A Homochiral Metal–Organic Material with Permanent Porosity, Enantioselective Sorption Properties, and Catalytic Activity
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Recent reviews on porous metal–organic frameworks:
For other applications including magnetism nonlinear optics luminescence sensors conductivity ion‐exchange see comprehensive reviews [1a e] and selected recent papers:
2005, Angew. Chem. Int. Ed., 44, 5472
Guillou N., 2003, Angew. Chem., 115, 4137
For some homochiral metal–organic frameworks the porosity has been demonstrated either by reversible gas sorption or guest inclusion; see refs. [3d h] [5b–d] and
Our approach is based on the concept of the SBU which was developed by Yaghi O'Keeffe and co‐workers (see reference [1c]) and has been widely used in the synthesis of metal–organic frameworks. Note that the framework‐forming reaction does not necessarily proceed in a stepwise manner as it appears in Scheme 1. The strategy itself may not be novel but this is the first time that it has been successfully applied in the synthesis of 3D homochiral metal–organic porous materials.
The Zn–O distances between Zn2+ions and the hydroxy oxygen atom of the lactate anion in1(1.969 and 1.939 Å) clearly support the deprotonation of the OH group.
A. L. Spek PLATON a multipurpose crystallographic tool Utrecht University Utrecht The Netherlands 2001.
Recent reviews on chiral sulfoxides:
The material [Zn2(bdc)(L‐lac)(dmf)x] (x<1) with partially removed coordinating DMF ligands showed poorer sorption of3 b(about 0.05 molecules per formula unit of [Zn2(bdc)(L‐lac)(dmf)]) along with a lowereevalue (12 % in favor of theSenantiomer).
After the sorption experiment the crystalline material1was washed thoroughly with CH2Cl2(5 portions 4–5 mL each) to remove traces of sorbed sulfoxide collected by filtration and dried in air for 1 h before use in the next cycles of sorption experiments. The amount of sorbed3 bin1in the second cycle was found to be the same 0.18 molecules per formula unit of [Zn2(bdc)(L‐lac)(dmf)].
The heterogeneous nature of the catalysis was further confirmed in that no conversion was observed in the reaction of2 bwith UHP in the supernatant solution removed after stirring with1in CH2Cl2for 16 h.
To better understand the mechanism of the catalytic reaction with1 we are also investigating the same reaction using an analogous homogeneous catalyst.