Download 中文题目（3号黑体字，居中）

超分子自组装
Functional Organometallic Complexes
Ying-Feng Han*
1
College of Chemistry & Materials Science, Northwestern University, 710000, Xi’an China
2
Department of Chemistry, Fudan University, 200433 Shanghai, China
E-mail: [email protected]
Recently, based on the successful construction of organometallic
molecular assemblies1,2 using polydentate ligands with
N-heterocyclic carbene donor functions, we have recently been
able to perform photochemical modification (PCM) reactions on
rectangular metalacycles built from bridging dicarbene ligands
and featuring internal olefin groups via a photochemical [2+2]
cycloaddition reaction.3 These results indicate the suitability of
the [M2(dicarbene)2]2+ (M = Ag, Au) metalacycles as scaffolds
for the photodimerization of the olefinic bonds to yield
cyclobutane units within the molecular rectangles. While complexes feature an internal cyclobutane unit obtained
by [2+2] cycloaddition of internal olefinic bonds, we also became interested in utilizing [M2(dicarbene)2]2+ (M =
Ag, Au) complexes with terminal double bonds, which upon [2+2] cycloaddition would lead to complexes
featuring a macrocyclic ligand as in. Removal of the metal atoms from such assemblies leads to interesting new
macrocycles. The desired molecular size of the tetraimidazolium macrocycle can be tuned easily by changing the
length and breadth of the internal bridging groups of ligands. This system presents an excellent starting point for a
new method to multipurpose receptors.
We have found that H2 can initiate unusual
transformations between organometallic assemblies.4 If
the Cp* group acts as a monodentate ligand, then the
reversible constitutional switching between the two
distinct complexes is accompanied by reversible changes
in the coordination mode of the metal center from
triangular to tetrahedral coordination geometries. The
present system reversibly provides a foundation on which
to develop organometallic switching systems that can be
triggered by hydrogen.
References
1
a) Han, Y.-F.; Jia, W.-G.; Yu, W.-B.; Jin, G.-X. Chem. Soc. Rev. 2009, 38, 3419-3434; b) Han, Y.-F.; Jin, G.-X. Chem.
Soc. Rev. 2014, 43, 2799-2823; c) Han, Y.-F.; Jin, G.-X. Acc. Chem. Res. 2014, 47, 3571-3579.
2
a) Han, Y.-F.; Jia, W.-G.; Lin, Y.-J.; Jin, G.-X. Angew. Chem., Int. Ed. 2009, 48, 6234-6238; b) Li, H.; Han, Y.-F.; Lin,
Y.-J.; Guo, Z.-W.; Jin, G.-X. J. Am. Chem. Soc. 2014, 136, 2982-2985.
3
a) Han, Y.-F.; Jin, G.-X.; Hahn, F. E. J. Am. Chem. Soc. 2013, 135, 9263-9266; b) Han, Y.-F.; Jin, G.-X.; Daniliuc, C.
G.; Hahn, F. E. Angew. Chem. Int. Ed. 2015, 54, 4958-4962.
4
Han, Y.-F.; Zhang, L.; Weng, L.-H.; Jin, G.-X. J. Am. Chem. Soc. 2014, 136, 14608−14615.