*3.2. Methods*

Nuclear magnetic resonance spectroscopy (NMR) measurements (1H, 13C, and 29Si NMR) were conducted using spectrometers: Bruker Ultrashield 300 MHz and 400 MHz respectively (Bruker, Faellanden, Switzerland) with CDCl3, CD2Cl2, DMF-*d*7, and DMSO*d*6 as a solvent. Chemical shifts are reported in ppm with reference to the residual solvent signal peaks for 1H and 13C and to TMS for 29Si.

Fourier transform-infrared (FT-IR) spectra were recorded on a Nicolet iS5 (Thermo Scientific, Waltham, MA, USA) spectrophotometer equipped with a SPECAC Golden Gate, diamond ATR unit with a resolution of 2 cm<sup>−</sup>1. In all cases, 16 scans were collected to record the spectra in a range of 4000–430 cm<sup>−</sup>1.

Elemental analyses (EA) were performed using a Vario EL III instrument (Elementar Analysensysteme GmbH, Langenselbold, Germany).

High-resolution mass spectra (HRMS) were obtained using Impact HD mass spectrometerQ-TOF type instrument equipped with electrospray ion source (Bruker Daltonics, GmbH, Bremen, Germany). The sample solutions (DCM:MeOH) were infused into the ESI source by a syringe pump (direct inlet) at the flow rate of 3 μL/min. The instrument was operated under the following optimized settings: endplate voltage 500 V; capillary voltage 4.2 kV; nebulizer pressure 0.3 bar; dry gas (nitrogen) temperature 200 ◦C; dry gas flow rate 4 L/min. The spectrometer was previously calibrated with the standard tune mixture.

X-ray crystallography. Diffraction data were collected by the ω-scan technique, using graphite-monochromated MoKα radiation (λ = 0.71073 Å), at 100(1) on Rigaku XCalibur (Rigaku OD, Neu-Isenburg, Germany) four-circle diffractometer with EOS CCD detector. The data were corrected for Lorentz-polarization as well as for absorption effects [75]. Precise unit-cell parameters were determined by a least-squares fit of the 6861 reflections of the highest intensity, chosen from the whole experiment. The structures were solved with SHELXT [76] and refined with the full-matrix least-squares procedure on F2 by SHELXL [77]. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were placed in idealized positions and refined as 'riding model' with isotropic displacement parameters set at 1.2 (1.5 for CH3) times Ueq of appropriate carrier atoms.

Crystallographic data for the structural analysis has been deposited with the Cambridge Crystallographic Data Centre, no. CCDC–2045899. Copies of this information may be obtained free 589 of charge from: The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK; e-mail: deposit@ccdc.cam.ac.uk, or www.ccdc.cam.ac.uk.

Crystal data. C70H68N8O14Si10, Mr = 1526.22, monoclinic, P21/c, a = 14.8188(5) Å, b = 22.6566(9) Å, c = 11.1567(3) Å, β = 101.194(3)◦, V = 3674.5(2) Å3, Z = 2, dx = 1.379 <sup>g</sup>·cm<sup>−</sup>3, F(000) = 1592, μ = 0.248 mm<sup>−</sup>1, 16,862 reflections collected, 6455 symmetry-independent (Rint = 2.40%), 5402 withI>2σ(I). Final R(F) [I > 2σ(I)] = 0.0580, wR2 [I > 2σ(I) = = 0.1257, R(F) [all data] = 0.0709, wR2 [all data] = 0.1298, Δρmax/min = 1.398/−0.627 e/Å−3.

#### *3.3. General Procedure for Copper(I)-Catalyzed Azide-Alkyne Cycloaddition (CuAAC)*

3.3.1. Synthetic Procedure with the Use of CuSO4 as Cu(II) Ion Source

The exemplary synthetic procedure is presented for **iBuT8-A1**. To a solution of **iBuT8- N3** (300 mg, 0.33 mmol) in THF (15 mL), sodium L-ascorbate crystalline (in general 0.3–5 eq., herein 5 eq.), **A1** (in general 1.4–8 eq., herein 7.85 eq.) and copper(II) sulfate pentahydrate (in general 0.025–0.25eq., herein 0.25 eq.) diluted in water, were added respectively. The reaction was conducted in a closed system until full conversion of **iBuT8-N3**, confirmed

by FT-IR analysis (typically 72–96 h depending on alkyne used). The crude product was filtered off by column chromatography (silica gel 60, THF) to remove solid impurities and the solvent was evaporated. It was extracted with DCM and water. Organic layer was dried with anhydrous sodium sulfate. Then the solvent was removed under reduced pressure, and the product was precipitated in methanol as white solid. The product (83 mg, i.e., 78% isolated yield) was analyzed by 1H, 13C, and 29Si NMR and EA to confirm its structure. For the spectroscopic analysis please see Supplementary Materials.

#### 3.3.2. Synthetic Procedure with Use of CuBr as Cu(I) Ion Source

The exemplary synthetic procedure is presented for **iBuT8-A7** [33]. To a solution of **iBuT8-N3** (200 mg, 0,22 mmol) and **A7** (35 μL, 0.33 mmol) in THF (3 mL) stirring under argon, CuBr (3.2 mg, 0.02 mmol) and PMDTA (4.6 μL, 0.02 mmol) were added. The reaction mixture was stirred at room temperature for 30 h. After the reaction was completed (FT-IR analysis), the crude product was filtered off by column chromatography (silica gel 60, THF) to remove solid impurities and solvent was evaporated. The resulted solid was washed with methanol and dried in vacuo. Second option for isolation is the extraction in DCM and water. Organic layer was dried with sodium anhydrous sulfate, solvent was removed under reduced pressure, and product was precipitated in methanol as a pale yellow solid in 81% yield (181 mg). Product was analyzed by 1H, 13C, and 29Si NMR and EA to confirm its structure.

*3.4. General Procedure for Using SQs-Based Pyridyl-Triazole- and Thiophenyl-Triazole Derivatives as Ligands in the Formation of Coordination Complexes with Selected Transition Metals (Pd, Pt, Rh)*

3.4.1. Procedure for the Synthesis of **iBuT8-A7-Pd(NˆS)**, **DDSQ-A1-[Pd(NˆN)]2**, and **(iBuT8-A1)2-Rh(NˆN)**

The procedure for the synthesis of **iBuT8-A7-Pd(NˆS)** is described as an example.

A mixture of 1 equiv. of **iBuT8-A7** ligand and a stoichiometric amount of Pd(cod)Cl2 was dissolved in dichloromethane and stirred at room temperature for 24 h. After this time, a solvent was evaporated. The crude product was dissolved in hexane and filtrated off via cannula. The solvent was evaporated and afforded in pure **iBuT8-A7-Pd(NˆS)** as yellow solid in 60% yield (91 mg). It was dried in vacuo. Complex **DDSQ-A1-[Pd(NˆN)]2** was obtained analogously, however, it precipitated from the DCM solution. After 24 h, the solvent was evaporated and washed with hexane and dried in vacuo. Obtained products were yellow **DDSQ-A1-[Pd(NˆN)]2** (93%, 228 mg) and orange **(iBuT8-A1)2-Rh(NˆN)** (for Rh, the complexation was performed within 96 h) (55%, 70 mg) solids. **DDSQ-A1-[Pd(NˆN)]2** exhibits very restricted solubility in DCM, chloroform, THF or hexane and is soluble in DMF and DMSO.

#### 3.4.2. Procedure for Synthesis of **iBuT8-A1-Pt(NˆN)**

The complex was synthesized as described by Galanski and Keppler et al. with slight modifications [78]. To a solution of ligand **iBuT8-A1** (0.051 g, 0.05 mmol, 1.005 eq.) in THF, a solution of K2PtCl4 in water-MeOH (1:1) was added. The mixture was stirred overnight in a light-protected flask at 40 ◦C. After this time, the mixture was in a form of suspension and the addition of MeOH resulted in crude product precipitation. It was washed with methanol and afforded in pure **iBuT8-A1-Pt(NˆN)** as pale pale-yellow solid in 87% yield (55 mg) and then dried in vacuo.
