Figure S1. (a) The 1H NMR spectrum of starting diamine (AP0), recorded in CDCl3 at 400 MHz. The signal assigned to methylene protons directly linked to amine is shown in the detail, for a better visualization of the splitting pattern and (b) the 13C NMR spectrum of AP0, recorded in CDCl3 at 100 MHz.

Figure S2. Dielectric spectroscopy measurements of iCN.

Figure S3. Evolution in time of iCN in normal conditions; FT-IR spectrum of hydrolyzed iCN and the polymer (iCN-p) versus the initial sample.

Figure S4. DSC analysis of polymerized iCN.

Figure S5. a) Changes in the electronic absorption spectra of iCN in DMF (1.2 × 10−6 M), with increasing the K2PtCl6 concentration (0, 0.121, 0.234, 0.343, 0.447, 0.64, 0.773, 0.858 and 0.976 mM); inset: the Benesi – Hildebrand plot for the new emerged band around 380 nm; b) fluorescence quenching spectra of iCN in the presence of K2PtCl6, at 300 nm excitation; inset: the Stern-Volmer plot for the band at 342 nm; c) the fluorescence spectra of the Pt (IV) - iCN complex, at the K2PtCl6 concentrations of 0.234, 0.447, 0.644 and 0.976 mM, obtained under 360 nm excitation.

Figure S6. (a) The overlapped 1H NMR spectra of iCN complexes, recorded in DMSO-d6 (2.51 ppm) at 400 MHz. Because of the low solubility, the residual water from DMSO gives a very large and intense signal between 3.0 and 4.5 ppm, partially overlapping the methylene 2 signal. (b) the overlapped 13C NMR spectra of iCN complexes recorded at 100 MHz, using an acquisition time of 12 to 18 hours.

Figure S7. FT-IR spectra of metal complexes of bis (isocyanide)disiloxane (the vertical line marks the initial position of the isocyanide band).

Figure S8. H-NMR spectrum of the hydrosilylation product obtained from 1,3-divinyl tetramethyldisiloxane and 1,1,3,3-tetramethyldisiloxane with iCN-Pt as catalyst, at 100 °C for 2 h, in bulk

Figure S9. Reduction of p-nitrophenol with NaBH4 and iCN-Pt as pre-catalyst. a) Concentration vs. time; b) TEM image of Pt NPs formed during reaction.

Figure S10. Catalytic activity of iCN-Ag complex in alkaline decomposition of H2O2 and first order kinetic plot.

Figure S11. Color removal efficiency with iCN-Fe in different experimental conditions (a) and successive cycles in ambient (sunlight), with H2O2 added (b).