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Sequence, Stoichiometry, and Dimensionality Control in Porphyrin/Bis‐calix[4]arene Self‐Assemblies in Aqueous Solution
Author(s) -
D'Urso Alessandro,
Cristaldi Domenico Andrea,
Fragalà Maria Elena,
Gattuso Giuseppe,
Pappalardo Andrea,
Villari Valentina,
Micali Norberto,
Pappalardo Sebastiano,
Parisi Melchiorre F.,
Purrello Roberto
Publication year - 2010
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/chem.201000803
Subject(s) - porphyrin , supramolecular chemistry , calixarene , chemistry , aqueous solution , resorcinarene , self assembly , molecule , stoichiometry , sequence (biology) , crystallography , photochemistry , organic chemistry , biochemistry
The use of a water‐soluble octacationic bis‐calix[4]arene with divergent cavities (BC 4 ) as a templating agent for the assembly of a tetraanionic porphyrin (CuTPPS) has allowed the noncovalent synthesis of 2D or 3D multiporphyrin assemblies. Self‐assembly of CuTPPS and BC 4 molecules proceeded under hierarchical control in a stepwise fashion to yield discrete and isolable supramolecular nanostructures containing up to 33 molecular elements (i.e., the CuTPPS/BC 4 17:16 assembly, obtained in less than three hours). The formation of these species could be conveniently monitored by means of UV/Vis spectroscopy by following the absorbance of the Soret band at 412 nm. In particular, the attainment of the pivotal CuTPPS/BC 4 5:4 species with a cruciform structure, as the key fork‐point intermediate for the subsequent formation of the higher 2D and 3D assemblies, has been demonstrated by light‐scattering studies and by an unequivocal synthesis of mixed‐porphyrin/calixarene 5:4 species involving the use of two different types of metallated porphyrins, namely CuTPPS and MnTPPS. The remarkable stability of these assemblies permits a stepwise synthesis that makes it possible to choose the desired porphyrin sequence.