Avance 2 400 spectrometer

The FTIR spectra were recorded with an Alfa (Bruker) spectrometer (Bremen, Germany) within the range of 400–4000 cm⁻¹. Samples in the solid state were measured in KBr matrix pellets and using the ATR technique. The ¹H and ¹³CNMR spectra were measured on a Bruker Avance II 400 spectrometer (Bremen, Germany) in DMSO solution at 25 °C. TMS was used as an internal reference.

Chromone and its derivatives, DPPH (2,2-diphenyl-1-picrylhydrazyl), 2,4,6-tripyridyl-s-triazine (TPTZ), FeCl₃·6H₂O, FeSO₄ were purchased from Sigma-Aldrich Co. (St. Louis, MO, USA) and used without purification. Methanol was purchased from Merck (Darmstadt, Germany).
The FT-IR spectra were registered in KBr matrix pellets on Alfa Bruker spectrometer (Bremen, Germany) within the range of 400–4000 cm^-1 with the resolution of 2 cm^-1. The Raman spectra were recorded in the range of 100–4000 cm^-1 with the MultiRam Bruker spectrometer (Bremen, Germany) with the resolution of 1 cm^-1. The ¹H (400.15 MHz) and ¹³C (100.63 MHz) spectra were registered with the Bruker Avance II 400 spectrometer (Bremen, Germany) in DMSO-D6 solution. TMS was used as an internal reference.

NMR spectra were recorded with Bruker Avance II 400 spectrometer operating at 400 MHz, using CDCl₃ solutions with TMS as the internal standard (only selected signals in the ¹H NMR spectra are reported). Coupling constants (J) are given in Hz. The spectra of compounds 3–10 and 12 are included in the Supplementary Materials. The FTIR spectra were obtained using Nicolet™ 6700 spectrometer (Thermo Scientific, Waltham, MA, USA). The spectra were recorded in the range between 4000 and 500 cm⁻¹ with a resolution of 4 cm⁻¹ and 32 scans using Attenuated Total Reflectance (ATR) techniques. ESI and ESI-HRMS spectra were obtained on the Agilent 6530 Accurate-Mass Q-TOF ESI and LC/MS system. Melting points were determined using MP70 Melting Point System (Mettler Toledo, Greifensee, Switzerland). Thin-layer chromatography (TLC) was performed on aluminum plates coated with silica gel 60 F254 (Merck, Darmstadt, Germany), by spraying with ceric ammonium molybdate (CAM) solution, followed by heating. The reaction products were isolated by column chromatography, performed using 70–230 mesh silica gel (J. T. Baker).

¹H (400 MHz), ¹³C{1H} (100 MHz), ³¹P{1H} (161 MHz) and ¹⁹F{1H} (376 MHz) NMR spectra were recorded on an Avance II⁺ 400 spectrometer (Bruker, Wissembourg, France) at 299 K (probe temperature). The chemical shifts are reported in parts per million (δ, ppm) and referenced to residual solvent peaks for ¹H (CDCl₃: δ = 7.26 ppm). The ³¹P- and ¹⁹F-NMR were referenced to the external aqueous solution of 85% H₃PO₄ and KF at 0.5 M, respectively in CDCl₃ (or in a mixture of DMSO-D₆/D₂O for PPh₃ spectra—see Supplementary Material, Figure S9). The IR spectra were measured on an Avatar 360 FTIR (Nicolet, Thermo Scientific, Waltham, MA, USA) in KBr pellets; only significant bands are mentioned in the text. The mass spectra (ESI-TOF) were recorded with a Micromass LCT mass spectrometer (Waters, Milford, MA, USA). Elemental analyses (C, H, N) were performed in a VariolEL instrument from Elementar Analysensysteme (Langenselbold, Germany). In the processing of the elemental analysis results of compound 3 and 4, the theoretical values were calculated taking into account the addition of dichloromethane molecules since their presence is observed in the ¹H-NMR spectra of both compounds. This situation arises from the inclusion of solvent molecules and/or inorganic salts in the dendritic structures during the isolation of the compound by precipitation.

Fourier transform infrared spectroscopy (FTIR) of the isolated compound was performed with a Thermo Nicolet model 6700 IR source range from 500 to 4000 cm^–1 to obtain an IR spectrum to analyze the functional group present in the compound. High-resolution mass spectroscopy (HRMS) was used to determine the molecular mass of the compound using Agilent 6530B, Agilent mass Q-TOF LC/MS. The structure of the isolated pure compound was determined with the help of nuclear magnetic resonance (NMR) spectroscopy using a Bruker Avance II 400 spectrometer (US).

All solvents were purified by distillation prior to use and in case of anhydrous solvents dried and stored under nitrogen atmosphere. Commercially available reagents were used as supplied if not stated different. Synthesis using anhydrous solvents were carried out under Schlenk conditions. For purification by flash chromatography silica gel 60 (Merck) was used. ¹H and ¹³C NMR spectra were recorded at Bruker Avance II 200 spectrometer (¹H at 200 MHz; ¹³C at 50 MHz) and Bruker Avance II 400 spectrometer (¹H at 400 MHz; ¹³C at 100 MHz) in deuterated solvents. Chemical shifts were determined by reference to the residual solvent signals. High‐resolution ESI mass spectra (HRMS) were recorded in methanol using a ESImicroTOF spectrometer (Bruker Daltonics) in positive ion mode. The synthesis and analytical data of the bis‐3‐chloropiperidines 1–5, 7, 9–12^[1b] and 13^[1c] have been described elsewhere. Copies of the ¹H and ¹³C NMR spectra as well as the HRMS spectra of the new B‐CeP derivatives 6 and 8 are included in the supporting information.

1D- and 2D-NMR spectra were recorded in CDCl₃ with a Bruker AVANCE II 400 spectrometer (Bruker, Billerica, MA, USA) operated at 400 MHz for ¹H and at 100 MHz for the ¹³C nucleus. Tetramethylsilane (TMS) was used as the internal reference (δ 0.00). The high resolution mass spectra were determined in a Bruker MicroQTOF-II mass spectrometer (Bruker), equipped with an ESI source operated in positive mode at 180 °C with a capillary voltage of 4500 V. Mass accuracy was verified by calibration before and after sample introduction, using sodium formate (1 mM). Both samples and calibrant were introduced using a syringe pump at 10 µL min⁻¹. Electron impact mass spectra (EI-MS) were obtained at 70 eV by GC–MS on a Hewlett–Packard 5970 Series mass spectrometer interfaced (Hewlwtt-Packard, Palo Alto, CA, USA) with a Hewlett–Packard 5890 gas chromatograph fitted with a column (HP-5MS, 15 m × 0.25 mm i.d., temperature from 200–290 °C, 10 °C/min). HPLC was performed in a Shimadzu chromatograph with a diode array UV-Vis detector (Shimadzu, Kyoto, Japan). Fourier transform infrared spectra were acquired on a FTIR Nicolet 510P spectrometer (Thermo Scientific, Waltham, MA, USA). Spectra over a range of 4000–500 cm⁻¹ with a resolution of 2 cm⁻¹ (50 scans) were recorded using KBr pellets.