ABSTRACT
A 2 : 4 mixture of tetrakis[4-(4-pyridyl)phenyl]cavitand (1) or tetrakis[4-(4-pyridyl)phenylethynyl]cavitand (2) and Pd(dppp)(OTf)2 self-assembles into a homocapsule {12 â [Pd(dppp)]4 }8+ â (TfO- )8 (C1) or {22 â [Pd(dppp)]4 }8+ â (TfO- )8 (C2), respectively, through Pd-Npy coordination bonds. A 1 : 1 : 4 mixture of 1, 2, and Pd(dppp)(OTf)2 produced a mixture of homocapsules C1, C2, and a heterocapsule {1 â 2 â [Pd(dppp)]4 }8+ â (TfO- )8 (C3) in a 1 : 1 : 0.98 mole ratio. Selective formation (self-sorting) of homocapsules C1 and C2 or heterocapsule C3 was controlled by guest-induced encapsulation under thermodynamic control. Applications of Pd-Npy coordination capsules with the use of 1 were demonstrated. Capsule C1 serves as a guard nanocontainer for trans-4,4'-diacetoxyazobenzene to protect against the trans-to-cis photoisomerization by encapsulation. A chiral capsule {12 â [Pd((R)-BINAP)]4 }8+ â (TfO- )8 (C5) was also constructed. Capsule C5 induces supramolecular chirality with respect to prochiral 2,2'-bis(alkoxycarbonyl)-4,4'-bis(1-propynyl)biphenyls by diastereomeric encapsulation through the asymmetric suppression of rotation around the axis of the prochiral biphenyl moiety.
ABSTRACT
The components of a 4:1 mixture of Rh(III)Cl tetrakis(4-methylphenyl)porphyrin 1 and a bowl-shaped tetra(4-pyridyl)cavitand 4 self-assemble into a 4:1 complex 14â¢4 via Rh-pyridyl axial coordination bonds. The single-crystal X-ray diffraction analysis and variable-temperature (VT) (1)H NMR study of 14â¢4 indicated that 14â¢4 behaves as a quadruple interlocking gear with an inner space, wherein (i) four subunits-1 are gear wheels and four p-pyridyl groups in subunit-4 are axes of gear wheels, (ii) one subunit-1 and two adjacent subunits-1 interlock with one another cooperatively, and (iii) four subunits-1 in 14â¢4 rotate quickly at 298 K on the NMR time scale. Together, the extremely strong porphyrin-Rh-pyridyl axial coordination bond, the rigidity of the methylene-bridge cavitand as a scaffold of the pyridyl axes, and the cruciform arrangement of the interdigitating p-tolyl groups as the teeth moiety of the gear wheels in the assembling 14-unit make 14â¢4 function as a quadruple interlocking gear in solution. The gear function of 14â¢4 was also supported by the rotation behaviors of other 4:1 complexes: 24â¢4 and 34â¢4 obtained from Rh(III)Cl tetrakis[4-(4-methylphenyl)phenyl]porphyrin 2 or Rh(III)Cl tetrakis(3,5-dialkoxyphenyl)porphyrin 3 and 4 also served as quadruple interlocking gears, whereas 14â¢5 obtained from 1 and tetrakis[4-(4-pyridyl)phenyl]cavitand 5 did not behave as a gear. The results of activation parameters (ΔH(⧧), ΔS(⧧), and ΔG(⧧)) obtained from Eyring plots based on line-shape analysis of the VT (1)H NMR spectra of 14â¢4, 24â¢4, and 34â¢4 also support the interlocking rotation (geared coupled rotation) mechanism.
ABSTRACT
The components of a 1:2 mixture of meso-tetrakis(4-dodecyl-3,5-dihydroxyphenyl)porphyrin (1) and a bowl-shaped tetrakis(4-pyridylethynyl)cavitand (2) in CDCl3 or C6 D6 self-assemble quantitatively into the doubly cavitand-capped porphyrin capsule 2â 1â 2 through eight ArOHâ â â Npy hydrogen bonds. Capsule 2â 1â 2 possesses two cavities divided by the porphyrin ring and encapsulates two molecules of 1-acetoxy-3,5-dimethoxybenzene (G) as a guest to form G/G@(2â 1â 2). Remarkable solvent effect was observed, in which the apparent association constant of 2â 1â 2 with G in C6 D6 was much greater than that in CDCl3.