Mechanism of Hydrogen Bond Array Isomerization in Tetrahydroxycalix[4]arene and Tetrahydroxythiacalix[4]arene

MATOUŠEK, Jiří, Michal ČAJAN, Petr KULHÁNEK and Jaroslav KOČA. Mechanism of Hydrogen Bond Array Isomerization in Tetrahydroxycalix[4]arene and Tetrahydroxythiacalix[4]arene. Journal of Physical Chemistry A. USA: The American Chemical Society, 2008, vol. 112, No 1, p. 1076-1084. ISSN 1089-5639.

Basic information

• Original name: Mechanism of Hydrogen Bond Array Isomerization in Tetrahydroxycalix[4]arene and Tetrahydroxythiacalix[4]arene
• Name in Czech: Mechanismus přesmyku řetězce vodíkových vazeb v Tetrahydroxycalix[4]arenu a Tetrahydroxythiacalix[4]arenu
• Authors: MATOUŠEK, Jiří (203 Czech Republic), Michal ČAJAN (203 Czech Republic), Petr KULHÁNEK (203 Czech Republic) and Jaroslav KOČA (203 Czech Republic, guarantor).
• Edition: Journal of Physical Chemistry A, USA, The American Chemical Society, 2008, 1089-5639.

Other information

• Original language: English
• Type of outcome: Article in a journal
• Field of Study: 10403 Physical chemistry
• Country of publisher: United States of America
• Confidentiality degree: is not subject to a state or trade secret
• Impact factor: Impact factor: 2.871
• RIV identification code: RIV/00216224:14310/08:00024135
• Organization unit: Faculty of Science
• UT WoS: 000252815100038
• Keywords in English: Calixarene DFT RIMP2 Hydrogen bond array mechanism
• Tags: International impact, Reviewed

Abstract

Possible rearrangement mechanisms of hydrogen bond array formed at the lower rim of tetrahydroxycalix[4]arene and tetrahydroxythiacalix[4]arene were studied by means of the density functional theory and RI/MP2 modification of Moller Plesset perturbation theory. Influence of solvent to height of energy barriers was quantified using the COSMO model of implicit solvent (chloroform). Generally, two types of mechanisms were investigated. The first is represented by synchronous single step jump of all four hydroxyl protons. Pathways of the second mechanism include the rotation of one or more hydroxyl groups around the CArO bond. Theoretical results, in agreement with recently published experimental data (Lang, J. et al. J. Chem. Phys. 2005, 122, 044056), prefer jump mechanism for the methylene bridged calix[4]arene. Concerning the thiacalix[4]arene, results obtained by COSMO as well as RI-MP2 calculations show, that the rotational mechanism is very competitive and it could even be more favorable.

Abstract (in Czech)

Possible rearrangement mechanisms of hydrogen bond array formed at the lower rim of tetrahydroxycalix[4]arene and tetrahydroxythiacalix[4]arene were studied by means of the density functional theory and RI/MP2 modification of Moller Plesset perturbation theory. Influence of solvent to height of energy barriers was quantified using the COSMO model of implicit solvent (chloroform). Generally, two types of mechanisms were investigated. The first is represented by synchronous single step jump of all four hydroxyl protons. Pathways of the second mechanism include the rotation of one or more hydroxyl groups around the CArO bond. Theoretical results, in agreement with recently published experimental data (Lang, J. et al. J. Chem. Phys. 2005, 122, 044056), prefer jump mechanism for the methylene bridged calix[4]arene. Concerning the thiacalix[4]arene, results obtained by COSMO as well as RI-MP2 calculations show, that the rotational mechanism is very competitive and it could even be more favorable.

Links

• GD204/03/H016, research and development project: Name: Strukturní biofyzika makromolekul

Investor: Czech Science Foundation, Structural biophysics of macromolecules

• IAA400200503, research and development project: Name: Léčiva na bázi sacharidů a calixarenů - design, struktura, protinádorová a protivirová aktivita

Investor: Academy of Sciences of the Czech Republic, Calixarenes based glycodrugs - design, structure, antitumor and antiviral activity

• LC06030, research and development project: Name: Biomolekulární centrum

Investor: Ministry of Education, Youth and Sports of the CR, Biomolecular centre

• MSM0021622413, plan (intention): Name: Proteiny v metabolismu a při interakci organismů s prostředím

Investor: Ministry of Education, Youth and Sports of the CR, Proteins in metabolism and interaction of organisms with the environment