International Summer School PROGRAM - Laboratoire d'Infochimie ...

Conjugates of thiacalixarenes and clathrochelates - new inclusion
M n+
Hal
Hal
Clathrochelate
precursor
+
HS
HS
O
O
S
S
S S
O
O
SH
SH
Thiacalix[4]arene in the
1,3-alternate conformation
compounds
S.E. Soloveva a , A.A.Tyuftin a , Y.Z.Voloshin b , M.Gruner c , W. Habicher c , I.S.Antipin a ,
A.I.Konovalov a
a A.E.Arbuzov Institute of Organic & Physical Chemistry, 420088, Kazan, Russia,
Arbuzov str., 8. , b A.N.Nesmeyanov Institute of Organoelement Compounds RAS,
119991, Moscow, Vavilova str. 28, Russia, c
Technical University, Institute of Organic
Chemistry, Technical Univercity, Bergstr.,66c D-01062 Dresden, Germany/
E-mail: svsol@iopc.knc.ru
Nanosized polytopic molecular systems are usually formed from several
relatively independent building blocks, which are bounded either covalently or via weak
intermolecular interactions. The most effective strategy to obtain such systems is based
on the “bottom – up” principle that uses the appropriate molecular precursors.
Thiacalixarene scaffolds can be regarded as the precursors of more complex nanosized
systems, in particular, hybrid and polytopic molecules.
M n+
Tris-dioximate clathrochelates
are the macrobicyclic compounds with a metal ion encapsulated in a three-dimensional
macropolycyclic ligand cavity. These complexes demonstrate unique thermodynamic
and kinetic stabilities and have unusual redox and photochemical properties. Here we
report the synthesis and the characterization of the first hybrid calixarenoclathrochelates.
Their synthesis was performed by the macrocyclization of the tetra-O-
substituted thiacalix[4]arenes in 1,3-alternate conformation and monoribbedfunctionalized
clathrochelate iron(II). These hybrids contain of two novel macrocyclic
cavities.
S
S
O
Guest
O
S
S
S S
O
O
Hybrid complex
The support from RFBR (N 11-03-00985) is gratefully acknowledged.
S
S
M n+