Structural and Coordination Studies of 'Pearl Oysterlike' Porphyrins

摘要

We report the coordination studies of porphyrins with pre-organized but yet flexible straps,each bearing over the center of the porphyrin either a 2,2-malonic acid diethyl ester residue or a 2,2-malonic acid residue.The straps are attached to the porphyrin via two adjacent meso positions,5,10 and 15,20,respectively,and the 2,2-malonic acid diethyl ester groups are connected to the straps on benzylic carbon atoms.These two structural features allow a significant flexibility of the straps,as confirmed by the comparison of the X-ray structures of the zinc,nickel,and lead complexes of porphyrin 1.In the latter,the influence of the lone-electron pair of lead is clearly demonstrated.The coordination of bismuth is also reported.