Electronic Supplementary Information

Unusual Chemistry of Cu(II) Salan Complexes: Synthesis, Characterization and

Superoxide Dismutase Activity

Satabdi Roy,a Atanu Banerjee,a Sudhir Lima,a Adolfo Horn Jr.,b,c Raquel M. S. N. Sampaio,b Nádia Ribeiro,d Isabel

Correia,d Fernando Avecilla,e M. Fernanda N. N. Carvalho,d Maxim L. Kuznetsov,d João Costa Pessoa*d Werner

Kaminsky f and Rupam Dinda*a

a Department of Chemistry, National Institute of Technology, Rourkela 769008, Odisha, India.b Laboratório de Ciências Químicas, Universidade Estadual do Norte Fluminense Darcy Ribeiro, 28013-602, Campos do Goytacazes, RJ, Brazil.c Universidade Federal de Santa Catarina, Campus Universitário Trindade, 88040-900 Florianópolis, SC, Brazil.d Centro de Química Estrutural and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, 1049-001,

Lisboa, Portugale Grupo Xenomar, Centro de Investigacións Científicas Avanzadas (CICA), Departamento de Química, Facultade de Ciencias, Universidade da Coruña, Campus de A

Coruña, 15071A Coruña, Spain.f Department of Chemistry, University of Washington, Seattle, Washington 98195, United States

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2020

Electronic spectral data for complexes

Table S1 Electronic spectral data for complexes 1-4 in DMSO.

Complexes λmax/nm (ε/M–1 cm–1)

1 296 (15109), 352 (2121), 424 (2445), 609 (657)

2 286 (23121), 344 (2023), 424 (2788), 613 (589)

3 295 (20338), 397 (1555), 429 (2223), 605 (770)

4 294 (11384), 371 (1563), 419 (2312), 601 (431)

Supplementary single crystal X-ray diffraction data.

Table S2(a) Selected bond parameters in H2L3.

Bond lengths (Å)

O(1)-C(10) 1.367(2) N(1)-C(4) 1.485(3)

O(2)-C(21) 1.367(2) N(1)-C(3) 1.461(2)

N(2)-C(25) 1.468(3) N(2)-C(3) 1.465(2)

Bond angles (°)

N(1)-C(3)-N(2) 104.44(15) N(2)-Cu(1)-O(2) 92.2(2)

Table S2(b) Intramolecular hydrogen bonds in compound H2L3.

D-H...A d(D-H) d(H...A) d(D...A) <(DHA)

O(1)-H(1O)...N(1) 0.84(3) 1.83(3) 2.615(2) 155(3)

O(2)-H(2O)...N(2) 0.90(3) 1.80(3) 2.628(2) 153(3)

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Table S3 Selected geometric parameters (Å, °) for the Cu-complexes 1A, 3 and 4

[Cu(L1)(DMSO)] (1A)

Bond lengths (Å)

N(1)-Cu(1) 2.054(7) N(2)-Cu(1) 2.047(5)

O(1)-Cu(1) 1.863(5) O(2)-Cu(1) 1.901(5)

O(3)-Cu(1) 2.41(1)

Bond angles (°)

N(1)-Cu(1)-N(2) 86.0(3) N(2)-Cu(1)-O(2) 92.2(2)

N(1)-Cu(1)-O(1) 91.3(2) N(2)-Cu(1)-O(3) 89.7(3)

N(1)-Cu(1)-O(2) 162.8(2) O(1)-Cu(1)-O(2) 88.2(2)

N(1)-Cu(1)-O(3) 97.3(3) O(1)-Cu(1)-O(3) 98.1(3)

N(2)-Cu(1)-O(1) 172.0(2) O(2)-Cu(1)-O(3) 99.8(3)

N(1)-Cu(1)-N(2) 86.0(3) N(2)-Cu(1)-O(2) 92.2(2)

[Cu(L3A)]2 (3)

Bond lengths (Å)

O(1)-Cu(1) 1.971(8) N(1)-Cu(1) 1.968(10)

O(2)-Cu(1) 1.909(8) N(2)-Cu(1) 2.042(9)

O(1i)-Cu(1) 2.786(10) O(3)-Cu(1) 2.544(9)

Cu(1)-Cu(1i) 3.732(4) Cu(2)-Cu(2i) 3.381(3)

Bond angles (°)

O(2)-Cu(1)-N(1) 151.5(4) O(2)-Cu(1)-O(1) 100.2(3)

N(1)-Cu(1)-O(1) 91.3(4) O(2)-Cu(1)-N(2) 91.9(4)

N(1)-Cu(1)-N(2) 86.2(4) O(1)-Cu(1)-N(2) 158.7(4)

[Cu(L4A)] (4)

Bond lengths (Å)

N(2)-Cu(1) 2.002(2) O(2)-Cu(1) 1.896(3)

N(1)-Cu(1) 2.052(3) O(1)-Cu(1) 1.878(2)

Bond angles (°)

N(2)-Cu(1)-N(1) 85.8(1) N(1)-Cu(1)-O(2) 173.4(1)

N(2)-Cu(1)-O(2) 92.9(1) N(1)-Cu(1)-O(1) 93.2(1)

N(2)-Cu(1)-O(1) 170.2(1) O(2)-Cu(1)-O(1) 89.1(1)

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1H and 13C NMR spectra of ligand precursor

Fig. S1 1H NMR (A) and 13C NMR (B) spectrum of H2L3 in CDCl3 (* marks the solvent signal).

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A

B

ESI-MS spectra

SR-1 #155-338 RT: 0.85-1.85 AV: 184 NL: 9.13E4F: ITMS - c ESI Full ms [100.00-1000.00]

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z

0

5

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Rel

ativ

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bund

ance

477.47

512.93

281.69

802.24539.61 566.41183.39 955.39672.72325.51 774.14225.33149.21 612.63 742.19465.64 978.97848.98265.55 882.78347.50 414.28 917.97

Fig. S2(a) ESI-MS spectrum of H2L3 in the negative ion mode (MeOH solution).

SR-1 #10-119 RT: 0.05-0.65 AV: 110 NL: 8.45E4F: ITMS + c ESI Full ms [100.00-1000.00]

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z

0

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Rel

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479.17

283.15 327.00

500.80212.21106.92 190.89

295.15 584.48138.64 388.82 723.94516.70353.18 445.22271.20 619.15 677.01 994.42954.92855.72769.16 802.19 912.79

Fig. S2(b) ESI-MS spectrum of H2L3 in the positive ion mode (MeOH solution).

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O

O

N N

O

O

Cu

O

O

N N

O

O

Cu

H+

Exact mass (2M+H+) = 1003.37

Fig. S3 Proposed molecular formulae for species found in the ESI-MS spectrum of 2.

.

O

O

N N

O

O

Cu

N

N O

O

Cu

Exact mass = 827.29

H+

Fig. S4 Proposed molecular formulae for deaminated species found in the ESI-MS spectrum of 2.

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NR_L2 #9-192 RT: 0.05-1.11 AV: 184 NL: 1.80E5F: ITMS + c ESI Full ms [50.00-1100.00]

100 200 300 400 500 600 700 800 900 1000 1100m/z

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827.31

766.03

1002.89

441.31

941.52

102.00 813.23502.18 990.96265.27 708.89 1024.68884.56403.85326.25 602.75522.41 973.00 1088.99664.2273.91 455.31234.24177.17116.90

Fig. S5 ESI-MS spectrum of 2 in the positive ion mode (MeOH solution).

SA-1 #322-485 RT: 1.92-2.82 AV: 164 NL: 1.72E4F: ITMS + c ESI Full ms [100.00-1000.00]

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z

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572.06

190.83106.90

212.17

415.77 528.09 594.11138.52 613.45

655.32180.06 479.21 784.78283.16229.89 904.95332.17 431.47389.49 686.84501.02 840.85 950.87741.09 988.74

Fig. S6 ESI-MS spectrum of 3 in the positive ion mode (MeOH solution).

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Fig. S7 First derivative EPR spectra of frozen solutions of the Cu-complexes 1-4 in DMF (ca. 3 mM), measured at ca. 100 K.

Fig S8 X-band EPR spectrum of 4 evidencing the superhyperfine structure in the perpendicular region resulting from spin-

coupling of the unpaired electron with two 14N nuclei.

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Additional Electrochemical data

a)

b)

Fig. S9 Cyclic voltammogram of complex 1. (a) anodic scan; (b) cathodic scan. The cyclic

voltammograms were obtained in NBu4BF4/DMF (0.1 M) at 200 mV/s.

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a)

b)

Fig. S10 Cyclic voltammogram of complex 2. (a) anodic scan; (b) cathodic scan. The cyclic

voltammograms were obtained in NBu4BF4/DMF (0.1M) at 200 mV/s.

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a)

b)

Fig. S11 Cyclic voltammogram of complex 3. (a) anodic scan; (b) cathodic scan. The cyclic

voltammograms were obtained in NBu4BF4/DMF (0.1M) at 200 mV/s.

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a)

b)

Fig. S12 Cyclic voltammogram of complex 4. (a) anodic scan; (b) cathodic scan. The cyclic

voltammograms were obtained in NBu4BF4/DMF (0.1M) at 200 mV/s.

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Fig. S13 ORTEP diagram of [Cu(L3A)]2 (3) showing the weak interactions 50% probability level (Bond distance, Cu(1)-Cu(1i)= 3.732(4) Å)

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Evaluation of Superoxide dismutase activity

Fig. S14 Plot of V/v vs. complex concentration of [CuL1] (1) employed for IC50 calculation. V/v is the ratio between the NBT

reduction rate in the absence (V) and in the presence (v) of different concentration of complex 1. The IC50 is the value at V/v =

2.

Fig. S15 Plot of V/v vs. complex concentration of [(CuL3A)]2 (3) employed for IC50 calculation. V/v is the ratio between the NBT

reduction rate in the absence (V) and in the presence (v) of different concentration of complex 3. The IC50 is the value at V/v =

2.

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