[논문 뽀개기] Chlathrochelate Metalloligands in Supramolecular Chemistry and Materials Science

[Abstract]

 

1. The term "clathrochelate" : a complex in which coordinately saturated metal ion is surrounded by a macropolycyclic ligand

 

2. Boron-capped clathrochelates

 (1) They are facile to synthesize by metal-templated condensation reactions

 (2) The synthesis is modular

 (3) It is possible to attach functional groups such as amines, pyridines, or carboxlic acids to the ligand periphery

 (4) high thermodynamic, kinetic stability, tunable redox potential, and good solubility

 (5) can be decorated with functional groups in lateral and apical position, and it is possible to use these complexes as multiconnected nodes in polymeric structures. 

 

3. It can be used to build molecularly defined metal-ligand assemblies of nanoscale dimensions

 

4. Metalloligands containing multiple clathrochelate complexes are particularly well suited to build large metal-ligand assemblies (>3nm) with minimal synthetic efforts

 

5. Linear or cross-linked clathrochelate polymers were found to display permanent porosity(다공성). 

 

6. The high stability of clathrochelates ensures compatibility with harsh reaction conditions, and it mitigates(완화시키다) potential problems such as exchange reactions. 

 

7. Be worth to study...

 (1) the properties of nanostructures based on chiral clathrochelate complexes 

 (2) the redox and magnetic propeties of clathrochelates which may give rise to novel functional mateirals

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[Introduction]

 

1. Clathrochelate = cage complexes

 

2. If the encapsulated ions are alkali or alkaline earth metal ions(주기율표에서 1족과 2족), the term "cryptate" is commonly employed

 

3. Arylboron-capped clathrochelates

 -> convenient way to prepare these complexes is via a metal-templated condensation reaction of a dioxime and an arylboronic acid or alkylboronic acid. 

 -> Arylboronic acids are more relevant(적절한). 

 -> Efficiency and yield : Fe2+ > Co2+

 

4. Co : 1+/2+/3+

   Fe : 1+/2+

   Ru : 1+/2+

 

5. Clathrochelate complexes can be decorated with functional groups in apical position by using the corresponding arylboronic acid. 

 -> Donor groups such as pyridine or carboxylic acids can be employed without compromising the metal-templated reaction. 

 

6. The lateral groups attached to the clathrochelate can be modified via the dioxime.

 

7. Clathrochelate complexes are often very stable

 -> the boronate ester groups are not susceptible to hydrolysis, and ligand exchange reactions are only observed under very forcing conditions. 

 -> Fe2+ clathrochelates are not air and moisture sensitive

 

8. Dinuclear iron clathrochelates stand out because they are thermodynamically more stable than the corresponding cobalt or zinc complexes.