Rotaxanes Derived from Dimetallic Polyynediyl Complexes: Extended Axles and Expanded Macrocycles

A new 35-membered macrocycle <bold>3b</bold> derived from 1,10-phenanthroline and two 2,9-p-C6H4O(CH2)(6)O substituents that tether a 2,7-naphthdiyl moiety is synthesized. CuI complexes of <bold>3b</bold> and a previously reported analog in which the naphthdiyl is replaced by a m-C6H4 group (<bold>3a</bold>) are reacted with the hexatriynyl complex trans-(C6F5)(p-tol(3)P)(2)Pt(C=C)(3)H (1.0:2.5 mol ratios) in the presence of K2CO3 (4.05.0 equiv) and I-2 (1.31.8 equiv) in THF at 55 degrees C. Workups afford the rotaxanes <bold>5</bold>.<bold>3a</bold> and <bold>5</bold>.<bold>3b</bold> (4523%), in which the macrocycles are threaded by the sp carbon chain of the diplatinum dodecahexaynediyl complex trans,trans-(C6F5)(p-tol(3)P)(2)Pt(C=C)(6)Pt(Pp-tol(3))(2)(C6F5) (<bold>5</bold>), which is also obtained as a byproduct. The yields of <bold>5</bold>.<bold>3a</bold> and <bold>5</bold>.<bold>3b</bold> are much higher than in the case with octatetraynediyl (C-8) analogs, and their spectroscopic properties and crystal structures are analyzed in detail, especially with reference to recent DFT studies.