Calix[4]arene-bis(t-octylbenzo-18-crown-6) as an extraordinarily effective macrocyclic receptor for the univalent thallium cation

Journal Article · Tue Jan 01 00:00:00 EST 2013 · Structural Chemistry

OSTI ID:1097514

Makrlik, Emanuel ^[1]; Toman, Petr ^[2]; Vanura, Petr ^[3]; Moyer, Bruce A ^[4]

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1. Czech University of Life Sciences, Prague, Kamy´cká
2. Institute of Macromolecular Chemistry, Prague
3. Institute of Chemical Technology, Prague, Czech Republic
4. ORNL

From extraction experiments and -activity measurements, the exchange extraction constant corresponding to the equilibrium Tl+ (aq) + 1 Cs+ (org) 1 Tl+ (org) + Cs+ (aq) taking place in the two-phase water phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as log Kex (Tl+, 1 Cs+) = 1.7 0.1. Further, the extraordinarily high stability constant of the 1 Tl+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log org(1 Tl+) = 13.1 0.2. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1 Tl+ was derived. In the resulting 1 Tl+ complex, the central cation Tl+ is bound by eight bond interactions to six oxygen atoms from the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent receptor 1 via cation interaction.

• Research Organization: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• DOE Contract Number: DE-AC05-00OR22725
• OSTI ID: 1097514
• Journal Information: Structural Chemistry, Vol. 25, Issue 3
• Country of Publication: United States
• Language: English

Related Subjects

Thallium
calix[4]arene-bis(t-octylbenzo-18-crown-6)
Complexation
Extraction and stability constants
DFT calculations
structures