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Two‐Point Self‐Coordination of a Dizinc( II ) Bispyridylporphyrin Ruthenium Complex Leading Selectively to a Discrete Molecular Assembly: Solution and Solid‐State Characterization
Author(s) -
Iengo Elisabetta,
Zangrando Ennio,
Geremia Silvano,
Graff Roland,
Kieffer Bruno,
Alessio Enzo
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20021018)8:20<4670::aid-chem4670>3.0.co;2-x
Subject(s) - ruthenium , solid state , characterization (materials science) , coordination complex , chemistry , nanotechnology , materials science , catalysis , organic chemistry , metal
The dizinc( II ) bispyridylporphyrin ruthenium complex trans,cis,cis ‐[RuCl 2 (CO) 2 (Zn⋅4′‐ cis DPyP) 2 ] ( 1Zn , 4′‐ cis DPyP=5,10‐bis(4′‐pyridyl)‐15,20‐diphenylporphyrin) features two donor (the uncoordinated 4′‐N(py) atoms) and two acceptor (the Zn atoms) sites and is thus a building block suited for two‐point coordination. 1 H NMR spectroscopy indicates that 1Zn self‐assembles in solution through Zn–4′‐N(py) interactions to yield selectively a highly symmetrical discrete species, in which all donor and all acceptor sites of 1Zn are mutually saturated. Single‐crystal X‐ray analysis established that this adduct is a dimeric species, ( 1Zn ) 2 , with a global S 4 symmetry, in which the four porphyrins have a propeller‐like arrangement. The dimeric species ( 1Zn ) 2 is a meso form derived from the combination of two 1Zn units with opposite helical chirality. The geometry of this highly symmetrical tetraporphyrin assembly in solution, as determined by NMR spectroscopy, is essentially the same as that found in the solid state. Thus 1Zn is an unprecedented example of metal‐containing self‐complementary building block that selectively recognizes itself through four Zn–N(py) interactions, and thus yields a very stable and symmetrical dimeric species, ( 1Zn ) 2 , that features four porphyrins and six metal atoms (two Ru and four Zn).