Supporting Information. Selective Synthesis of Iridium(III) End-Capped. Polyynes by Oxidative Addition of 1-Iodopolyynes

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1 Electronic Supplementary Material (ES) for Dalton Transactions. This journal is The Royal Society of Chemistry 2018 Supporting nformation Selective Synthesis of ridium() End-Capped Polyynes by Oxidative Addition of 1-odopolyynes to Vaska s Complex Bartłomiej Pigulski. Agata Jarszak, Sławomir Szafert* Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie, Wrocław, Poland S1

2 Table of contents X-ray Crystallography Details...3 UV/Vis Spectra...5 DFT Calculations Details...7 Cyclic Voltammetry...10 MR Spectra...10 S2

3 X-ray Crystallography Details Table S1. Details of X-ray single crystal diffraction experiment for 2-C 4 [r] C 7 H 8 2-C 4 [r] Chemical formula C 47 H 34 ClrO 3 P 2 C 7 H 8 M r Crystal system, space Monoclinic, P2 1 /n group Temperature (K) 100 a, b, c (Å) (3), (5), (9) β ( ) (3) V (Å 3 ) 4642 (2) Z 4 Radiation type Mo Kα µ (mm 1 ) 3.71 Crystal size (mm) Data collection Diffractometer KUMA KM-4 CCD Absorption correction Analytical CrysAlis PRO, Oxford Diffraction Ltd., Version (release CrysAlis171.ET) (compiled Apr ,14:27:37) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, ) T min, T max 0.679, o. of measured, 37593, 12946, 5253 { > 2σ()} independent and observed reflections R int (sin θ/λ) max (Å 1 ) Refinement R[F 2 > 2σ(F 2 )], 0.061, 0.124, 0.76 wr(f 2 ), S o. of reflections o. of parameters 540 o. of restraints 76 H-atom treatment H-atom parameters constrained Δρ max, Δρ min (e Å 3 ) 1.62, 1.83 S3

4 Figure S1. Molecular structure of 2-C 4 [r] C 7 H 8. Thermal ellipsoids are given with 50% probability. S4

5 UV/Vis Spectra Figure S2. UV-Vis spectra of 1-C 4-10 [r] polyynes. Figure S3. UV-Vis spectra of 2-C 4-8 [r] polyynes. S5

6 Figure S4. Plot of HOMO/LUMO gap calculated from UV/Vis spectra versus n (n = number of triple bonds) for 1-C n [r] series of complexes. S6

7 DFT Calculations Details Table S2. HOMO and HOMO-1 orbitals. HOMO-1 1-C 4 [r] HOMO 1-C 6 [r] 1-C 8 [r] 1- C 10 [r] 2-C 4 [r] 2-C 6 [r] 2-C 8 [r] S7

8 Table S3. LUMO and LUMO+1 orbitals. LUMO 1-C 4 [r] LUMO+1 1-C 6 [r] 1-C 8 [r] 1-C 10 [r] 2-C 4 [r] 2-C 6 [r] 2-C 8 [r] S8

9 Table S4. Energies of frontier molecular orbitals. HOMO-1 [ev] HOMO [ev] LUMO [ev] LUMO+1 [ev] 1-C 4 [r] C 6 [r] C 8 [r] C 10 [r] C 4 [r] C 6 [r] C 8 [r] HOMO/LUMO gap [ev] S9

10 Cyclic Voltammetry Table S5. Potentials of reduction and oxidation peaks versus SCE (E 1/2 ferrocenium/ferrocene (Fc+ /Fc) redox couple = V vs. SCE in CH 2 Cl 2 /(Bu 4 )[PF 6 ])). Compound E red p E ox p 1-C 10 [r] C 4 [r] C 6 [r] , , C 8 [r] ; , Figure S4. Cyclic voltammograms of 1-C 10 [r], 2-C 4 [r], 2-C 6 [r], 2-C 8 [r] with added ferrocene. S10

11 MR Spectra 1 Title BP1154B 4 Spectrometer Frequency ucleus 1H Figure S5. 1 H MR spectrum of 1-C 4 [r]. Parameter Value 1 Title BP1154B Spectrometer Frequency ucleus 13C Figure S6. 13 C MR spectrum of 1-C 4 [r]. S11

12 1 Title BP1154P Spectrometer Frequency ucleus 31P Figure S7. 31 P MR spectrum of 1-C 4 [r]. 1 Title BP926 4 Spectrometer Frequency ucleus 1H DCM Figure S8. 1 H MR spectrum of 1-C 6 [r]. S12

13 Parameter Value 1 Title BP Spectrometer Frequency ucleus 13C Figure S9. 13 C MR spectrum of 1-C 6 [r]. 1 Title BP1190P 4 Spectrometer Frequency ucleus 31P Figure S P MR spectrum of 1-C 6 [r]. S13

14 1 Title BP924B 4 Spectrometer Frequency ucleus 1H Figure S11. 1 H MR spectrum of 1-C 8 [r]. Parameter Value 1 Title BP924B Spectrometer Frequency ucleus 13C Figure S C MR spectrum of 1-C 8 [r]. S14

15 1 Title BP930 4 Spectrometer Frequency ucleus 31P Figure S P MR spectrum of 1-C 8 [r]. Parameter Value 1 Title BP1308B 4 Spectrometer Frequency ucleus 1H Figure S14. 1 H MR spectrum of 1-C 10 [r]. S15

16 Title BP Solvent MeOD 3 Temperature Spectrometer Frequency ucleus 13C * * * Figure S C MR spectrum of 1-C 10 [r]. Parameter Value Title BP1308C 4 Spectrometer Frequency ucleus 31P Figure S P MR spectrum of 1-C 10 [r]. S16

17 1 Title BP1187B 4 Spectrometer Frequency ucleus 1H O Figure S17. 1 H MR spectrum of 2-C 4 [r]. 1 Title BP1187D Spectrometer Frequency ucleus 13C O Figure S C MR spectrum of 2-C 4 [r]. S17

18 1 Title BP1187P 4 Spectrometer Frequency ucleus 31P O Figure S P MR spectrum of 2-C 4 [r]. 1 Title BP Spectrometer Frequency ucleus 1H O Figure S20. 1 H MR spectrum of 2-C 6 [r]. S18

19 Parameter Value 1 Title BP1153B Spectrometer Frequency ucleus 13C O Figure S C MR spectrum of 2-C 6 [r]. 1 Title BP1153P 4 Spectrometer Frequency ucleus 31P O Figure S P MR spectrum of 2-C 6 [r]. S19

20 1 Title BP Spectrometer Frequency ucleus 1H O Figure S23. 1 H MR spectrum of 2-C 8 [r]. Parameter Value 1 Title BP1152B Spectrometer Frequency ucleus 13C O Figure S C MR spectrum of 2-C 8 [r]. S20

21 1 Title BP1152P 4 Spectrometer Frequency ucleus 31P O Figure S P MR spectrum of 2-C 8 [r] S21