Luminescent and Proton Conducting. Lanthanide Coordination Networks Based. on a Zwitterionic Tripodal Triphosphonate

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1 Supporting information For Luminescent and Proton Conducting Lanthanide Coordination Networks Based on a Zwitterionic Tripodal Triphosphonate Montse Bazaga-García, Giasemi K. Angeli, Konstantinos E. Papathanasiou, Inés R. Salcedo, Pascual Olivera-Pastor, Enrique R. Losilla, Duane Choquesillo-Lazarte, Gary B. Hix, Aurelio Cabeza,, * and Konstantinos D. Demadis,* Crystal Engineering, Growth and Design Laboratory, Department of Chemistry, University of Crete, Voutes Campus, Crete, GR-71003, Greece Universidad de Málaga, Departamento de Química Inorgánica, Campus Teatinos s/n Málaga, Spain Laboratorio de Estudios Cristalográficos, IACT-CSIC, Granada, Spain School of Science and Technology, Nottingham Trent University, Clifton Lane, Nottingham, NG11 8NS, United Kingdom 1

2 TABLE OF CONTENTS: Figures: S1. Rietveld plot for [Ce 2(H 3NMP) 2(H 2O) ].H 2O. S2. Rietveld plot for [Sm(H NMP)(H 2O) 2]Cl 2H 2O. S3. Rietveld plot for [Eu(H NMP)(H 2O) 2]Cl 2H 2O. S. Rietveld plot for [Gd(H NMP)(H 2O) 2]Cl 2H 2O. S. Rietveld plot for [Tb(H NMP)(H 2O) 2]Cl 2H 2O. S. Rietveld plot for [Dy(H NMP)(H 2O) 2]Cl 2H 2O. S7. Extended hydrogen bonding interactions observed in the crystal structure of [Ce 2(H 3NMP) 2(H 2O) ].H 2O. S8. TG-MS curves for [Gd(H NMP)(H 2O) 2]Cl 2H 2O and H 2O (m/z = 18). S9. TG-MS curves for [Gd(H NMP)(H 2O) 2]Cl 2H 2O and HCl (m/z = 3). S10. TGA curves for [Ce 2(H 3NM) 2(H 2O) ].H 2O as-synthesized (blue) and post-impedance analysis (red). S11. Variation of unit cell parameters and volume with the temperature for [Sm- (H NMP)(H 2O) 2]Cl. 2H 2O. (open and fill symbols stand for decreasing and increasing temperatures respectively). S12. Rietveld plot for [Sm(H NMP)(H 2O)]Cl at 120 C and 10% RH. The inset shows the coordination environment around Sm 3+ ions in [Sm(H NMP)(H 2O)]Cl. S13. Le Bail fit for [La 2(H 3NMP) 2(H 2O) ].H 2O obtained by exposing [La(H NMP)(H 2O) 2]Cl 2H 2O at 80 ºC and 9% RH for 30 h. S1. Powder XRD patterns for [Ce 2(H 3NMP) 2(H 2O) ].H 2O at: (a) 2 C and 0% RH; (b) 80 C and 9% RH after 1 h; and (c) 80 C and 9% RH after 18 h. S1. TGA curves of [Gd(H NMP)(H 2O) 2]Cl 2H 2O as-synthesized (blue) and post-impedance (red). S1. Complex impedance plane plots at 2 ºC and 70 ºC (9% RH) for (a) [Gd(H NMP)(H 2O) 2]Cl 2H 2O and (b) [Ce 2(H 3NMP) 2(H 2O) ].H 2O. S17. (a) UV-visible absorption and (b) emission spectra of Sm-H NMPCl. S18. Emission spectrum for Eu-H NMPCl. S19. UV-visible absorption spectrum for Gd-H NMPCl. S20. (a) UV-visible absorption and (b) emission spectra for Dy-H NMPCl. 2

3 S21. UV-visible absorption spectrum for Ho-H NMPCl. Tables: S1. Selected bond distances (Å) for Ln-H NMPCl, (Ln= La, Pr, Sm, Eu, Gd, Tb, Dy and Ho) and Ce-H 3NMP. S2. H-bond interactions (Å) for [Ce 2(H 3NMP) 2(H 2O) ].H 2O. S3. Absorption and emission bands observed for [Pr(H NMP)(H 2O) 2]Cl 2H 2O. S. Absorption and emission bands observed for [Sm(H NMP)(H 2O) 2]Cl 2H 2O. S. Absorption and Emission bands observed for [Eu(H NMP)(H 2O) 2]Cl 2H 2O. S. Absorption and emission bands observed for [Tb(H NMP)(H 2O) 2]Cl 2H 2O. S7. Absorption and emission bands observed for [Dy(H NMP)(H 2O) 2]Cl 2H 2O. S8. Absorption and emission bands observed for [Ho(H NMP)(H 2O) 2]Cl 2H 2O. 3

4 Figure S1. Rietveld plot for [Ce 2(H 3NMP) 2(H 2O) ].H 2O. Experimental data (red scatters); the best-fit profile (upper trace) and the difference pattern (lower trace) are drawn as solid green and magenta lines, respectively. Black vertical bars indicate the angular positions of the allowed Bragg reflections. Figure S2. Rietveld plot for [Sm(H NMP)(H 2O) 2]Cl 2H 2O. Experimental data (red scatters); the best-fit profile (upper trace) and the difference pattern (lower trace) are drawn as solid green and magenta lines, respectively. Black vertical bars indicate the angular positions of the allowed Bragg reflections.

5 Figure S3. Rietveld plot for [Eu(H NMP)(H 2O) 2]Cl 2H 2O Experimental data (red scatters); the best-fit profile (upper trace) and the difference pattern (lower trace) are drawn as solid green and magenta lines, respectively. Black vertical bars indicate the angular positions of the allowed Bragg reflections. Figure S. Rietveld plot for [Gd(H NMP)(H 2O) 2]Cl 2H 2O Experimental data (red scatters); the best-fit profile (upper trace) and the difference pattern (lower trace) are drawn as solid green and magenta lines, respectively. Black vertical bars indicate the angular positions of the allowed Bragg reflections.

6 Figure S. Rietveld plot for [Tb(H NMP)(H 2O) 2]Cl 2H 2O Experimental data (red scatters); the best-fit profile (upper trace) and the difference pattern (lower trace) are drawn as solid green and magenta lines, respectively. Black vertical bars indicate the angular positions of the allowed Bragg reflections. Figure S. Rietveld plot for [Dy(H NMP)(H 2O) 2]Cl 2H 2O. Experimental data (red scatters); the best-fit profile (upper trace) and the difference pattern (lower trace) are drawn as solid green and magenta lines, respectively. Black vertical bars indicate the angular positions of the allowed Bragg reflections.

7 Figure S7. Extended hydrogen bonding interactions observed in the crystal structure of [Ce 2(H 3NMP) 2(H 2O) ].H 2O. 7

8 Figure S8. TG-MS curves for [Gd(H NMP)(H 2O) 2]Cl 2H 2O and H 2O (m/z = 18). Figure S9. TG-MS curves for [Gd(H NMP)(H 2O) 2]Cl 2H 2O and HCl (m/z = 3). 8

9 % Ce-AMP (1D) as-syn Ce-AMP post-imped Weight (%) % % Temperature (ºC) Figure S10. TGA curves for [Ce 2(H 3NM) 2(H 2O) ].H 2O as-synthesized (blue) and postimpedance analysis (red). 18,0 17,9 V ,8 17,7 b 120 Å 17, 100 V (Å) a , , Temperature (ºC) Figure S11. Variation of unit cell parameters and volume with the temperature for [Sm(H NMP)(H 2O) 2]Cl 2H 2O (open and filled symbols denote decreasing and increasing temperatures, respectively). 9

10 Figures S12. Rietveld plot of [Sm(H NMP)(H 2O)]Cl heated at 120 C and 10% RH. The powder pattern was collected using Mo K 1 radiation ( = Å). The inset shows the coordination environment around Sm 3+ in [Sm(H NMP)(H 2O)]Cl. Selected crystallographic data: a= 11.12(2) Å; b= 17.3() Å; c= 8.10(1) Å; = 11.13(8) ; V= 120.(7) Å 3 ; s.g. C c; R WP= ; R P= 0.078; R F= Figure S13. Le Bail fit for [La 2(H 3NMP) 2(H 2O) ].H 2O obtained by exposing [La(H NMP)(H 2O) 2]Cl. 2H 2O at 80 ºC and 9% RH for 30 h. 10

11 Figure S1. Powder XRD patterns for [Ce 2(H 3NMP) 2(H 2O) ].H 2O at: (a) 2 C and 0% RH; (b) 80 C and 9% RH after 1 h; and (c) 80 C and 9 % RH after 18 h Gd-AMP post-im Gd-AMP as-syn Weight (%) % 2.71% Temperature (ºC) Figure S1. TGA curves of [Gd(H NMP)(H 2O) 2]Cl 2H 2O as-synthesized (blue) and postimpedance (red). 11

12 3.0x10 2x10 2 ᵒC Cp=1.3 x 10-8 (F cm -1 ) 70 ᵒC Z" ( cm) 1.x10 Cp=1. x (F cm -1 ) Z" ( cm) 1x x10 3.0x10 Z' ( cm) 0 0 1x10 2x10 Z' ( cm) x10 3.0x10 2 ᵒC 70 ᵒC Z" ( cm) 3x10 Z" ( cm) 1.x10 Cp=1.2 x 10-8 (F cm -1 ) Cp=1. x (F cm -1 ) 0 0 3x10 x10 Z' ( cm) x10 3.0x10 Z' ( cm) Figure S1. Complex impedance plane plots at 2 and 70 ºC (9% RH) for (a) [Gd(H NMP)(H 2O) 2]Cl 2H 2O and (b) [Ce 2(H 3NMP) 2(H 2O) ].H 2O. 12

13 Abs. / arbitrary units Abs. / arbitrary units (a) 0, (b) 0, 0,3 0,3 0,2 G /2 H /2 G /2 H 7/2 G /2 H 9/2 0,2 0,1 0,1 0, / nm / nm Figure S17. (a) UV-visible absorption and (b) emission spectra for Sm-H NMPCl. Eu-HNMPCl exc = 3 nm D 0 7 F 3 D 0 7 F 2 D 0 7 F 1 L 7 F 0 D 0 7 F 0 D 1 7 F Figure S18. Emission spectrum for Eu-H NMPCl. 13

14 Abs. 0,3 0,3 0,2 0,2 0,1 0,1 0, / nm Figure S19. UV-visible absorption spectrum for Gd-H NMPCl. F 9/2 H 13/2 F 9/2 H 1/2 F 9/2 H 11/2 Figure S20. (a) UV-visible absorption and (b) emission spectra for Dy-H NMPCl. 1

15 Abs. 0, 0, 0,3 0,2 0, / nm Figure S21. UV-visible absorption spectrum for Ho-H NMPCl. 1

16 Table S1. Selected bond distances (Å) for Ln-H NMPCl, (Ln= La, Pr, Sm, Eu, Gd, Tb, Dy and Ho) and Ce-H 3NMP. [La(H NMP)(H 2O) 2]Cl 2H 2O Length (Å) Length (Å) Length (Å) La1-O8 2.39(2) P2-O (3) P-O (2) La1-O20 2.8(2) P2-O (2) P-O (2) La1-O10 2.(3) P2-O2 1.89(2) P-O (3) La1- O (2) P2-C () P-C (3) La1-O11 2.8(2) P3-O20 1.9(2) N9-C () La1-O (2) P3-O8 1.9(2) N9-C () La1-O1 2.9(3) P3-O1 1.70(3) N9-C22 1.2() La1-O 2.9(3) P3-C (3) [Ce 2(H 3NMP) 2(H 2O) ].H 2O Length (Å) Length (Å) Length (Å) Ce1-O1w 2.08(3) P1-O1 1.2() P-O () Ce1-O2w 2.832(3) P1-O2 1.33() P-O1 1.() Ce1-O1 2.30(1) P1-O3 1.3() P-O1 1.39() Ce1-O 2.89(2) P1-C () P-C 1.810() Ce1-O10 2.9(2) P2-O 1.39() P-O1 1.() Ce1-O (2) P2-O 1.3() P-O () Ce1-O (2) P2-O 1.() P-O18 1.2() Ce1-O1 2.77(2) P2-C () P-C 1.80() Ce1-O1 2.(1) P3-O7 1.0() N1-C1 1.07() Ce2-O3w 2.8(3) P3-O8 1.33() N1-C2 1.9() Ce2-Ow 2.27(3) P3-O9 1.0() N1-C3 1.07() Ce2-O 2.713(2) P3-C () N2-C 1.03() Ce2-O 2.729(2) P-O10 1.3() N2-C 1.01() Ce2-O 2.37(2) P-O11 1.3() N2-C 1.09() Ce2-O7 2.97(2) P-O12 1.8() Ce2-O8 2.33(2) P-C 1.80() Ce2-O13 2.0(1) Ce2-O1 2.0(1) [Pr(H NMP)(H 2O) 2]Cl 2H 2O Length (Å) Length (Å) Length (Å) Pr1-O8 2.39(8) P2-O19 1.9(9) P-O13 1.8(9) Pr1-O (9) P2-O10 1.0(11) P-O11 1.9(9) Pr1-O10 2.2(1) P2-O2 1.8(9) P-O12 1.8(9) Pr1-O19 2.(8) P2-C (13) P-C18 1.8(12) Pr1-O11 2.0(8) P3-O (10) N9-C (1) Pr1-O13 2.7(8) P3-O8 1.88(9) N9-C22 1.0(1) Pr1-O1 2.8(1) P3-O1 1.72(11) N9-C (1) Pr1-O 2.10(1) P3-C (12) 1

17 Table S1(cont.). Selected bond distances (Å) for Ln-H NMPCl, (Ln= La, Pr, Sm, Eu, Gd, Tb, Dy and Ho) and Ce-H 3NMP. [Sm(H NMP)(H 2O) 2]Cl 2H 2O Length (Å) Length (Å) Length (Å) Sm-O1 2.01(1) P1-O1 1.3() P3-O7 1.0() Sm-O3 2.1(2) P1-O2 1.31() P3-O8 1.33() Sm-O 2.73(2) P1-O3 1.1() P3-O9 1.() Sm-O 2.81(1) P1-C () P3-C3 1.80() Sm-O7 2.31(2) P2-O 1.3() C1-N1 1.19() Sm-O (2) P2-O 1.39() C2-N1 1.03() Sm-Ow1 2.90(1) P2-O 1.32() C3-N1 1.2() Sm-Ow2 2.3(9) P2-C2 1.80() [Eu(H NMP)(H 2O) 2]Cl 2H 2O Length (Å) Length (Å) Length (Å) Eu-O1 2.19(11) P1-O1 1.28() P3-O7 1.39() Eu-O3 2.29(12) P1-O2 1.37() P3-O8 1.2() Eu-O 2.01(12) P1-O3 1.1() P3-O9 1.32() Eu-O 2.2(9) P1-C () P3-C () Eu-O7 2.02(9) P2-O 1.3(1) C1-N1 1.11() Eu-O (1) P2-O 1.3() C2-N1 1.02() Eu-Ow1 2.7(7) P2-O 1.38() C3-N1 1.9() Eu-Ow2 2.80(7) P2-C () [Gd(H NMP)(H 2O) 2]Cl 2H 2O Length (Å) Length (Å) Length (Å) Gd-O1 2.0(1) P1-O1 1.33() P3-O7 1.3() Gd-O3 2.3(1) P1-O2 1.39() P3-O8 1.1() Gd-O 2.7(2) P1-O3 1.32() P3-O9 1.37() Gd-O 2.72(9) P1-C () P3-C () Gd-O7 2.(1) P2-O 1.32() C1-N1 1.99() Gd-O9 2.73(2) P2-O 1.3() C2-N1 1.97() Gd-Ow1 2.78(9) P2-O 1.1() C3-N1 1.00() Gd-Ow2 2.93(9) P2-C () [Tb(H NMP)(H 2O) 2]Cl 2H 2O Length (Å) Length (Å) Length (Å) Tb-O1 2.23(1) P1-O1 1.30() P3-O7 1.32() Tb-O (1) P1-O2 1.32() P3-O8 1.3() Tb-O 2.30(1) P1-O3 1.3() P3-O9 1.38() Tb-O 2.70(9) P1-C () P3-C () Tb-O7 2.1(1) P2-O 1.0() C1-N1 1.21() Tb-O (1) P2-O 1.3() C2-N1 1.97() Tb-Ow1 2.79(8) P2-O 1.0() C3-N1 1.9() Tb-Ow2 2.02(8) P2-C2 1.80() 17

18 Table S1 (cont.). Selected bond distances (Å) for Ln-H NMPCl, (Ln= La, Pr, Sm, Eu, Gd, Tb, Dy and Ho) and Ce-H 3NMP. [Dy(H NMP)(H 2O) 2]Cl 2H 2O Length (Å) Length (Å) Length (Å) Dy-O1 2.18(2) P1-O1 1.39() P3-O7 1.3() Dy-O (2) P1-O2 1.() P3-O8 1.8() Dy-O 2.332(2) P1-O3 1.32() P3-O9 1.3() Dy-O 2.07(1) P1-C1 1.81() P3-C () Dy-O7 2.33(2) P2-O 1.32() C1-N1 1.09() Dy-O (2) P2-O 1.37() C2-N1 1.99() Dy-Ow1 2.0(9) P2-O 1.0() C3-N1 1.88() Dy-Ow2 2.9(9) P2-C2 1.81() [Ho(H NMP)(H 2O) 2]Cl 2H 2O Length (Å) Length (Å) Length (Å) Ho01-O (2) P1-O 1.91(2) P3-O (2) Ho01-O (2) P1-O 1.91(2) P3-O12 1.9(2) Ho01-O (2) P1-O 1.8(2) P3-O (1) Ho01-O (2) P1-C1 1.81(2) P3-C (2) Ho01-O 2.330(2) P2-O9 1.9(2) N1-C2 1.0(3) Ho01-O 2.380(2) P2-O8 1.10(1) N1-C1 1.0(3) Ho01-O (2) P2-O7 1.8(2) N1-C3 1.11(3) Ho01-O1 2.0(2) P2-C (3) Table S2. H-bond interactions (Å) for [Ce 2(H 3NMP) 2(H 2O) ].H 2O (length < 3 Å). Vector Length (Å) Vector Length (Å) Vector Length (Å) O1 O 2.90(29) O8 Ow3 2.09(33) Ow1 Ow3 2.97() O1 O (28) O8 Ow 2.32(27) Ow1 Ow 2.0() O1 Ow2 2.72(33) O9 O (2) Ow1 Ow7 2.98() O2 Ow2 2.71(33) O10 O (31) Ow3 Ow 2.8() O2 Ow 2.87(3) O11 O1 2.87(32) Ow3 Ow (29) O3 O1 2.78(2) O12 Ow 2.33(33) Ow3 Ow9 2.72(30) O O (31) O13 Ow (32) Ow Ow9 2.87(2) O Ow 2.922(31) O13 O1 2.80(2) Ow Ow 2.9() O O 2.913(3) O1 Ow8 2.83(19) Ow Ow8 2.7(30) O O8 2.78(32) O1 Ow (23 Ow Ow (30) O O (23) O1 Ow 2.797(32) Ow8 Ow () O Ow 2.7() O17 Ow (20) Ow9 Ow (8) O Ow7 2.78(3) O18 Ow7 2.92() O7 O (27) O7 O1 3.00(2) 18

19 Table S3. Absorption and emission bands observed for [Pr(H NMP)(H 2O) 2]Cl 2H 2O. Absorption Luminescence (λ exc = 3 nm) Transition Wavelength (nm) Transition Wavelength (nm) 3 H 3 P 0 3 F F 3 3, F 19 1 G D H 21 3 P H 3 3 P 1 1, I 9 3 H 81 3 P 2 19

20 Table S. Absorption and emission bands observed for [Sm(H NMP)(H 2O) 2]Cl 2H 2O. Absorption Luminescence ( exc =3 nm) Transition Wavelength Transition Wavelength H /2 (nm) G /2 (nm) H 1/2, F 3/2, F 1/2 100 F /2 139 F 7/2 12 F 9/ F 11/2 98 H 9/2 G 7/2, I 9/2, M 1/2, 7 H 7/2 98 I 11/2, I 13/2 H /2 2 F /2, M 17/2, G 9/2, I 1/2 0 P /2 17 P /2, F 7/2, F 9/2, K 11/2, M 21/2, L 1/2, 02 G 11/2 L 13/2, D 1/2, P 7/2, L 17/2, K 13/2, F 9/2 32 D 3/2, D /2, P /2, H 7/2 3 K 1/2, H 9/2, D 7/2 20

21 Table S. Absorption and Emission bands observed for [Eu(H NMP)(H 2O) 2]Cl 2H 2O. Absorption Luminescence (λ exc = 3 nm) Transition Wavelength (nm) Transition Wavelength (nm) 7 F 0 D 0 D 0, D 1, D L F 3 2 G 2, G, G 37 7 F 2 11 D 32 7 F F 0 79 D 1 7 F 2 L 7 F

22 Table S. Absorption and emission bands observed for [Tb(H NMP)(H 2O) 2]Cl 2H 2O. Absorption Luminescence (λ exc = 3 nm) Transition 7 F Wavelength (nm) Transition G Wavelength (nm) 7 F 3 7 F 7 0, F 7 1, F F F 83 D 87 7 F F 89 G, D 3, L G, G 2, G, L 9 32 D 2, L 8, L 7, G 3 32 H 7, D 0, D

23 Table S7. Absorption and emission bands observed for [Dy(H NMP)(H 2O) 2]Cl 2H 2O. Absorption Luminescence ( ex=3 nm) Transition Wavelength Transition Wavelength H 1/2 (nm) F 9/2 (nm) H 11/2 171 H 9/2, F 11/ H 7/2, F 9/ H /2, F 7/2 907 F /2 80 H 11/2 1 F 3/2 7 H 13/2 73 F 9/2 7 H 1/2 82 I 1/2 1 G 11/2 27 M 21/2, I 13/2, F 7/2, K 17/2, M 19/2 388 I 11/2, P /2, P 3/2 3 M 1/2, P 9/2 30 G 9/2, F /2, I 9/2 337 K 1/2, L 19/2, P 3/2, M 17/2, G 7/

24 Table S8. Absorption and emission bands observed for [Ho(H NMP)(H 2O) 2]Cl 2H 2O. Transition I 8 I 7 I I F F, S 2 F 3 F 2 F 1 G G 3 H G 3, 3 F, 3 K 3 M 10 *Shoulder Wavelength (nm) ,3*

ELECTRONIC SUPPLEMENTARY INFORMATION

Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2015 ELECTRONIC SUPPLEMENTARY INFORMATION to A family of dinuclear lanthanide(iii) complexes