Supporting Information

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1 Supporting Information A Molecular Chameleon: Reversible ph- and Cation- Induced Control of the Optical Properties of Phthalocyanine-Based Complexes in the Visible and Near-Infrared Spectral Ranges Evgeniya A. Safonova, Alexander G. Martynov, * Sergey E. Nefedov, Gayane A. Kirakosyan,, Yulia G. Gorbunova,, * Aslan Yu. Tsivadze, Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, Russia Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, Russia yulia@igic.ras.ru Fig. S1 Molecular structure of 1 with thermal ellipsoids drawn at the 30% probability level. Fig. S2 Top and side views of superimposed structures of A (red) and B (blue) molecules of nitrile 1 found within its crystal lattice. Fig. S3 Fragment of crystal packing of molecules of nitrile, with the formation of infinite chains, constructed from dimers of molecules A (red) and B (blue). Hydrogen atoms are omitted for clarity. Fig. S4 Molecular structure of zinc phthalocyaninate 2Zn with thermal ellipsoids drawn at the 30% probability level. Hydrogen atoms are omitted for clarity. Fig. S5 Molecular structure of magnesium phthalocyaninate 2Mg with thermal ellipsoids drawn at the 30% probability level. Hydrogen atoms are omitted for clarity. Fig. S6a UV-Vis spectra of 2M (M=Zn, Mg, H 2 ) in CHCl 3 at the same concentrations (6.41x10-6 M). Fig. S6b Comparison of UV-Vis spectra of 2M and 3M normalized in CHCl 3. Fig. S7 UV-Vis spectra of 2Mg in toluene. Fig. S8 UV-Vis spectra of Zn[(15C5) 4 Pc] in CHCl 3 and its 1 st protonated form in a 30% solution of CF 3 COOH in CHCl 3. Fig. S9 UV-Vis spectra of 2Mg and its 1 st protonated form in CHCl 3. Fig. S10 UV-Vis spectra of 2H 2 and its 1 st and 2 nd protonated forms in CHCl 3 with different amounts of CF 3 COOH. Fig. S11 Changing in UV-Vis spectra of solution of 2Mg in CHCl 3 by adding solution of Ph 3 PO in CHCl 3 and solution of KBPh 4 in CH 3 CN. Fig. S12 Fluorescence spectra of 2M (M=Zn, Mg, H 2 ) excited at 400 nm under the same conditions. Fig. S13 1 H NMR spectrum of 1 in CDCl 3. Fig. S14 13 C NMR spectrum of 1 in CDCl 3. Fig. S15 1 H NMR spectrum of 2Mg in a 4 : 1 mixture of CDCl 3 with CD3OD. Fig. S16 1 H NMR spectrum of 2Zn in CDCl 3 in the presence of K 2 CO 3. Fig. S17 1 H NMR spectrum of 2H2 in CDCl 3. Fig. S18 HR ESI mass spectrum of 2H2. Fig. S19 HR ESI mass spectrum of 2Mg. Fig. S20 HR ESI mass spectrum of 2Zn. Table 1 X-ray crystal data and refinement parameters for 1, 2Mg and 2Zn. Table 2 Selected bond lengths and angles of 2Mg and 2Zn complexes. Table 3 Wavelengths and extinction coefficients of protonated forms of 2Zn in different concentrations of CF 3 COOH.

2 Table 4 Table 5 Wavelengths and extinction coefficients of protonated forms of 2H2 in different concentrations of CF 3 COOH. Photochemical data of 2M in chloroform (λmax=400 nm). Fig.S1 Molecular structure of 1 with thermal ellipsoids drawn at the 30% probability level. Fig S2. Top and side views of superimposed structures of A (red) and B (blue) molecules of nitrile 1 found within its crystal lattice.

3 Fig. S3. Fragment of crystal packing of molecules of nitrile, with the formation of infinite chains, constructed from dimers of molecules A (red) and B (blue). Hydrogen atoms are omitted for clarity. Fig. S4 Molecular structure of zinc phthalocyaninate 2Zn with thermal ellipsoids drawn at the 30% probability level. Hydrogen atoms are omitted for clarity.

4 Fig. S5. Molecular structure of magnesium phthalocyaninate 2Mg with thermal ellipsoids drawn at the 30% probability level. Hydrogen atoms are omitted for clarity. Fig S6a. UV-Vis spectra of 2M (M=Zn, Mg, H 2 ) in CHCl 3 at the same concentrations (6.41x10-6 M) Fig S6b. Comparison of normalized UV-Vis spectra of 2Zn (green) and zinc tetra-15-crown- 5-phthalocyaninate (blue) in CHCl 3.

5 Fig. S7. UV-Vis spectra of 2Mg in toluene. Fig S8. UV-Vis spectra of zinc tetra-15-crown-5-phthalocyaninate in CHCl 3 and its 1 st protonated form in 30% solution of CF 3 COOH in CHCl 3.

6 Fig S9. UV-Vis spectra of 2Mg and its 1 st protonated form in CHCl 3. Fig S10. UV-Vis spectra of 2H 2 and its 1 st and 2 nd protonated forms in CHCl 3 with different amounts of CF 3 COOH.

7 Y Axis Title Mg 2Mg+Ph 3 PO 2Mg+Ph 3 PO+KBPh X Axis Title Fig S11. Changing in UV-Vis spectra of solution of 2Mg in CHCl 3 by adding solution of Ph 3 PO in CHCl 3 and solution of KBPh 4 in CH 3 CN. Fig S12. Fluorescence spectra of 2M (M=Zn, Mg, H 2 ) excited at 400 nm under the same conditions.

8 Fig S13. 1 H NMR spectrum of 1 in CDCl 3. Fig S C NMR spectrum of 1 in CDCl 3.

9 Fig S15. 1 H NMR spectrum of 2Mg in a 4 : 1 mixture of CDCl 3 with CD 3 OD. Fig S16. 1 H NMR spectrum of 2Zn in CDCl 3 in the presence of K 2 CO 3.

10 Fig S17. 1 H NMR spectrum of 2H2 in CDCl 3. Fig S18. HR ESI mass spectrum of 2H2.

11 Fig S19. HR ESI mass spectrum of 2Mg. Fig S20. HR ESI mass spectrum of 2Zn.

12 Table S1 X-ray crystal data and refinement parameters for 1, 2Mg and 2Zn. Crystal parameters 1 2Mg x CHCl 3 x 2H 2 O 2Zn x 0.5 CHCl 3 x 0.5H 2 O CCDC Empirical Formula C 30 H 36 N 2 O 9 C 120 H 150 MgN 8 O 39 (CHCl 3 ) C 120 H 146 N 8 O 37 Zn(x 0.5 CHCl 3 x 0.5H 2 O Formula weight (g.mol -1 ) Color Yellow Dark-green Dark-green Temperature (K) 150(2) 150(2) 150(2) Crystal system monoclinic monoclinic monoclinic Space group P 2 1 /c P 2 1 P 2 1 a (Å) (10) (2) (19) b (Å) (8) (4) (3) c (Å) (11) (2) (2) α( ) β( ) (10) (2) (2) γ( ) Cell volume (Å 3 ) Z ρ calcd (mg.m 3 ) μ (mm 1 ) F(000) Crystal size (mm) 0.24 x 0.22 x x 0.18 x x 0.24 x 0.22 θ range for data collection 1.74 to to to 30 (deg). index ranges -25<=h<=25, -21<=k<=21, -29<=l<=29-20<=h<=20, -37<=k<=37, -20<=l<=20-21<=h<=21, -38<=k<=38, -23<=l<=23 reflns collected independent reflns [R(int) = [R(int) = [R(int) = ] ] ] data / restraints / params / 0 / / 52 / / 7 / 1267 goodness-of-fit on F a final R indices R1 = , wr2 R1 = , wr2 = R1 = , wr2 =

13 [I>2sigma(I)] = a R indices (all data) R1 = , wr2 = R1 = , wr2 = R1 = , wr2 = b largest diff. peak and hole(e.a -3 ) and and and a R 1 = F o - F c / F o ; wr 2 = { [w(f 2 o - F 2 c ) 2 ]/ w(f 2 o ) 2 } 1/2 b In all structures the largest diff. peak is observed in the vicinity of heavy atom.

14 Table S2. Selected bond lengths and angles of 2Mg and 2Zn complexes 2Mg 2Zn Bond lengths, Å Mg1-N (8) Zn1-N (6) Mg1-N (8) Zn1-N (6) Mg1-N (7) Zn1-N (6) Mg1-N (8) Zn1-N (6) Mg1-O (7) Zn1-O (7) Mg1-O (7) Angles, degree N7-Mg1-N5 89.8(3) N3-Zn1-N5 89.5(2) N7-Mg1-N1 90.3(3) N3-Zn1-N1 89.1(2) N5-Mg1-N (3) N5-Zn1-N (3) N7-Mg1-N (3) N3-Zn1-N (3) N5-Mg1-N3 90.1(3) N5-Zn1-N7 88.9(2) N1-Mg1-N3 89.8(3) N1-Zn1-N7 89.4(2) N7-Mg1-O2 89.9(3) N3-Zn1-O (3) N5-Mg1-O2 91.7(3) N5-Zn1-O (3) N1-Mg1-O2 91.0(3) N1-Zn1-O (3) N3-Mg1-O2 92.5(3) N7-Zn1-O (3) N7-Mg1-O1 91.2(3) N5-Mg1-O1 90.6(3) N1-Mg1-O1 86.7(3) N3-Mg1-O1 86.4(3) O2-Mg1-O (3)

15 Table S3. Wavelengths and extinction coefficients of protonated forms of 2Zn in different concentrations of CF 3 COOH. Form 2Zn 2ZnH 2ZnH 2 2ZnH 3 2ZnH 4 λ max (lgε) 732 (5.13) 758 (4.79), 799 (5.00) 749 (4.53), 797 (4.59), 915 (4.63), 974 (4.66) 1007 (4.79), 1028 (4.82) 867 (4.85) C(CF 3 COOH) E-06 (1.5 eq) 5.17E % (8.75E-01) 90% (11.76) Table S4. Wavelengths and extinction coefficients of protonated forms of 2H2 in different concentrations of CF 3 COOH. Form 2H2 2H2H 2H2H 2 λ max (lgε) 737 (4.95), 800 (4.67), 931 (4.58) 759 (5.03) 848 (4.81) C(CF 3 COOH) % 12% Table S5. Photochemical data of 2M in chloroform ( max =400 nm). Compound MgPc ZnPc H 2 Pc λ F, nm Stokes shift Φ F 0,22 0,13 0,18 It is clear that quantum yields of all investigated compounds are higher in toluene than in CHCl 3. The largest increase is for free phthalocyanine in toluene, quantum yield is almost twice as high! (1) Zimmer, H.; Lankin, D. C.; Horgan, S. W. Oxidations with Potassium Nitrosodisulfonate (Fremy s Radical). Teuber Reaction. Chem. Rev. 1971, 408, (2) Fulmer, G. R.; Miller, A. J. M.; Sherden, N. H.; Gottlieb, H. E.; Nudelman, A.; Stoltz, B. M.; Bercaw, J. E.; Goldberg, K. I. NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist. Organometallics 2010, 29, (3) Shekhar Reddy, D.; Ovchinnikov, Y. E.; Shishkin, O. V.; Struchkov, Y. T.; Desiraju, G. R. Supramolecular Synthons in Crystal Engineering. 3. Solid State Architecture and Synthon Robustness in Some 2,3-Dicyano-5,6-Dichloro-1,4-Dialkoxybenzenes. J. Am. Chem. Soc. 1996, 118,