Selective formation of a self-assembling homo or hetero cavitand cage via metal coordination based on thermodynamic or kinetic control.
The selective formation of a homo or hetero cavitand cage composed of two molecules of tetra(4-pyridyl)-cavitand (1), tetrakis(4-cyanophenyl)-cavitand (2), or tetrakis(4-pyridylethynyl)-cavitand (3), and four molecules of Pd(dppp)(OTf)(2) (4) or Pt(dppp)(OTf)(2) (5) has been studied. A 1:1:4 mixture of 1 with more steric restriction, 2 with less coordination ability, and 4 or 5 specifically self-assembled into a hetero cavitand cage 6 or 7, respectively. In contrast, a 1:1:4 mixture of 2, 3, and 4 in CDCl(3) at room temperature assembled into the most labile homo cyanophenyl cavitand cage 8 and the most stable homo pyridylethynyl cavitand cage 9 in a 1:1 ratio. Upon heating at 50 degrees C, the thermodynamic equilibrium was shifted to a 1:1:1 mixture of 8, 9, and a hetero cavitand cage 10. When 1 equiv of 3 was added to 8 at room temperature, 8, 9, and 10 were formed initially in a 1:1:3 ratio and finally shifted to a 1:1:1 ratio. In the Pt-system, upon addition of 1 equiv of 3 to homo cyanophenyl cavitand cage 11 in CDCl(3) at room temperature, the ratio of hetero to homo cavitand cage (13/12) initially attained was 8.7 and remained above 5.6 at room temperature. Upon heating at 50 degrees C, 13 was finally converted to 11 and 12. Thus, the selectivity for the self-assembly of the homo or hetero cavitand cage is controlled by the balance between kinetic and thermodynamic stabilities of cages based on a combination of factors such as coordination ability and steric demand of the cavitands.
Yamanaka
Masamichi
M
Department of Chemistry, Faculty of Science, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka 422-8529, Japan.
Yamada
Yoshifumi
Y
Sei
Yoshihisa
Y
Yamaguchi
Kentaro
K
Kobayashi
Kenji
K