Neutral interlocked assemblies from anionic pseudorotaxanes coordinated to Sn(IV) and Cu(I) metallic centers

作者：Baum Robert R; Veach Jedidiah J; Semeniuc Radu F^*; Wheeler Kraig A; Pellechia Perry J

来源：Inorganica Chimica Acta, 2017, 455: 52-60.

DOI：10.1016/j.ica.2016.10.006

• Pseudorotaxanes
• Supramolecular chemistry
• X-ray crystal structures
• Phosphor-1,1-dithiolates
• Metal complexes

Anionic [2]pseudorotaxanes have been prepared by threading an axle consisting of two dithiophosphonate donor groups attached to a 1,4,5,8-naphthalenediimide (NDI) core through the cavity of the bis-1,5-(dinaphtho)-38-crown-10 ether (15DN38C10). The subsequent coordination of these interlocked, negatively charged species to R3SnCl (R = Me, Ph) and (Ph3P)(2)CuNO3 yields neutral (pseudo)rotaxanes of the general formula NDIRCH2CH2O)(n)(An)PS2"M"](2) subset of 15DN38C10 (n = 1, 2; An = anisole; "M" = R3Sn or (Ph3P)(2)Cu). Solution and solid state studies of the rotaxanation process show that there are two factors influencing the interaction between the axles and the wheel: the size of the stopper and the length of the side-arms of the axles. When the axle termini are bulky enough to prevent threading, the length of the side-arms has little influence over the self-assembly process. In contrast, when the size of the stopper does not preclude the threading of the axle through the cavity of the crown, the length of the side-arms is the determining factor in the rotaxanation process. These results presented here provide an alternative method for the synthesis of counter-ion free interlocked species, based on anionic axles with donor capabilities that would produce a neutral interlocked architecture upon threading and coordination to cationic metal-containing centers.

• 出版日期2017-1-30