Self-assembled coordination cage as a molecular flask*

نویسندگان

  • Michito Yoshizawa
  • Makoto Fujita
چکیده

Cavity-directed chemical transformations represent one of the most important features in 3-D host chemistry, yet they are unexplored as synthetic receptors. We are developing such functions with the large cavity of self-assembled cages, particularly an M6L4-type cage. The photodimerization of olefins within this cage shows remarkable rate enhancement, perfect regioand stereoselection, and high pairwise selection (when two different olefins are used) giving only the cross [2+2] adduct. Another intriguing property of the cavity is the stabilization of labile molecules by encapsulation. We succeeded in trapping labile molecules by in situ preparation from small components coming through small portals of the cage. For example, hydrolysis and condensation of PhSi(OMe)3, which ordinarily provides a sophisticated Si–O 3-D network (so-called sol-gel condensation), selectively gave a cyclic trimer, [PhSi(OH)O]3, in a “ship-in-a-bottle” fashion. Cavity-sensitized photochemical oxidation of alkanes within the cage is also discussed.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Crystallographic observation of an olefin photodimerization reaction that takes place via thermal molecular tumbling within a self-assembled host.

In situ crystallography reveals that the solid state [2 + 2] photodimerization of acenaphthylene in a coordination cage takes place smoothly without preorganizaiton of reaction centers at a preferred geometry, because the substrate tumbles thermally in the large hollow of the cage.

متن کامل

Networking a hollow cage via guest coordination.

A hollow coordination cage with a highly symmetric cavity was successfully self-assembled to form a 2D-network having a less symmetric cavity via networking of disordered guests with a metal connector.

متن کامل

Self-assembled cage as an endo-template for cyclophane synthesis.

An organic-pillared coordination cage templated the quantitative formation of siloxane-bridged cyclophanes within its cavity via hydrolysis and condensation of 1,6- and 1,8-bis(trimethoxysilyl)pyrene.

متن کامل

Coordination-driven self-assembly of an iridium-cornered prismatic cage and encapsulation of three heteroguests in its large cavity.

A hollow iridium-cornered prismatic cage was self-assembled without the assistance of any template. The cage was found to be capable of encapsulating heteroguest's triplet in its perfect sized cavity, producing the first demonstration of quintuple structure by an octahedral metal cornered prismatic cage.

متن کامل

Archimedean solids: transition metal mediated rational self-assembly of supramolecular-truncated tetrahedra.

A family of nanoscale-sized supramolecular cage compounds with a polyhedral framework is prepared by self-assembly from tritopic building blocks and rectangular corner units via noncovalent coordination interactions. These highly symmetrical cage compounds are described as face-directed, self-assembled truncated tetrahedra with T(d) symmetry.

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:

دوره   شماره 

صفحات  -

تاریخ انتشار 2005