The new Me2Si-bridged [1]­ferrocenophane ([1]­FCP) with one iPr group in α position on a Cp ring was synthesized in an enantiopure (S p -4) and a racemic form (rac-4). The molecular structure of rac-4 was determined by single-crystal X-ray analysis (tilt angle α = 20.15(14)°). Experimental and calculated molecular structures of the related [1]­FCPs with one (S p -4 and rac-4) or two iPr groups (S p ,S p -4) are compared to that of the nonsubstituted [1]­FCP Me2Sifc. Differential scanning calorimetry (DSC) measurements resulted in ΔH ROP of −72(±2) kJ mol–1 for rac- 4 and −62(±2) kJ mol–1 for the known S p ,S p -4. While thermal ring-opening polymerization of S p ,S p -4 gave insoluble material, the monosubstituted monomers S p -4 and rac- 4 resulted in soluble polymers with molecular weights (M w) of 5.3 × 106 and 2.6 × 106 Da, respectively. Investigation of the polymer structures by 29Si NMR spectroscopy gave further evidence that the breakage of Si–Cp bonds occurs in the thermal ROP process of sila[1]­ferrocenophanes.

A mixture of cis/trans isomers of phospha[1]ferrocenophanes equipped with one iPr group at the α position to the bridging PhP moiety was prepared. Both isomers (cis-4 and trans-4) were obtained as racemates and could be separated so that their thermal properties were investigated individually. The molecular structure of cis-4 was determined by single-crystal X-ray analysis showing a tilt angle α=26.35(8)°. Interconversion between both isomers occurred in the melt at elevated temperatures and revealed that the trans isomer is thermodynamically more stable. Structural and thermodynamic data was complemented by DFT calculations (B3PW91/6-311+G(d,p) and B3PW91-D3(BJ)/6-311+G(d,p)). Performance of thermal ring-opening polymerization (ROP) of trans-4 at 230 °C gave polymers and cyclic oligomers. Gel permeation chromatography (GPC) of the sulfurized polymer resulted in a molecular weight of 62.5 kDa (M ) and a polydispersity index of 1.39 (PDI). Mass spectrometric analysis of the oligomers showed the presence of cyclic species from dimers to heptamers. After sulfurization, preparative thin layer chromatography led to the separation of three isomeric dimers. Structural characterization of these dimers by single-crystal X-ray analysis led to the conclusion that the Fe-Cp bond breaks during the thermal ROP process. A mechanism similar to the known mechanism of the photolytic ROP of ferrocenophanes is proposed.

In recent years, copper-64 and copper-67 have been considered as a useful theranostic pair in nuclear medicine, due to their favourable and complementary decay properties. As 67Cu and 64Cu are...

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