Tetrakis triphenylphosphine palladium 0

Chalcone (Acros), 4-fluorochalcone (TCI America), 4’-fluorochalcone (TCI America), 4,4’-difluorochalcone (TCI America), 1-ethynyl-4-fluorobenzene (Aldrich), 4-ethynyl-α,α,α-trifluorotoluene (Aldrich), n-butyllithium solution (Aldrich), tributyltin chloride (Fisher), tributyl(phenylethynyl)tin (Aldrich), tetrakis(triphenylphosphine)palladium(0) (Aldrich), n-iodosuccinimide (abbreviated NIS, Aldrich) were used as received. All other reagents and solvents were used as received unless otherwise specified. Xylenes and tetrahydrofuran were distilled over sodium and benzophenone, degassed and stored under nitrogen. ADP, ADPI₂, WS3, BF₂(WS3), and Zn(WS3)₂ were synthesized and purified according to literature procedures with minor modifications [2 (link),5 (link),9 (link),33 (link)–34 (link)]. (4-Fluorophenylethynyl)tributyltin (for the synthesis of L3), and [4-(trifluoromethyl)phenyl](tributyltin)acetylene (for the synthesis of L4) were synthesized according to literature procedures with minor modifications and used without purification [35 (link)–36 (link)].

n-Butyllithium (2.5 M in hexane), trimethyltin chloride (1.0 M in THF), 2-(tributylstannyl)pyridine (85%), 3,4-ethylenedioxytiophene (97%), selenophene (97%), 2-thienylboronic acid (95%), bis(triphenylphosphine)palladium (II) dichloride (98%), tetrakis(triphenylphosphine)palladium (0) (99%), and 4,7-bis(5-bromothiophen-2-yl)benzothiadiazole (99%) were purchased from Sigma Aldrich. Anhydrous potassium carbonate (99%) was received from Chempur. Anhydrous tetrahydrofuran, toluene, and methanol were purchased from POCH. Tetrahydrofuran was dried over Na/benzophenone ketal before use. Other commercially available substances and reagents were used without any prior purification. Preparative column chromatography was performed on the glass column with Acros Organics silica gel for chromatography, 0.035–0.075 mm, 60 Å. ¹H-NMR and ¹³C-NMR spectra were recorded in deuterated chloroform (CDCl₃) on Brüker Avance III 400 MHz Instruments or on Bruker Avance II 600 Instruments, respectively. Chemical shifts were locked to chloroform δH 7.26 (s) and δC 77.16 (t) signals. The molecular weights of the products were determined using a Brüker micrOTOF-Q spectrometer, FWHM-17500, 20 Hz (Billerica, MA, USA). The percentage composition of the elements was measured on a vario EL cube Analyzer from Elementar Americas (Ronkonkoma, New York, NY, USA).

4-Trifluoromethylphenylboronic acid, 4-(dimethylamino)phenylboronic
acid, o-phenylenediamine, 2-aminothiophenol, 4-(trifluoromethyl)benzyl
bromide, 5-bromo-2-thiophenecarboxaldehyde, potassium triflate, trifluoroacetic
acid, cesium carbonate, potassium carbonate, sodium bisulfite, tetrakis(triphenylphosphine)palladium(0),
and bis(triphenylphosphine)palladium(II) chloride were obtained from
Sigma-Aldrich (Madrid, Spain). IrCl₃ was obtained from
Johnson Matthey. Deuterated solvents were obtained from Euriso-top.
The purities ≥95% of the synthesized complexes used for biological
evaluation were determined by RP-HPLC.

Poly(ethylene glycol) methyl ether (mPEG, M_n 2 kDa) was purchased from Rapp Polymers. XPhos Pd G2 (Sigma), bis(pinacolato)diboron (99%, Sigma), potassium acetate (99%, Sigma), zinc powder (99%, Sigma), tetrakis(triphenylphosphine)palladium(0) (99%, Sigma), titanium(IV) chloride (99%, Sigma), 4-chloro-4-hydroxybenzophenone (98%, Sigma), bis(4-methoxyphenyl)methanone (98%, TCI), 4-bromobenzophenone (98%, Sigma), potassium carbonate (K₂CO₃, 99%, Sigma), trifluoromethanesulfonic acid (99%, Sigma), bis(pentafluorophenyl) carbonate (Apollo scientific, 97%), cesium fluoride (CsF, Sigma 99%), 2,2-bis(hydroxymethyl)propionic acid (Sigma, 99%), Cyanine7 NHS ester (Lumiprobe), Gold-Nanoshells (160 nm NanoXactTM Gold Nanoshells, nanoComposix), and all other chemicals were supplied by Sigma-Aldrich. Dialysis Membrane MWCO 12,000−14,000 Da from Spectra/Pro® was used for dialysis. Wheat Germ Agglutinin (WGA)-Alexa Fluor^TM 488 Conjugate, Hoechst 33342, LysoTracker^TM Green DND-26, propidium iodide (PI), Dulbecco’s modified eagle medium (DMEM), phosphate-buffered salines (PBS, pH 7.4), no mycoplasma fetal bovine serum (FBS), trypsin-EDTA, and penicillin-streptomycin were obtained from ThermoFisher. All other chemicals were used as received without further treatment. All experiments conducted in this work use ultrapure Milli Q (Millipore) water (18.2 MΩ·cm).

Tetraphenylmethane (95%, ABCR, Karlsruhe, Germany), 1,3,5-tribromobenzene (98%, Acros Organics, Geel, Belgium), bromine (99%, Acros Organics, Geel, Belgium) trimethylsilylacetylene (98%, ABCR, Karlsruhe, Germany), CuBr (98%, Sigma-Aldrich, Darmstadt, Germany), CuI (98%, Fluka, Dresden, Germany), tetrakis(triphenylphosphine)palladium(0) (99%, Sigma-Aldrich, Darmstadt, Germany), bis(triphenylphosphine)palladium(II) dichloride (98%, Sigma-Aldrich, Darmstadt, Germany), Bu4NF (1M solution in THF, ABCR, Karlsruhe, Germany), bis(4-bromophenyl)ether (99%, Sigma-Aldrich, Darmstadt, Germany), 1,4-diiodobenzene (98%, ABCR, Karlsruhe, Germany), phenylacetylene (98%, Acros Organics, Geel, Belgium), 1,3-diphenyl-2-propanone (99%, Sigma-Aldrich, Darmstadt, Germany), potassium hydroxide (99%, Acros Organics, Geel, Belgium), glacial acetic acid (99%, Sigma-Aldrich, Darmstadt, Germany), potassium permanganate, triethylamine (99%, Acros Organics, Geel, Belgium), toluene (99.5%, Component Reactive, Moscow, Russia), ethanol (96%, Component Reactive, Moscow, Russia), diphenylether (99%, ABCR, Karlsruhe, Germany), THF ( HPLC grade, Carlo Erba reagents, Milan, Italy), and gases: N₂ (99.999%) and CO₂ (99.999%) were used as received.