| 17441109 |
Khoshbin MS, Ovchinnikov MV, Salaita KS, Mirkin CA, Stern CL, Zakharov LN, Rheingold AL: Metallomacrocycles that incorporate cofacially aligned diimide units. Chem Asian J. 2006 Nov 20;1(5):686-92.
Pyromellitic diimide and naphthalene diimide moieties were incorporated into hemilabile phosphanylalkyl thioether ligands. These ligands reacted with [Cu (CH3CN) 4] PF6 and [Rh (NBD) Cl] 2 (NBD = norbornadiene) by the weak-link approach to form condensed intermediates. Upon reaction of each diimide ligand with these transition-metal precursors, the two diimide units became cofacially aligned within a supramolecular macrocyclic architecture. The introduction of ancillary ligands to each of these condensed intermediates caused the weak thioether-metal bonds to break, thus generating a large macrocycle in which the distance between diimide units is significantly larger than for the condensed intermediates. The two Rh (I) cationic condensed intermediates were characterized by single-crystal X-ray diffraction studies, and the electrochemical activity of these macrocycles was demonstrated with the naphthalene diimide-Cu (I) macrocycles. |
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