Abstract
The synthesis of organometallic complexes [{Ru(p-MeC6H4CHMe2)}n(C21H24S3)][CF3SO3]2n (n = 1, 6; n = 2, 7) and [{Ir(C5Me5)}2(C21H24S3)][CF3SO3]4 (9) based upon the trimeric macrocycle cyclotris(dimethylthiophenylene) (4) is reported. A saddle conformation is identified for the free ligand 4 and complexes 6 and 9 by X-ray crystallography. The anion complexation behavior of complex 9 is compared with the related cyclotriveratrylene complex [{Ru(p-MeC6H4CHMe2)}2(C27H30O6)][CF3SO3]4 (2), which possesses a bowl-shaped conformation, by 1H NMR titration studies in a variety of solvents. While host 2 displays a significant affinity for halides with binding constants of up to 1.25(7) × 103 M-1 in nitromethane solution, the absence of a molecular cavity in 9 results in very little specific anion affinity. The 1,3-alternate calix[4]arene complex [{Ru(η6-p-MeC6H4CHMe2)}2(η6:η6-C40H48)][BF4]4 (11) is also reported and shown to bind anions in an unusual C−H···anion hydrogen-bonding fashion by X-ray crystallography and 1H NMR.
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