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Self‐Assembled, Kinetically Locked, Ru II ‐Based Metallomacrocycles: Physical, Structural, and Modeling Studies
Author(s) -
de Wolf Paul,
Waywell Phil,
Hanson Matt,
Heath Sarah L.,
Meijer Anthony J. H. M.,
Teat Simon J.,
Thomas Jim A.
Publication year - 2006
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.200500623
Subject(s) - luminescence , chemistry , density functional theory , ion , ruthenium , electrochemistry , crystallography , metal , self assembly , ligand (biochemistry) , photochemistry , materials science , computational chemistry , electrode , organic chemistry , receptor , catalysis , biochemistry , optoelectronics
By using a “complex as ligand approach,” the metal‐ion‐templated self‐assembly of heterometallic teteranuclear metallomacrocycles containing kinetically locked Ru II centers is described. Depending on the metal‐ion template employed in the self‐assembly process, the final macrocycle can be kinetically labile or inert. Electrochemical studies reveal that the kinetically inert macrocycles display reversible Ru III/II oxidation couples. The crystal structure of a kinetically inert Ru 2 Re 2 macrocycles reveals a structurally complex palmate anion‐binding pocket. Host–guest studies carried out with the same macrocyle in organic solvents reveals that the complex functions as a luminescent sensor for anions and that binding affinity and luminescent modulation is dependent on the structural nature and charge of the guest anion. Computational density functional theory (DFT) studies support the hypothesis that the luminescence of the macrocycle is from a 3 MLCT state and further suggests that the observed guest‐induced luminescence changes are most likely due to modulation of nonradiative decay processes.