermal behavior of the H-shape compounds. The thus-newly synthesized H-shape alkane compounds should give us new insight into the packing topology of complicated molecules, leading to the development of new functionality unexpected for normal linear alkane compounds.

Original languageEnglish
Pages (from-to)9537-9546
Number of pages10
JournalJournal of Physical Chemistry B
Volume115
Issue number31
DOIs
Publication statusPublished - Aug 11 2011

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Alkanes
Entropy
Paraffins
alkanes
Hydrogen
Hydrogen bonds
Agglomeration
Hot Temperature
Molecules
entropy
hydrogen bonds
Crystal lattices
Freezing
Melting point
Conformations
molecules
crystal lattices
melting points
Molecular Conformation
Grignard reactions

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Systematic study of aggregation structure and thermal behavior of a series of unique H-shape alkane molecules. / Yamamoto, Hiroko; Tashiro, Kohji; Nemoto, Norio; Motoyama, Yukihiro; Takahashi, Yoshiaki.

In: Journal of Physical Chemistry B, Vol. 115, No. 31, 11.08.2011, p. 9537-9546.

Research output: Contribution to journalArticle

Yamamoto, Hiroko ; Tashiro, Kohji ; Nemoto, Norio ; Motoyama, Yukihiro ; Takahashi, Yoshiaki. / Systematic study of aggregation structure and thermal behavior of a series of unique H-shape alkane molecules. In: Journal of Physical Chemistry B. 2011 ; Vol. 115, No. 31. pp. 9537-9546.
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