S1

Electronic Supplementary Information

Title:

Efficient synthetic method for organometallic radicals: Structures and properties of gold(I)–

(nitronyl nitroxide)-2-ide complexes

Authors:

Shuichi Suzuki,*ab Sayaka Kira,a Masatoshi Kozaki,a Masaki Yamamura,c Toru Hasegawa,c

Tatsuya Nabeshima,c Keiji Okada*a

Affiliation: aGraduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, Osaka 558-8585,

Japan bGraduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531,

Japan cGraduate School of Pure and Applied Sciences and Tsukuba Research Center for

Interdisciplinary Materials Science (TIMS), University of Tsukuba, 1-1-1, Tennodai, Tsukuba,

Ibaraki 305-8571, Japan

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017

S2

Table of Contents

UV-vis spectra of NN-Au-P complexes (Fig. S1–4) p. S3−S4

MO-interaction diagram of transition 1, 2 for NN-Au-1 (Fig. S5) p. S5

MO-interaction diagram of transition 1, 2 for NN-Au-4 (Fig. S6) p. S6

MO-transitions 1,2 contributing for the longest absorption of NN-H (Fig. S7) p. S7

ESR spectra of NN-Au-P complexes (Fig. S8–S12) p. S8–S10

Calculated spin density distribution of NN-Au-P complexes (Fig. S13) p. S11

Cyclic voltammograms of NN-Au-P complexes (Fig. S14) p. S12

Reference p. S13

S3

Fig. S1. Absorption spectrum of NN-Au-2 in CH2Cl2.

Fig. S2. Absorption spectrum of NN-Au-3 in CH2Cl2.

300 400 500 600 700Wavelength / nm

0

0.5

1ε

/ 104

M–1

cm

–1

300 400 500 600 700Wavelength / nm

0

0.5

1

ε / 1

04 M

–1 c

m–1

S4

Fig. S3. Absorption spectrum of NN-Au-5 in CH2Cl2.

Fig. S4. Absorption spectrum of NN-Au-6 in CH2Cl2.

300 400 500 600 700Wavelength / nm

0

0.5

1

ε / 1

04 M

–1 c

m–1

300 400 500 600 700Wavelength / nm

0

0.5

1

ε / 1

04 M

–1 c

m–1

S5

Fig. S5. MO-interaction diagram for NN-Au-1.S1 a) for α-orbitals, b) for β-orbitals.

S6

Fig. S6. MO-interaction diagram for NN-Au-4.S1 a) for α-orbitals, b) for β-orbitals.

S7

Fig. S7. MO-transitions 1,2 contributing for the longest absorption of NN-H.S1 The calculated longest wavelength and the transition coefficients were as follows: NN-H (43 α-orbitals and 42 β-orbitals), 447.2 nm (f = 0.01), transition 1: 43α → 44α (c = 0.556), 42β → 43β (c = 0.669). For the strong absorption around 300 nm was calculated: 283.1 nm (f = 0.24), 43α → 44α (c = 0.741), 42β → 43β (c = -0.647).

S8

Fig. S8. Observed (in CH2Cl2: solid line) and simulated (red dashed line) ESR spectra of

NN-Au-1.

Fig. S9. Observed (in CH2Cl2: solid line) and simulated (red dashed line) ESR spectra of

NN-Au-3.

329 330 331 332 333 334Magnetic Field / mT

330 331 332 333 334 335Magnetic Field / mT

S9

Fig. S10. Observed (in CH2Cl2: solid line) and simulated (red dashed line) ESR spectra of

NN-Au-4.

Fig. S11. Observed (in CH2Cl2: solid line) and simulated (red dashed line) ESR spectra of

NN-Au-5.

330 331 332 333 334 335Magnetic Field / mT

330 331 332 333 334 335Magnetic Field / mT

S10

Fig. S12. Observed (in CH2Cl2: solid line) and simulated (red dashed line) ESR spectra of

NN-Au-6.

330 331 332 333 334 335Magnetic Field / mT

S11

Fig. S13. Spin density distributions of (a) NN-Au-1 (b) NN-Au-2 (c) NN-Au-3, (d) NN-Au-4,

(e) NN-Au-5, and (f) NN-Au-6 calculated by Gaussian 09 using at the UB3PW91 level of

theory with 6-31G(d) basis set for C, H, N, O, P, and S atoms, and LANLSDZ basis set for

Au atom.S1

S12

Fig. S14. Cyclic voltammograms of (a) NN-Au-1, (b) NN-Au-2, (c) NN-Au-3, (d) NN-Au-4,

and (e) NN-Au-6 in 1,2-dichloroethane.

V vs Fc/Fc++0.4 +0.2 0 –0.2 –0.4

a)

b)

c)

d)

e)

S13

Reference

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