Tuning stoichiometry and supramolecular assembly in perfluorinated indazolato coinage metal complexes

Abstract

The reaction of 3-pentafluoroethyl-4,5,6,7-tetrafluoro-1-H-indazole [3-(C₂F₅)IndF₄]H with Ag₂O or [Cu(CH₃CN)₄]BF₄ leads to the formation of two different types of complexes: a trinuclear {[3-(C₂F₅)IndF₄]Ag}₃ complex (1) in the case of silver, and an unprecedented type of pentanuclear complex [Et₃NH]{Cu₅[3-(C₂F₅)IndF₄]₆} (2) in the case of copper. When crystallised from Et₂O, 1 appears as a dimer with d¹⁰–d¹⁰ interactions. When crystallized from toluene, 1 affords the [(toluene)(1)(toluene)] adduct, testifying to its strong π-acid properties. The formation and the aggregation pattern of 1 and 2 can be traced to the extended aromaticity and high electron withdrawing properties of the perfluorinated [3-(C₂F₅)IndF₄]⁻ indazolate.