Metallomacrocycles that incorporate cofacially aligned diimide units.
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.
Khoshbin
Meisa S
MS
Department of Chemistry and Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, USA.
Ovchinnikov
Maxim V
MV
Salaita
Khalid S
KS
Mirkin
Chad A
CA
Stern
Charlotte L
CL
Zakharov
Lev N
LN
Rheingold
Arnold L
AL
D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007094:Imides; D007096:Imidoesters / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009281:Naphthalenes; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010618:Phenanthrolines / Q000737:chemistry*; D000097566:Cyclophanes
D003300:Copper; D007094:Imides; D007096:Imidoesters; D008024:Ligands; D009281:Naphthalenes; D009942:Organometallic Compounds; D010618:Phenanthrolines; C542131:naphthalenediimide; C045143:pyromellitic diimide; D000097566:Cyclophanes