A family of pyridine dipyrrolide bismuth complexes (Mes,PhL)MX (1–6 (M = Bi, X = O-2,6-Me-C6H3 = OXyl (1); M = Sb, X = OXyl (2); M = Bi, X =...

We describe the use of the cyaphide‐azide 1,3‐dipolar cycloaddition reaction for the synthesis of a new class of inorganic rotaxanes containing gold(I) triazaphosphole stoppers. Electron‐deficient bis‐azides, which thread perethylated pillar[5]arene in aromatic solvents, readily react with two equivalents of Au(IDipp)(CP) (IDipp=1,3‐bis‐(2,6‐diisopropylphenyl)‐imidazol‐2‐ylidene) to afford interlocked molecules via an inorganic click reaction. These transformations proceed in good yields (ca. 65 %) and in the absence of a catalyst. The resulting organometallic rotaxanes are air‐ and moisture‐stable and can be purified by column chromatography under aerobic conditions. The targeted rotaxanes were characterized by multi‐element nuclear magnetic resonance (NMR) spectroscopy, mass‐spectrometry, and single‐crystal X‐ray diffraction.

A series of dynamic metalloporphyrin [2]rotaxane molecular shuttles comprising of bis-functionalised Zn(II) porphyrin axle and pyridyl functionalised macrocycle components are prepared in high yield via active metal template synthetic methodology. Extensive variable temperature 1 H NMR and quantitative UV-Vis spectroscopic titration studies demonstrate dynamic macrocycle translocation is governed by an inter-component co-ordination interaction between the macrocycle pyridyl and axle Zn(II) metalloporphyrin, which serves to bias a 'resting state' co-conformation.The dynamic shuttling behaviour of the interlocked structures is dramatically inhibited by the addition of a neutral Lewis base such as pyridine, but can also be tuned via postsynthetic rotaxane demetallation of the porphyrin axle core to give free-base, or upon subsequent metallation, Ni(II) [2]rotaxane analogues. Importantly, the Lewis acidic Zn(II) porphyrin axle component is also capable of coordinating anions which induces mechanical bond shuttling behaviour resulting in a novel optical sensing response.

We describe the use of the cyaphide‐azide 1,3‐dipolar cycloaddition reaction for the synthesis of a new class of inorganic rotaxanes containing gold(I) triazaphosphole stoppers. Electron‐deficient bis‐azides, which thread perethylated pillar[5]arene in aromatic solvents, readily react with two equivalents of Au(IDipp)(CP) (IDipp=1,3‐bis‐(2,6‐diisopropylphenyl)‐imidazol‐2‐ylidene) to afford interlocked molecules via an inorganic click reaction. These transformations proceed in good yields (ca. 65 %) and in the absence of a catalyst. The resulting organometallic rotaxanes are air‐ and moisture‐stable and can be purified by column chromatography under aerobic conditions. The targeted rotaxanes were characterized by multi‐element nuclear magnetic resonance (NMR) spectroscopy, mass‐spectrometry, and single‐crystal X‐ray diffraction.