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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
(S1) Gaussian 09, Revision C.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E.
Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.
A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J.
Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J.
Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A.
Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K.
N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari,
A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam,
M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts,
R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R.
L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J.
Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J.
Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2010.