Electronic supplementary information (ESI)

Multinuclear Ni(II), Cu(II) and Zn(II) complexes of chiral macrocyclic nonaazamine

Marta Löffler*, Janusz Gregoliński, Maria Korabik, Tadeusz Lis and Jerzy Lisowski

Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie, 50-383, Wrocław, Poland. E-mail: marta.loffler@chem.uni.wroc.pl

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2016

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CD spectra

Supporting Figure 1S. The CD spectra of the two enantiomeric complexes [Ni3(L)(H2O)2Cl5]Cl in methanol (C = 1∙10-3 M ): [Ni3(R-L)(H2O)2Cl5]Cl (red)/ [Ni3(S-L)(H2O)2Cl5]Cl (blue).

Supporting Figure 2S.The CD spectra of the two enantiomeric complexes [Cu3( L)Cl4]Cl2 in methanol (C = 1∙10-3 M): [Cu3(R- L)Cl4]Cl2 (red)/ [Cu3(S- L)Cl4]Cl2 (blue).

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Supporting Figure 3S.The CD spectra of the two enantiomeric complexes [Zn2(L)Cl2](ZnCl4) in methanol (C = 1∙10-3 M): [Zn2(R-L)Cl2](ZnCl4) (red)/ [Zn2(S-L)Cl2](ZnCl4) (blue).

NMR spectra

Supporting Figure S4. 1H NMR spectrum (500 MHz) of [Ni3(R-L)(H2O)2Cl5]Cl in CD3CN solution.

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Supporting Figure 5S. VT-1H NMR spectra (500 MHz) of [Ni3(R-L)(H2O)2Cl5]Cl in CD3CN solution.

Supporting Figure 6S. 1H NMR spectrum (500 MHz) of [Cu3(R- L)Cl4]Cl2 in D2O solution.

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Supporting Figure 7S. VT- 1H NMR spectra (300 MHz) of [Cu3(R- L)Cl4]Cl2 in D2O solution.

Supporting Figure 8S. 1H NMR spectrum (500 MHz) of [Zn2(R-L)Cl2](ZnCl4) in CDCl3/CD3OD (v/v 2/1) solution.

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Supporting Figure 9S. COSY spectrum (500 MHz, CDCl3/CD3OD v/v 2/1 solution) of [Zn2(R-L)Cl2](ZnCl4) complex.

Supporting Figure 10S. Fragment of COSY spectrum (500 MHz, CDCl3/CD3OD v/v 2/1 solution) of [Zn2(R- L)Cl2](ZnCl4) complex.

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Supporting Figure 11S. Aromatic region of the COSY spectrum(500 MHz, CDCl3/CD3OD v/v 2/1 solution) of [Zn2(R-L)Cl2](ZnCl4) complex.

Supporting Figure 12S. HMQC spectrum (500 MHz, CDCl3/CD3OD v/v 2/1 solution) of [Zn2(R-L)Cl2](ZnCl4) complex.

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Supporting Figure 13S. Fragment of HMQC spectrum (500 MHz, CDCl3/CD3OD v/v 2/1 solution) of [Zn2(R-L)Cl2](ZnCl4) complex.

Supporting Figure 14S. Fragment of HMQC spectrum (500 MHz, CDCl3/CD3OD v/v 2/1 solution) of [Zn2(R-L)Cl2](ZnCl4) complex.

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Supporting Figure 15S. Fragments of 1H NMR spectra (500 MHz) received during the titration of R-L ligand with ZnCl2 in CDCl3/CD3OD solution. Bottom - spectrum of R-L ligand, top - spectrum of [Zn2(R-L)Cl2](ZnCl4) complex. Asterisk denotes the residual solvent signal.

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Supporting Figure 16S. 1H NMR spectra (500 MHz) received during the titration of R-L ligand with ZnCl2 in CDCl3/CD3OD solution.

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Crystallographic data

Supporting Table 1S Selected bond distances and angles for complex [Ni3(R-L)(H2O)2Cl5]Cl·0.4CH3CN·4.2H2O.Bond distances (Å)Ni1∙∙∙Ni2 4.579(2) Ni1-Cl2 2.388 (3) Ni2-N5 2.041 (9) Ni3-Cl1 2.554 (3)Ni1-Cl1 2.745 (3) Ni1-Cl3 2.433 (3) Ni2-N6 2.093 (9) Ni3-N7 2.163 (9)Ni1-N1 2.098 (1) Ni2∙∙∙Ni3 4.468(3) Ni2-Cl4 2.374 (3) Ni3-N8 2.096 (8)Ni1-N2 2.034 (9) Ni2-Cl1 2.642 (3) Ni2-O1W 2.109 (7) Ni3-N9 2.094 (9)Ni1-N3 2.083 (8) Ni2-N4 2.133 (9) Ni3∙∙∙Ni1 4.496(2) Ni3-Cl5 2.394 (4)

Ni3-O2W 2.086 (7)Bond angles (°)Ni1-Cl1-Ni2 116.45 (11) N3-Ni1-Cl1 80.9 (2) N6-Ni2-O1W 95.0 (3) N8-Ni3-Cl1 166.6 (3)N1-Ni1-Cl1 113.1 (3) Cl2-Ni1-Cl3 165.74 (12) N6-Ni2-N4 162.3 (4) N9-Ni3-N8 82.6 (4)N1-Ni1-Cl2 86.3 (2) Cl2-Ni1-Cl1 83.72 (11) N6-Ni2-Cl4 93.5 (2) N9-Ni3-N7 161.7 (3)N1-Ni1-Cl3 87.0 (3) Cl3-Ni1-Cl1 87.34 (11) N6-Ni2-Cl1 85.6 (3) N9-Ni3-Cl5 98.0 (3)N2-Ni1-N3 83.9 (3) Ni2-Cl1-Ni3 118.62 (12) Cl4-Ni2-Cl1 87.57 (10) N9-Ni3-Cl1 85.5 (3)N2-Ni1-N1 82.0 (4) N4-Ni2-Cl4 88.5 (2) O1W-Ni2-N4 86.6 (3) O2W-Ni3-Cl1 77.9 (2)N2-Ni1-Cl2 96.6 (3) N4-Ni2-Cl1 112.2 (3) O1W-Ni2-Cl1 82.36 (19) O2W-Ni3-Cl5 164.0 (2)N2-Ni1-Cl3 94.9 (3) N5-Ni2-N6 82.5 (3) Ni3-Cl1-Ni1 116.05 (11) O2W-Ni3-N7 88.4 (3)N2-Ni1-Cl1 164.9 (3) N5-Ni2-O1W 97.9 (3) N7-Ni3-Cl1 112.0 (3) O2W-Ni3-N8 96.1 (4)N3-Ni1-N1 165.8 (4) N5-Ni2-N4 79.7 (4) N7-Ni3-Cl5 88.1 (3) O2W-Ni3-N9 90.1 (3)N3-Ni1-Cl2 93.8 (3) N5-Ni2-Cl4 93.9 (3) N8-Ni3-N7 79.4 (4) Cl5-Ni3-Cl1 89.00 (12)N3-Ni1-Cl3 95.8 (3) N5-Ni2-Cl1 168.1 (2) N8-Ni3-Cl5 98.6 (3) N8-Ni3-Cl1 166.6 (3)

Supporting Table 2S Selected bond distances and angles for complex [Cu3(R-L)Cl4]Cl2·CH3CN·7.5(H2O).

Bond distances (Å)Cu1∙∙∙Cu2 3.970(3) Cu1-Cl2 2.323 (2) Cu2-N6 2.040 (4) Cu3-N8 2.004 (4)Cu1-Cl1 2.345 (2) Cu2∙∙∙Cu3 4.424(2) Cu2-Cl3 2.271 (2) Cu3-N9 2.004 (4)Cu1-N1 2.345 (2) Cu2-Cl1 2.675 (1) Cu3∙∙∙Cu1 4.358(2) Cu3-Cl4 2.463 (1)Cu1-N2 1.990 (4) Cu2-N4 2.061 (4) Cu3-Cl1 2.438(1)Cu1-N3 2.051 (4) Cu2-N5 1.995 (4) Cu3-N7 1.998 (4)

Bond angles (°)Cu1-Cl1-Cu2 104.37 (5) Cl2-Cu1-N1 102.20 (10) N5-Cu2-Cl3 152.02 (13) N7-Cu3-N8 82.36 (16)N2-Cu1-N3 83.66 (15) Cl2-Cu1-Cl1 93.39 (5) N5-Cu2-Cl1 106.11 (12) N7-Cu3-Cl1 97.29 (11)N2-Cu1-Cl2 94.06 (12) Cl1-Cu1-N1 99.76 (9) N6-Cu2-N4 163.24 (16) N7-Cu3-Cl4 99.48 (11)N2-Cu1-Cl1 172.42 (12) Cu2-Cl1-Cu3 119.77 (5) N6-Cu2-Cl3 98.80 (11) N8-Cu3-Cl1 154.74

(12)N2-Cu1-N1 77.27 (14) N4-Cu2-Cl3 95.37 (11) N6-Cu2-Cl1 89.35 (12) N8-Cu3-Cl4 99.83 (12)N3-Cu1-Cl2 138.37 (12) N4-Cu2-Cl1 96.50 (12) Cl3-Cu2-Cl1 101.76 (5) N9-Cu3-N8 86.13 (16)N3-Cu1-Cl1 91.70 (11) N5-Cu2-N6 84.07 (16) Cu3-Cl1-Cu1 131.30 (6) N9-Cu3-Cl1 88.16 (11)N3-Cu1-N1 117.55 (15) N5-Cu2-N4 79.22 (16) N7-Cu3-N9 163.58 (16) N9-Cu3-Cl4 93.97 (11)

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Supporting Table 3S Selected bond distances and angles for complex [Zn2(R- L)Cl2](ZnCl4)· CHCl3·0.8CH3OH·3.7H2O.Bond distances (Å)Zn1-Cl1 2.287 (2) Zn1-N8 2.196 (7) Zn2-N2 2.091 (7) Zn2-N4 2.046 (7)Zn1-N6 2.213 (6) Zn1-N9 2.080 (7) Zn2-N3 2.208 (8) Zn2-N5 2.306 (7)Zn1-N7 2.068 (7) Zn2-Cl2 2.305 (3)Bond angles (°)N7-Zn1-N9 147.7 (3) N8-Zn1-N6 144.9 (3) N2-Zn2-N3 82.4 (3) N3-Zn2-Cl2 97.7 (2)N7-Zn1-N8 77.7 (3) N7-Zn1-Cl1 106.42 (19) N2-Zn2-Cl2 114.3 (2) N4-Zn2-N5 76.2 (3)N9-Zn1-N8 85.1 (3) N9-Zn1-Cl1 103.50 (18) N4-Zn2-N2 133.3 (3) N2-Zn2-N5 105.7 (3)N7-Zn1-N6 74.4 (3) N8-Zn1-Cl1 100.57 (18) N4-Zn2-N3 78.9 (3) N3-Zn2-N5 151.9 (3)N9-Zn1-N6 108.0 (2) N6-Zn1-Cl1 107.31 (18) N4-Zn2-Cl2 110.3 (2) Cl2-Zn2-N5 102.96 (19)

Supporting Figure 17S. The comparison of macrocyle conformation and metal ion positions in protonated R-L and trinuclear complexes [Cu3(R- L)(-OH)2]Cl2(ClO4)2, [Cu3(R- L)Cl4]Cl2, [Ni3(R-L)(H2O)2Cl5]Cl, and [Zn2(R-L)Cl2](ZnCl4), respectively.

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Supporting Figure 18S. Very week intermolecular H-bonds for complex [Ni3(R-L)(H2O)2Cl5]Cl·0.4CH3CN·4.2H2O between nitrogen atom of macrocyclic ligand and terminal chloride atom [N8∙∙∙Cl3` 3.696 Å; N8-H8∙∙∙Cl3` 169.6°; -x+1, y-1/2, -z+3/2 ] which forms 1D zig-zag polymer. The shortest intermolecular distance between two nickel atoms of adjacent molecules is equal to 6.709(6) Å for Ni3-Ni1`.

Supporting Figure 19S. Intermolecular H-bonds for complex [Cu3(R-L)Cl4]Cl2·CH3CN·7.5(H2O) between nitrogen atoms of macrocyclic ligand and chloride atoms [N2∙∙∙Cl4` 3.215 Å; N2-H2∙∙∙Cl4` 169.13°; -x+3/2, -y+1, z+1/2 and N8∙∙∙Cl2` 3.499 Å; N8-H8∙∙∙Cl2` 163.19°; -x+3/2, -y+1, z+1/2] which forms 1D polymer. The shortest intermolecular distance between two copper atoms of adjacent molecules is equal to 5.846(4) Å for Cu1-Cu3`[x+3/2, -y+1, z+1/2 ].

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MS spectra

Supporting Figure 20S. ESI MS spectra of [Ni3(R-L)(H2O)2Cl5]Cl.

Supporting Figure 21S. ESI MS spectra of [Cu3(R- L)Cl4]Cl2.

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Supporting Figure 22S. ESI MS spectra of [Zn2(R-L)Cl2](ZnCl4).