Networking Nanoswitches for ON/OFF Control of Catalysis

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1 Supporting Information for etworking anoswitches for O/OFF Control of Catalysis ikita Mittal, Susnata Pramanik, Indrajit Paul, Soumen De, Michael Schmittel* Center of Micro and anochemistry and Engineering, Organische Chemie I, Universität Siegen, Adolf-Reichwein Str. 2, Siegen, Germany Table of Contents 1 Synthesis S2 General Information Synthesis and Characterization of the anoswitch Complexes etwork States and Communication between Two Switches 2 Experiments Toward Establishing the Catalytic Conjugate Addition S8 Synthesis Catalysis Control Experiments Catalytic Cycle 3 MR Spectra S12 1 H MR of Switches and Self-sorting S12 1 H MR of Catalytic Experiments S17 4 ESI-MS Spectra S21 5 UV-vis Experiments S23 6 References S28 Abbreviations: DCM : dichloromethane ZnTPP : zinc(ii)-5,10,15,20-tetraphenylporphyrin TCE : 1,1,2,2-tetrachloroethane S2 S3 S6 S8 S9 S11 S1

2 Synthesis General Information All commercial reagents were used without further purification. Solvents were dried with the appropriate desiccants and distilled prior to use. 1 H MR and 13 C MR were recorded on a Bruker Avance 400 MHz using the deuterated solvent as the lock and residual protiated solvent as the internal reference (CD 2 Cl 2 : H = 5.32 ppm and C = 53.8 ppm). The following abbreviations were utilized to describe peak patterns: s = singlet, d = doublet, t = triplet, dd = doublet of doublet, td = triplet of doublet, dt = doublet of triplet, br = broad, bs = broad singlet, bd = broad doublet and m = multiplet. The numbering of the carbon atoms in the molecular formulae (vide infra) is used only for the assignments of the MR signals and thus is not necessarily in accordance with IUPAC nomenclature. Electrospray ionization mass spectra (ESI- MS) were recorded on a Thermo-Quest LCQ Deca. Melting points were measured on a Büchi SMP-20 instrument. Infrared spectra were recorded using a Varian 1000 FT-IR instrument. Elemental analysis was done on the EA 3000 CHS. Ligands 1 1 and 2 2 were synthesized according to known procedures. S2

3 Synthesis and Characterization of the anoswitch Complexes Synthesis of Complex [Fe(1) 2 ] f f m m Br g h l 1 k i j e d c a b = Fe 2+ Br [Fe(1) 2 ] 2+ Fe 2 Fe(BF 4 ) 2 6H 2 O (201 g, μmol) and molecular switch 1 (1.27 mg, 1.19 μmol) were placed in a 25 ml flask and refluxed in 15 ml of CH 2 Cl 2 /CH 3 C = 3:1 for 30 min. After removal of the solvent under reduced pressure the resultant mixture was subjected to analytical characterization without any purification. Yield: Quantitative; 1 H MR (400 MHz, 298 K, CD 2 Cl 2 ): = 8.74 (s, 4 H, e -H), 8.44 (s, 2 H, 4 -H), 8.31 (d, 3 J = 8.0 Hz, 2 H, 7 -H), 8.05 (d, 3 J = 8.0 Hz, 4 H, d -H), 7.89 (d, 3 J = 8.8 Hz, 2 H, 5 -H), 7.88 (d, 3 J = 8.4 Hz, 4 H, [g /h ]-H), 7.81 (td, 3 J = 8.0 Hz, 4 J = 1.2 Hz, 4 H, c -H), 7.78 (d, 3 J = 8.8 Hz, 2 H, 6 -H), 7.72 (bs, 2 H, f -H), 7.68 (d, 3 J = 8.4 Hz, 4 H, [h /g ]-H), 7.68 (bs, 2 H, f -H), 7.54 (d, 3 J = 8.0 Hz, 2 H, 8 -H), 7.43 (dd, 3 J = 7.6 Hz, 4 J = 1.6 Hz, 2 H, i -H), 7.24 (td, 3 J = 7.6 Hz, 4 J = 1.6 Hz, 2 H, [j /k ]-H), 7.24 (td, 3 J = 7.6 Hz, 4 J = 2.0 Hz, 2 H, [k / j ]-H), (m, 6H, b -,l -H), 6.97 (bd, 3 J = 5.2 Hz, 4 H, a -H), 6.88 (s, 4 H, [m/m ]-H), 6.80 (s, 4 H, [m /m]-h), 2.50 (s, 6 H, Me-H), 2.28 (s, 6 H, Me-H), 2.25 (s, 6 H, Me-H), 1.97 (s, 12 H, Me-H), 1.90 (s, 12 H, Me-H) ppm; IR (KBr) ν 3428, 2967, 2933, 2854, 2331, 1614, 1084, 1028, 799, 427, 420, 412, 405; ESI-MS: m/z (%) (100) [M] 2+ = [Fe(1) 2 ] 2+ ; Anal calcd for C 144 H 100 B 2 Br 2 F 8 Fe 10 10H 2 O 2CH 2 Cl 2 : C, 64.71; H, 4.61;, 5.17; found: C, 64.84; H, 5.05,, S3

4 Synthesis of Complex [Cu(1)]PF 6 2 Compound 1 (547 g, μmol) and [Cu(CH 3 C) 4 ]PF 6 (191 µg, μmol) were taken in an MR tube directly and dissolved in CD 2 Cl 2. The resultant mixture was subjected to analytical characterization without any purification. Yield: Quantitative; 1 H MR (400 MHz, 298 K, CD 2 Cl 2 ): δ = 8.81 (s, 1 H, 4 -H), 8.65 (d, 3 J = 8.4 Hz, 1 H, 7 -H), 8.25 (d, 3 J = 8.8 Hz, 1 H, 6 /5 - H), 8.18 (d, 3 J = 8.8 Hz, 1 H, 5 /6 -H), 8.15 (bd, 3 J = 4.8 Hz, 1 H, a -H), 8.03 (d, 4 J = 1.2 Hz, 1 H, f /f -H), 7.87 (td, 3 J = 7.6 Hz, 4 J = 1.6 Hz 1 H, c -H), 7.85 (d, 4 J = 1.2 Hz, 1 H, f /f -H), 7.78 (d, 3 J = 8.4 Hz, 1 H, 8 -H), 7.76 (bd, 3 J = 7.6 Hz, 1 H, d -H), 7.64 (bd, 3 J = 7.6 Hz, 1 H, d -H), (m, 2 H, e -, i /l -H), 7.57 (d, 3 J = 8.4 Hz, 2 H, g /h -H), (m, 2 H, e -, l /i -H), (m, 4 H, b -, c -, j -, k -H), 7.28 (d, 3 J = 8.4 Hz, 2 H, h /g -H), 6.78 (ddd, 3 J = 7.6 Hz, 3 J = 4.8 Hz, 4 J = 1.2 Hz, 1 H, b -H), 6.67 (d, 3 J = 4.8 Hz, 1 H, a -H), 6.43 (s, 1 H, m-h), 6.28 (s, 1 H, m-h), 5.89 (s, 1 H, m -H), 4.48 (s, 1 H, m -H), 2.43 (s, 3 H, Me-H), 1.88 (s, 6 H, Me-H), 1.82 (s, 3 H, Me-H), 1.63 (s, 3 H, Me-H), 1.09 (s, 3 H, Me-H), 1.05 (s, 3 H, Me-H) ppm. S4

5 Synthesis of Complex [Cu(2)]PF 6 1 Compound 2 (790 g, μmol) and [Cu(CH 3 C) 4 ]PF 6 (169 µg, μmol) were taken in an MR tube directly and dissolved in CD 2 Cl 2. The resultant mixture was subjected to analytical characterization without any purification. Yield: Quantitative; 1 H MR (400 MHz, 298 K, CD 2 Cl 2 ): δ = 9.00 (s, 1 H, 4-H), 8.84 (d, 3 J = 4.4 Hz, 2 H, β-h), 8.72 (d, 3 J = 4.4 Hz, 2 H, β-h), 8.70 (d, 3 J = 4.4 Hz, 2 H, β-h), 8.68 (d, 3 J = 4.4 Hz, 2 H, β-h), 8.67 (d, 3 J = 8.4 Hz, 1 H, 7-H), 8.24 (d, 3 J = 8.8 Hz, 1 H, 6/5-H), 8.21 (d, 3 J = 8.8 Hz, 1 H, 5/6-H), 8.20 (d, 3 J = 8.4 Hz, 2 H, p/o- H), 8.13 (bs, 1 H, f-h), 8.11 (dd, 3 J = 8.4 Hz, 4 J = 2.0 Hz, 1 H, e-h), 7.91 (d, 3 J = 8.4 Hz, 2 H, o/p-h), 7.88 (d, 3 J = 8.4 Hz, 1 H, d-h), 7.85 (d, 3 J = 8.4 Hz, 1 H, 8-H), 7.67 (bd, 3 J = 4.8 Hz, 1 H, c-h), (m, 1 H, j/g-h), 7.54 (bs, 1 H, n/m-h), (m, 1 H, g/j-h), (m, 5 H, h-, i-, m/n-, l/k-h), (m, 10 H, q-, r-, a-, b-, k/l-h), 6.37 (s, 1 H, 9/9 -H), 6.26 (s, 1 H, 9/9 -H), 6.16 (s, 1 H, 9/9 -H), 5.93 (s, 1 H, 9/9 -H), 2.61 (s, 9 H, Me-H), 2.42 (s, 3 H, Me-H), 1.94 (s, 3 H, Me-H), 1.86 (s, 3 H, Me-H), 1.84 (s, 3 H, Me-H), 1.82 (s, 6 H, Me-H), 1.80 (s, 6 H, Me-H), 1.79 (s, 6 H, Me-H), 1.71 (s, 3 H, Me-H), 1.64 (s, 3 H, Me-H), 1.09 (s, 3 H, Me- H) ppm. S5

6 etwork States and Communication between Two Switches Br = Cu + + Zn 9 [Cu(1)] + -Fe 2+ = Fe 2+ 2 etstate I 9 m Br a b Fe + Zn b a m [Fe(1) 2 ] 2+ 2 etstate II [Cu(2)] + = Cu + Preparation of etstate I [Cu(CH 3 C) 4 ]PF 6 (191 µg, µmol) was added to the solution of compound 1 (547 µg, µmol) and nanoswitch 2 (891 µg, µmol) in CD 2 Cl 2 in an MR tube. The mixture was sonicated for 2-3 min to afford a clear greenish pink solution. Then the mixture was subjected to 1 H MR analysis. 1 H MR clearly shows that 90% Cu + binds with switch 1 and the remaining 10% Cu + binds with switch 2 (see Figures S4 and S5). Preparation of etstate II Fe(BF 4 ) 2 6H 2 O (94.2 µg, µmol) dissolved in 1 ml of CH 3 C was added into the solution of compound 1 (595 µg, µmol) in 9 ml of CH 2 Cl 2. After stirring for 2-3 min, compound 2 (969 µg, µmol) and [Cu(CH 3 C) 4 ]PF 6 (208 µg, µmol) were added into the same flask. After stirring for five more minutes, the solvents were evaporated under reduced pressure S6

7 and the sample was subjected to 1 H MR measurement in CD 2 Cl 2 without any further purification. Analysis of 1 H MR confirms the formation of etstate II, i.e. [Fe(1) 2 ](BF 4 ) 2 + [Cu(2)]PF 6 (see Figures S6 and S7). Switching etstates by Self-Sorting (Fig. S7 and S8): In an MR tube switch 1 (547 µg, µmol), switch 2 (891 µg, µmol) and [Cu(CH 3 C) 4 ]PF 6 (191 µg, µmol) were dissolved in 500 µl of CD 2 Cl 2. After formation of a clear solution the sample was subjected to MR measurement (see Figure S7d). After the measurement, Fe(BF 4 ) 2 6H 2 O (87.0 µg, µmol) was added to the same MR tube and the sample was subjected to sonication for 2 min. The MR measurement was done for the sample without any further purification (see Figure S7e). To check the reversibility of the system, finally 4 -,-dimethylamino-2,2 :6,2 -terpyridine (143 µg, µmol) was added into the same sample that was heated at 40 C for 10 min (in a sonication chamber). Thereafter, the sample was cooled to room temperature. Then the 1 H MR spectrum was recorded (see Figure S7f). Alternatively, etstate II and 4 -,-dimethylamino-2,2 :6,2 -terpyridine were heated in a thermostat at 40 C. Samples were withdrawn after 10, 20 and 30 min and immediately cooled in ice. 1 H MR spectra were recorded as rapidly as possible (see Figure S8). S7

8 Experiments Toward Establishing the Catalytic Conjugate Addition Synthesis of Complex [(8)(5)] Zinc(II)-5,10,15,20-tetraphenylporphyrin (8) (4.00 mg, 5.90 mmol) and -methylpyrrolidine (5) (502 µg, 5.90 mmol) was taken in an MR tube and the mixture was dissolved in CD 2 Cl 2. The resultant solution was then subjected to 1 H MR analysis without any further purification. Yield: Quantitative. 1 H MR (400 MHz, 298 K, CD 2 Cl 2 ): δ = 8.88 (s, 8 H, β -H), (m, 8 H, Ph- H), (s, 12 H, Ph-H), 1.21 (bs, 2 H, β-h), 1.83 (bs, 2 H, α-h), 2.42 (s, 3 H, γ-h) ppm. Synthesis of Compound 6 Thiophenol (3) (658 mg, 5.97 mmol), 2-cyclopentenone (4) (490 mg, 5.97 mmol) and - methylpyrrolidine (5) (50.8 mg, 597 µmol) was dissolved in 25 ml of CH 2 Cl 2. The resultant solution was then refluxed for 12 h. After completion, the reaction mixture was directly subjected to 1 H MR measurement in CDCl 3. The 1 H MR spectrum perfectly matches that given in the literature. 3 Yield: Quantitative. 1 H MR (400 MHz, 298 K, CDCl 3 ): δ = (m, 2 H, α-h), (m, 3 H, β-, γ-h), (m, 1 H, a-h), (m, 1 H, d-h), (m, 1 H, c-h), (m, 3 H, d- & b-h), (m, 1 H, c-h) ppm. General Procedure: All catalytic reactions were performed in CD 2 Cl 2 directly in an MR tube put into a thermostat held at 40 (±1) C. Spurious acid traces were removed from CD 2 Cl 2 by a short filtration over basic alumina (Brockman activity 1). Solids were transferred first, followed by addition of the solvent and finally liquids were added (as standard solutions in CD 2 Cl 2 ). Product yields were determined by using TCE as an internal standard. S8

9 Catalysis Control Experiment A1 To a mixture of thiophenol (3) (658 µg, 5.97 µmol), cyclopentenone 4 (490 µg, 5.97 µmol) and -methylpyrrolidine (5) (45.8 µg, µmol) 500 µl of CD 2 Cl 2 were added. The reaction was heated at 40 C for 2 h, then the mixture was cooled to room temperature and directly subjected to 1 H MR measurements. The yield of product 6 was 33% (See Fig. S11). Catalysis Control Experiment A2 Thiophenol (3) (592 µg, 5.37 µmol), cyclopentenone 4 (441 µg, 5.37 µmol), -methylpyrroledine (5) (41.0 µg, µmol) and ZnTPP (327 µg, µmol) were dissolved in 500 µl of CD 2 Cl 2. The mixture was then heated at 40 C for 2 h and characterized by 1 H MR. o product formation was observed due to the strong binding between -methylpyrrolidine and ZnTPP (See Fig. S12). Catalysis Control Experiment A3 Thiophenol (3) (275 µg, 2.50 µmol), cyclopentenone 4 (205 µg, 2.50 µmol) and nanoswitch 1 (266 µg, µmol) were dissolved in 500 µl of CD 2 Cl 2 and allowed to heat at 40 C for 2 h. The reaction mixture was then cooled down to 0 C to stop the reaction and analyzed by 1 H MR. o product was observed (See Fig. S13). S9

10 Catalysis Control Experiment A4 Thiophenol (3) (168 µg, 1.53 µmol), cyclopentenone 4 (125 µg, 1.53 µmol) and nanoswitch 2 (265 µg, µmol) were dissolved in 500 µl of CD 2 Cl 2 and allowed to heat at 40 C for 2 h. The reaction mixture was then cooled down to 0 C to stop the reaction and analyzed by 1 H MR. o product was observed (See Fig. S14). Catalysis Control Experiment A5 Thiophenol (3) (608 µg, 5.52 µmol), cyclopentenone 4 (453 µg, 5.52 µmol), nanoswitch 2 (958 µg, µmol) and -methylpyrrolidine (5) (42.0 µg, µmol) were dissolved in 500 µl of CD 2 Cl 2 and allowed to heat at 40 C for 2 h. The reaction mixture was then cooled down to 0 C to stop the reaction and analyzed by 1 H MR. The product 6 was formed in 32% yield. (See Fig. S15). Catalysis Control Experiment A6 anoswitch 2 (449 µg, µmol) and [Cu(CH 3 C) 4 ]PF 6 (96.0 µg, µmol) were dissolved in 500 µl of CD 2 Cl 2. To the same MR tube, thiophenol (3) (285 µg, 2.59 µmol), cyclopentenone 4 (212 µg, 2.59 µmol) and -methylpyrrolidine (5) (20.0 µg, µmol) were added and the mixture was allowed to heat at 40 C for 2 h. The reaction mixture was then cooled down to 0 C to stop the reaction and analyzed by 1 H MR. o product formation was observed (See Fig. S16). Catalysis Control Experiment A7 anoswitch 1 (552 µg, µmol), nanoswitch 2 (900 µg, µmol) and [Cu(CH 3 C) 4 ]PF 6 (193 µg, µmol) were dissolved in 500 µl of CD 2 Cl 2 to afford etstate I. To the same MR tube, thiophenol (3) (571 µg, 5.18 µmol), cyclopentenone 4 (425 µg, 5.18 µmol) and - methylpyrrolidine (5) (40.0 µg, µmol) were added and the mixture was allowed to heat at 40 C for 2 h. The reaction mixture was then cooled down to 0 C to stop the reaction and analyzed by 1 H MR. The yield of product 6 formed in the reaction mixture was 30% (See Fig. S17). Catalysis Control Experiment A8 anoswitch 1 (434 µg, µmol), nanoswitch 2 (707 µg, µmol), [Cu(CH 3 C) 4 ]PF 6 (193 µg, µmol) and Fe(BF 4 ) 2 6H 2 O (69.0 µg, µmol) were dissolved in 500 µl of CD 2 Cl 2 : CD 3 C = 9:1 ratio to furnish etstate I. To the same MR tube, thiophenol (3) (449 µg, 4.07 µmol), cyclopentenone 4 (334 µg, 4.07 µmol) and -methylpyrrolidine (5) (31.0 µg, µmol) were added and the mixture was allowed to heat at 40 C for 2 h. The reaction S10

11 mixture was then cooled down to 0 C to stop the reaction and analyzed by 1 H MR. o product formation was observed (See Fig. S18). Catalytic Cycle Reversible Catalysis in O-OFF Cycles The catalytic reaction was started with etstate I prepared directly in the MR tube. Switch 1 (595 µg, µmol), switch 2 (969 µg, µmol) and [Cu(CH 3 C) 4 ]PF 6 (208 µg, µmol) were dissolved in CD 2 Cl 2 to afford etstate I. Compounds 3 (615 µg, 5.58 µmol), 4 (458 µg, 5.58 µmol) and 5 (43.0 µg, µmol) were then added and the mixture was heated at 40 C for 2 h. The reaction mixture was then cooled down to 0 C to stop the reaction and immediately subjected to 1 H MR measurement. Formation of product 6 (30%) was observed in the first cycle (see Fig. S19(a)). Thereafter, Fe(BF 4 ) 2 6H 2 O (94.0 µg, µmol) dissolved in 10 µl of CD 3 C was added and the sample heated again for 2 h at 40 C. o further increase in the yield of product 6 (total of 30%) was observed in the MR (see Fig. S18b). To regenerate etstate I, 4 -,-dimethylamino-2,2 :6,2 -terpyridine (7, 154 µg, µmol) and the used-up thiophenol (3) and 2-cyclopentenone (4) were added to reinstate analogous reaction conditions as in cycle 1. After the second cycle, 1 H MR analysis indicated a total of 54% of product 6, and after the third cycle a total yield of 78% of product 6. S11

12 MR Spectra 1 H MR of Switches and Self-Sorting CDHCl 2 Figure S1. 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of complex [Fe(1) 2 ](BF 4 ) 2. An expanded part of the aromatic region is shown at the bottom. S12

13 CDHCl 2 Figure S2. 1 H MR spectra (400 MHz, CD 2 Cl 2, 298 K) of complex [Cu(1)]PF 6. An expanded part of the aromatic region is shown at the top. S13

14 CDHCl 2 Figure S3. 1 H MR spectra (400 MHz, CD 2 Cl 2, 298 K) of complex [Cu(2)]PF 6. An expanded part of the aromatic region is shown at the top Figure S4. Partial 1 H MR spectra (400 MHz, CD 2 Cl 2, 298 K) of (a) [Cu(2)]PF 6 ; (b) switch 2; (c) [Cu(1)]PF 6 and (d) etstate I = 1 : 2 : [Cu(CH 3 C) 4 ]PF 6 = 1:1:1. 90% of Cu + bind to switch 1 while the remaining 10% of Cu + bind to switch 2. S14

15 CDHCl 2 Figure S5. Partial 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of Figure S4d: etstate I = 1 : 2 : [Cu(CH 3 C) 4 ]PF 6 = 1:1:1 with an expanded part of the aromatic region Figure S6. Top: Partial 1 H MR spectra (400 MHz, CD 2 Cl 2, 298 K) of (a) switch 1; (b) switch 2; (c) [Fe(1) 2 ](BF 4 ) 2 ; (d) [Cu(2)]PF 6 ; and (e) etstate II = switches 1 and 2, [Cu(CH 3 C) 4 ]PF 6 and Fe(BF 4 ) 2 (2:2:2:1). Bottom: Expanded part of the aromatic region of Figure S6e ( 1 H MR, 400 MHz, CD 2 Cl 2, 298 K). S15

16 m&m CDHCl 2 (a) [Fe(1) 2 ] 2+ (b) b a m m m m [Cu(1)] + 9&9 (c) [Cu(2)] + 9&9 (d) b a m m m m etstate I a b m&m 9&9 (e) 9&9 etstate II (f) b a m m m m etstate I a b Figure S7. Comparison of partial 1 H MR (400 MHz, 298 K, CD 2 Cl 2 ) of a) [Fe(1) 2 ] 2+ ; b) [Cu(1)] + ; c) [Cu(2)] + ; d) switch 1, switch 2 and Cu + in 1:1:1 ratio (etstate I); e) after addition of 0.5 eq. of Fe 2+ to solution (d), indicating the complete translocation of Cu + from switch 1 to switch 2 (etstate II) and f) after addition of 1 eq. of 4 -,-dimethylamino-2,2 :6,2 -terpyridine (7) to solution (e) and sonication for 10 min at 40 C, indicating reappearance of etstate I in the mixture. etstate I 30 min 20 min 10 min etstate II Figure S8. Switching from etstate II etstate I by addition of 4 -,-dimethylamino-2,2 :6,2 - terpyridine (7) at 40 C in a thermostat (without stirring) monitored at different times. In Figure S7f the regeneration of etstate I is faster due to using sonication at 40 C. S16

17 1 H MR for Catalytic Experiments Figure S9. 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of complex [(8)(5)]. Figure S10. 1 H MR spectrum (400 MHz, CDCl 3, 298 K) of (1) product 6; (2) an extended and fully assigned spectra of product 6. S17

18 TCE CDHCl 2 Product Figure S11. 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of the reaction of substrates 3 and 4 in presence of 9 mol% of -methylpyrrolidine (5) at 40 C in CD 2 Cl 2 for 2 h. Product 6 was formed in 33% yield with respect to internal standard (TCE) added in the reaction mixture. CDHCl 2 o product Figure S12. 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of the reaction of substrates 3 and 4 in presence of catalytic amounts (9 mol%) of -methylpyrolidine (5) and ZnTPP (in a 1:1 ratio) at 40 C in CD 2 Cl 2 for 2 h. o product 6 was observed. CDHCl 2 o Product Figure S13. 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of the reaction of substrates 3 and 4 in presence of 10 mol% of switch 1 at 40 C for 2 h. o reaction was observed. CDHCl 2 o Product Figure S14. 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of the reaction of substrates 3 and 4 in presence of 10 mol% of switch 2 at 40 C for 2 h. o reaction was observed. S18

19 TCE CDHCl 2 Product Figure S15. 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of the reaction of substrates 3 and 4 in presence of catalytic amounts (9 mol%) of -methylpyrrolidine (5) and switch 2 (10 mol%) at 40 C in CD 2 Cl 2 for 2 h. Product 6 was formed in 32% yield. CDHCl 2 o Product Figure S16. 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of the reaction of substrates 3 and 4 in presence of catalytic amounts (9 mol%) of -methylpyrrolidine (5) and [Cu(2)]PF 6 (10 mol%) at 40 C in CD 2 Cl 2 for 2 h. o product 6 was observed in the reaction mixture. TCE CDHCl 2 Product Figure S17. 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of the reaction of substrates 3 and 4 in presence of catalytic amount (9 mol%) of -methylpyrrolidine (5) and etstate I, i.e. [Cu(1)]PF 6 + switch 2 (both 10 mol%) at 40 C in CD 2 Cl 2 for 2 h. Product 6 was formed in 30% yield. TCE CDHCl 2 o Product Figure S18. 1 H MR spectrum (400 MHz, CD 2 Cl 2, 298 K) of the reaction of substrates 3 and 4 in presence of catalytic amounts (9 mol%) of -methylpyrrolidine (5) and etstate II, i.e. 5 mol% of [Fe(1) 2 ](BF 4 ) 2 and 10 mol% of [Cu(2)]PF 6, at 40 C in CD 2 Cl 2 for 2 h. o product 6 was formed. S19

20 (e) TCE CDHCl 2 Product (d) (c) (b) (a) Figure S19. Switches 1 and 2, [Cu(CH 3 C) 4 ]PF 6, 3, 4 and catalyst 5 (10:10:10:100:100:9 mol%) were combined. Prior to each 1 H MR the mixture was heated at 40 C for 2 h and then cooled (for details, see page S11). Partial 1 H MR spectra (400 MHz, CD 2 Cl 2, 298 K) after (a) the first heating of etstate I (= O state), (b) addition of 5 mol% of Fe 2+ to form etstate II (OFF state), (c) regeneration of etstate I (O state) by addition of 7 (10 mol%), (d) again addition of 5 mol% of Fe 2+ to form etstate II (OFF state) and (e) again regeneration of etstate I (O state) by addition of 7 (10 mol%). Consumed amounts of 3 and 4 were also added in regeneration steps (c) and (e). Insets show the product signal used for integration. S20

21 ESI-MS Spectra [Fe(1) 2 ] Relative Abundance m/z Figure S20. ESI-MS spectrum of complex [Fe(1) 2 ](BF 4 ) 2 in CH 2 Cl 2 and experimental isotopic distribution (black lines) along with calculated isotopic distribution (red lines) for the peak associated with [Fe(1) 2 ] [Cu(1)] + Relative Abundance [Cu(2)] m/z Figure S21. ESI-MS spectrum of a 1:1:1 mixture of switch 1, switch 2 and [Cu(CH 3 C) 4 ]PF 6 in CH 2 Cl 2 and experimental isotopic distributions (black lines) along with calculated isotopic distribution (red lines) for peaks associated with [Cu(1)] + and [Cu(2)] +. S21

22 Figure S22. ESI-MS spectrum of a 2:2:2:1 mixture of switch 1, switch 2, [Cu(CH 3 C) 4 ]PF 6 and Fe(BF 4 ) 2 6H 2 O in CH 2 Cl 2. Peak assigned at and a.u. confirmed the formation of [Fe(1) 2 ](BF 4 ) 2 and [Cu(2)]PF 6 in the mixture that is etstate II. S22

23 UV-vis Experiments Figure S23. UV-vis spectra demonstrating the Cu + translocation between switches 1 and 2. Two milliliter of a stock solution of [Cu(2)] + in DCM (0.1 mm) was transferred into a 2 cm cuvette. Subsequently, 1 eq. of switch 1 was added into the solution as solid. Thereafter, measurements were done at 2 min intervals for a total of 30 min. The translocation reached equilibrium after 16 min. 561 Figure S24. UV-vis spectra depicting the changes during Cu + translocation between switches 1 and 2. Two stock solutions of [Cu(2)] + and switch 1 (both 0.1 mm) were independently prepared in DCM. One milliliter fractions of both solutions were then transferred into a 2 cm cuvette. Thereafter, measurements were done at 2 min intervals. The kinetic trace was followed at 550 nm. S23

24 k = ± s -1 r 2 = ln(a 0 - A )/(A t - A ) Time / s Figure S25. The Cu + translocation of [Cu(2)] + and 1 was monitored at 550 nm. The kinetic analysis furnishes a linear correlation over 3 half-life times indicative of a first order process. The calculated t 1/2 is 105 s. The A value was determined 16 min after mixing. Figure S26. UV-vis spectra of the Cu + translocation triggered by addition of 0.5 eq. of Fe 2+ into a 10 6 M solution of [Cu(1)] (1:1) in DCM. Measurement was done immediately after addition of 0.5 eq. Fe 2+ and then after 2 min the second measurement was done. S24

25 Figure S27. UV-vis spectra of the Cu + translocation from switch [Cu(1)] + to switch 2 triggered by addition of 0.5 eq. of Fe 2+ into 10 4 M solution of [Cu(1)] (1:1) in DCM. Translocation was fast and completed within 3 min. Figure S28. UV-vis spectra of a solution of complex [Cu(1)] + after addition of Fe 2+ furnishing the dimeric [Fe(Cu(1)) 2 ] 4+. Two milliliter of a stock solution of [Cu(1)] + in DCM (0.1 mm) was transferred into a 2 cm cuvette. Subsequently, 0.5 eq. of Fe 2+ was added into the solution (red trace). Further spectra were taken in 2 min intervals and recorded for a total of 16 min. The translocation was completed within 3-4 min. S25

26 Figure S29. UV-vis spectra of the formation of the dimeric [Fe(Cu(1)) 2 ] 4+ from monomer [Cu(1)] + complex after addition of Fe 2+. In a follow-up experiment, the translocation of Cu + from switch [Fe(Cu(1)) 2 ] 4+ to switch 2 was investigated. Two milliliter of a stock solution of [Cu(1)] + in DCM (0.1 mm) was transferred into a 2 cm cuvette. Subsequently, 0.5 eq. of Fe 2+ was added into the solution. After dimer formation had been completed, 1 eq. of switch 2 was added into the mixture as solid. The UV-vis measurement shows immediate translocation (less than one minute) of Cu + from switch 1 to switch 2. Figure S30. UV-vis traces of switch 2 (10 4 M) alone and after addition of Fe 2+ at 298 K. S26

27 Figure S31. Comparison of UV-vis spectra of switch 2, [Cu(2)] +, etstate II, i.e. [Fe(1) 2 ] 2+ + [Cu(2)] + and [Fe(Cu(1)) 2 ] 4+ (all at 10 4 M) at 298 K. Figure S32. UV-vis spectra of M ZnTPP (8) in CH 2 Cl 2 (2 ml) upon addition of -methylpyrrolidine (5, M) at 298 K to afford the complex [(8)(5)]. The full data (wavelength region: nm) was analyzed using the SPECFIT/32 global analysis system (Spectrum Software Associates, Marlborough, MA). Result: log K [(8)(5)] = 4.43 ± S27

28 Figure S33. Partial UV-vis absorption of M [Cu(2)]PF 6 in CH 2 Cl 2 (2 ml) upon addition of - methylpyrrolidine (5, M) at 298 K to afford complex [Cu(2)(5)]PF 6. The full data (wavelength region nm) was analyzed using the SPECFIT/32 global analysis system (Spectrum Software Associates, Marlborough, MA). Result: log K [Cu(2)(5)] + = 4.20 ± References 1 Schmittel, M.; Pramanik, S.; De, S. Chem. Commun. 2012, 48, De, S.; Pramanik, S.; Schmittel, M. Dalton Trans. 2014, 43, Civit, M. G.; Sanz, X.; Vogels, C. M.; Webb, J. D.; Geier, S. J.; Decken, A.; Bo, C.; Westcott, S.A.; Fernández, E. J. Org. Chem. 2015, 80, S28