Electronic Supplementary Information for: Effect of head group size on the photoswitching applications of azobenzene dispersered 1 analogues

Transcription

1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C. This journal is The Royal Society of Chemistry 204 Electronic Supplementary Information for: Effect of head group size on the photoswitching applications of azobenzene dispersered analogues Alexis Goulet-Hanssens, a,b T. Christopher Corkery, a Arri Priimägi, c Christopher J. Barrett a a Department of Chemistry, McGill University, 80 Sherbrooke St. West, Montreal, QC, Canada, H3A 0B8 b Current Address: Department of Chemistry, Humboldt-Universität zu Berlin, Brook- Taylor-Str. 2, 2489 Berlin, Germany. c Aalto University, ptics and Photonics Group, Department of Applied Physics, P.. BX 00, FI Aalto, Finland.

2 Material Syntheses With the goal of keeping these syntheses as facile as possible in the mildest conditions allowable, all reactions except for Sonogashira couplings (dry solvent, nitrogen atmosphere) were conducted under atmospheric conditions at room temperature. H MR spectra were acquired at 300 K, on a Varian-Mercury 300 MHz or 400 MHz spectrometer while C MR spectra were acquired on a Varian-Mercury 300 MHz MR. Chemical shifts are reported in ppm on the δ-scale using either the solvent signal for reference or internal TMS standard. High resolution mass spectrometry (HR-MS) was acquired on a Thermo Scientific Exactive Plus rbitrap. Samples were ionized using either atmospheric-pressure chemical ionization (APCI) or electrospray ionization (ESI). All observed ions in positive and negative ionization modes are reported. All chemicals were obtained from Sigma-Aldrich corporation (St. Louis, M, USA), with the exception of trimethylsilylacetylene which was obtained from akwood Chemicals (West Columbia, SC, USA). Synthesis of,-diethyl-4-((4-nitrophenyl)diazenyl)aniline (Compound 2) 2 In a 20 ml round-bottom flask containing a stir bar, 00 ml water and 0 ml acetone was set to cool in an ice bath. nce the solvent temperature was below C,.38 g of p- nitroaniline (0 mmol, eq.) was added and dissolved, forming an orange/brown solution after which 0.69 g of sodium nitrite (0 mmol,.2 eq.) and.8 ml concentrated HCl (20 mmol, 2 eq.) were added. This solution was stirred to form the reactive diazonium intermediate for 30 minutes after which.6 ml of,-diethylaniline was added (0 mmol, eq.). The solution rapidly turned red and was left to react for 2 hours, after which the acetone was removed under reduced pressure and the aqueous solution was extracted with 0 ml ethyl acetate. The organic phase was washed oncewith 00 ml water then once with 00 ml brine, dried with MgS 4, filtered, and evaporated. o further purification was necessary. Yield: 2.2 g, 74%.

3 H MR (300 MHz, chloroform-d) ppm.2 (t, J=7.03 Hz, 6 H), 3.48 (q, J=7.03 Hz, 4 H), 6.74 (d, J=8.0 Hz, 2 H), 7.90 (m, J=8.79, 8.0 Hz, 4 H), 8.3 (d, J=8.79 Hz, 2 H). _7_7_AGH_3-69.ESP M0(t,9,9) ormalized Intensity M0(d,4,6) M02(dd,3,,,7) M03(d,6,2) M04(q,8,8) Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm 6.7,.2, 47.0, 43.2, 26.4, 24., 22.4,.0, 44.8, 2.6.

4 AGH-3-69-CC_C.00.ESP ormalized Intensity Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C 6 H [M+H] + : , found: Synthesis of,-diethyl-4-((2-nitrophenyl)diazenyl)aniline (Compound 3) 2 In a 20 ml round-bottom flask containing a stir bar,.38 g of 2-nitroaniline (0 mmol, eq.) was dissolved in 00 ml water and 0 ml acetone to form a red solution g of sodium nitrite (0 mmol, eq.) and.7 ml concentrated HCl (20 mmol, 2 eq.) were then added. This solution was stirred for 30 minutes to form the reactive diazonium intermediate after which.6 ml of,-diethylaniline was added (0 mmol, eq.). The solution rapidly turned deep red and was left to react for 2 hours, after which the acetone was removed under reduced pressure, and the aqueous solution was extracted with 00 ml ethyl acetate. The organic phase was washed

5 twice with 00 ml water then 00 ml brine, dried with MgS 4, filtered, and evaporated. o further purification was necessary. Yield: 2. g, 84%. H MR (400 MHz, chloroform-d) ppm (m, 3 H), 7.70 (dd, J=8.0,.37 Hz, H), 7.60 (ddd, J=8.2, 7.23,.37 Hz, H), (m, H), (m, 2 H), 3.47 (q, J=7.29 Hz, 4 H),.24 (t, J=7.03 Hz, 6 H). 2_07_04_AGH_7-0.ESP,9 0.9 ormalized Intensity , , , Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm., 47., 46., 43.3, 2.7, 28.4, 26., 23.7, 8.6,.0, 44.8, 2.6.

6 _7_4_AGH_7-0CARB.ESP ormalized Intensity Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C 6 H [M+H] + : ; found: Calculated for C 6 H [M] - : ; found: Synthesis of 2-nitro-4-((trimethylsilyl)ethynyl)aniline (Compound 4a) H 2 2 Si In a 20 ml round-bottom flask containing a stir bar, 2.64 g of 4-iodo-2-nitroaniline (0 mmol, eq.), 0.3 g PdCl 2 (PPh 3 ) 2 (0.0 mmol, 0.00 eq.) and 9 mg CuI (0.0 mmol, 0.00 eq.) were dissolved in 80 ml dry THF and 40 ml dry triethylamine, forming a brown solution. The flask was capped with a septum and the solution purged with nitrogen for 30 minutes. Under a blanket of nitrogen, 2.2 ml trimethylsilylacetylene (2 mmol,.2 eq.) was injected. The solution was left to stir for 6 hours, at which point it was a dark solution with grey precipitate. The solution was filtered through a celite plug, rinsed with ethyl acetate and concentrated under

7 reduced pressure to ~60 ml. The concentrate was transferred to a separatory funnel and washed twice with 0 ml water, once with saturated 00 ml H 4 Cl solution, once with 0 ml brine, dried with a 2 S 4, filtered, and the solvent removed under reduced pressure. The crude product was purified by silica gel chromatography, 0 to 60% ethyl acetate in hexane. Yield:.92 g, 82%. H MR (300 MHz, chloroform-d) ppm 8.26 (d, J=.76 Hz, H), 7.4 (dd, J=8.64,.90 Hz, H), 6.73 (d, J=8.0 Hz, H), 6.20 (br. s., 2 H), 0.23 (s, 9 H). _6_2_AGH_0-3F4-ED.ESP 6,, ormalized Intensity H Si Chemical Shift (ppm) 93., -0.. C MR (300 MHz, chloroform-d) ppm 44., 8.,.4, 0.0, 8.7,.8, 03.,

8 _7_4_AGH_0-07F4-3CARB.ESP H ormalized Intensity Si Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C H 2 2 Si [M-H] - : ; found: Synthesis of 2-nitro-4-((trimethylsilyl)ethynyl)aniline (Compound 4b) H 2 2 In a 00 ml round-bottom flask containing a stir bar, g of 2-nitro-4- ((trimethylsilyl)ethynyl)aniline (Compound 4a,.64 mmol, eq.) was dissolved in 30 ml CH 2 Cl 2 and 20 ml methanol, followed by the addition of. g K 2 C 3 (8.2 mmol, eq.). The solution was left to stir 6 hours after which it was filtered on a plug of celite, rinsed with ethyl acetate and concentrated under reduced pressure. The concentrated product was dissolved in 0 ml ethyl acetate and washed twice with 0 ml water and once with 0 ml brine, after which the organic phase was dried with a 2 S 4, and filtered. nce the solvent was evaporated, the product was pure for further use. Yield: 0.26 g, 96%.

9 H MR (300 MHz, chloroform-d) ppm 8.29 (d, J=.76 Hz, H), 7.43 (dd, J=8.79,.76 Hz, H), 6.76 (d, J=8.79 Hz, H), 6.2 (br. s., 2 H), 3.00 (s, H). _7 AGH_-.ESP H ormalized Intensity Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm 44.6, 8., 0.2, 8.9, 0.7, 8.8, 76..

10 _7 AGH_-CARB.ESP H ormalized Intensity Chemical Shift (ppm) HR-MS (ESI, 4 kv): m/z Calculated for C 8 H [M+H] + :63.002; found: Calculated for C 8 H 2 2 [M-H] - :6.037; found:

11 Synthesis of,-diethyl-4-((4-ethynyl-2-nitrophenyl)diazenyl)aniline (Compound 4) 2 In a 20 ml round-bottom flask containing a stir bar, 40 ml acetone and 80 ml water was set to cool in an ice bath. nce the solvent temperature was below C, 0.06 g of 2-nitro-4- ((trimethylsilyl)ethynyl)aniline (Compound 4b, 0.34 mmol, eq.) was added, forming a deep red solution, after which 26 mg of sodium nitrite (0.38 mmol,.2 eq.) and 70 µl M HCl (0.7 mmol, 2.4 eq.) were added. This solution was stirred to form the reactive diazonium intermediate for 30 minutes after which 60 µl of,-diethylaniline was added (0.37 mmol,.2 eq.). The solution rapidly turned red and was left to react for 2 hours. The acetone was removed under reduced pressure and the product extracted from the aqueous solution with 0 ml ethyl acetate. The organic phase was washed twice with 00 ml water, once with 00 ml brine, dried with MgS 4, filtered, and evaporated. The crude product was purified by silica gel chromatography, 0 to 60% ethyl acetate in hexane. The azo product co-elutes with unreacted 2-nitro-4- ((trimethylsilyl)ethynyl)aniline which was removed by dissolving the crude in 20 ml THF with a trace of DMAP and adding an excess of di-tert-butyl dicarbonate until the reaction was complete by TLC. The solvent was removed and the product purified on a short silica column, 0 to 60% ethyl acetate in hexane. Yield: 0.04 g, 49%. H MR (300 MHz, chloroform-d) ppm 7.9 (d, J=.76 Hz, H), (m, 2 H), (m, 2 H), 6.70 (d, J=9.38 Hz, 2 H), 3.47 (q, J=7.23 Hz, 4 H), 3.2 (s, H),.24 (t, J=7.03 Hz, 6 H).

12 _4_8_AGH_8-8PURE.ESP 24, ormalized Intensity ,4,3,, , , Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm.4, 47., 4., 43.,.8, 27.3, 26.9, 22.3, 8.,., 8., 80.4, 44.9, 2.7. C MR (300 MHz, chloroform-d) ppm.4, 4., 43.,.8, 27.3, 26.9, 22.3, 8.,., 8., 80.4, 44.9, 2.7.

13 _4_8_AGH_8-8PUREC.ESP 76.9 ormalized Intensity Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C 8 H [M+H] + : ; found: Synthesis of,-diethyl-4-((2-nitro-4-(-phenyl-h-,2,3-triazol-4- yl)phenyl)diazenyl)aniline (Compound ) 2 In a 00 ml round-bottom flask containing a stir bar, g,-diethyl-4-((4-ethynyl-2- nitrophenyl)diazenyl)aniline (Compound 4, 0.29 mmol, eq.), 4 mg CuBr (0.29 mmol, eq.), 4 mg sodium ascorbate (0.8 mmol, 2 eq.) and 60 µl,,,, -

14 pentamethyldiethylenetriamine (PMDTA) (0.29 mmol, eq.) were dissolved in 20 ml DMF. After the reactants were dissolved, 03 mg phenyl azide (0.87 mmol, 3 eq.) was added and the solution was left to stir 6 hours. The red solution was concentrated to ~0 ml, added to a separatory funnel with 60 ml water and extracted twice with 0 ml ethyl acetate. The red organic extractions were combined and washed in sequence with 80 ml water, 80 ml saturated H 4 Cl, and 80 ml brine. The organic phase was dried with magnesium sulfate, filtered, and evaporated. The crude product was purified by silica gel chromatography, 0 to 00% ethyl acetate in hexane. Yield: 0.08 g, 64%. H MR (400 MHz, chloroform-d) ppm 8.33 (d, J=.6 Hz, H), 8.3 (s, H), 8.9 (dd, J=8.40,.76 Hz, H), (m, 3 H), 7.8 (d, J=7.42 Hz, 2 H), (m, 2 H), 7.0 (d, J=7.03 Hz, H), 6.74 (d, J=7.42 Hz, 2 H), 3.48 (q, J=7.03 Hz, 4 H),.2 (t, J=7.03 Hz, 6 H). 2_AGH_0-47F0-.ESP ormalized Intensity ,7, 0,8 23, , , , Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm 47.8, 46.2, 4.3, 6.8,.8, 0.8, 29.9, 29.4, 29., 27.3, 26.7, 20.8, 20.6, 9.2, 8.4,.3, 4.0, 2.6.

15 0. _7 AGH_0-47F0-.ESP ormalized Intensity Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C 24 H [M+H] + : ; found: Calculated for C 24 H [M] - : ; found: Synthesis of,-diethyl-4-((4-(-(naphthalen--yl)-h-,2,3-triazol-4-yl)-2- nitrophenyl)diazenyl)aniline (Compound 6) 2 In a 00 ml round-bottom flask containing a stir bar, g,-diethyl-4-((4-ethynyl-2- nitrophenyl)diazenyl)aniline (Compound 4, 0.29 mmol, eq.), 4 mg CuBr (0.29 mmol, eq.), 4 mg sodium ascorbate (0.8 mmol, 2 eq.) and 60 µl PMDTA (0.29 mmol, eq.) were

16 dissolved in 20 ml DMF. After the reactants were dissolved, 47 mg -azido-naphtalene (0.87 mmol, 3 eq.) was added and the solution was left to stir 6 hours. The red DMF solution was concentrated to ~0 ml, added to a separatory funnel with 60 ml water and extracted twice with 0 ml ethyl acetate. The red organic extractions were combined and washed in sequence with 80 ml water, 80 ml saturated H 4 Cl, and 80 ml brine. The organic phase was dried with magnesium sulfate, filtered, and evaporated. The crude product was purified by silica gel chromatography, 0 to 00% ethyl acetate in hexane. Yield: 0.08 g, 7%. H MR (400 MHz, chloroform-d) ppm 8.37 (d, J=.9 Hz, H), 8.27 (s, H), 8.23 (dd, J=8.40,.76 Hz, H), 8.07 (d, J=7.82 Hz, H), (m, H), 7.88 (m, J=8.60 Hz, 3 H), (m, H), 6.73 (d, J=8.99 Hz, 2 H), 3.48 (q, J=7.6 Hz, 4 H),.4.32 (m, 6 H). 2_AGH_0-3F-7.ESP 37,3 M0(d) M0(m) M0(m) M07(d) M06(m) M08(dd) M09(s).2 ormalized Intensity M04(m) M03(d) 28, ,34 M02(q) Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm.2, 47.8, 4., 4.2, 43., 4.2, 3.3, 0.7, 29.4, 28.4, 28., 27.2, 26.7, 2.0, 23.6, 23., 22.2, 20.8, 9.,., 44.9, 2.7.

17 _7_0_AGH_0-3F-7CARB.ESP ormalized Intensity Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C 28 H [M+H] + : ; found: Calculated for C 28 H [M] - : ; found: Synthesis of 4-((4-(-(anthracen-2-yl)-H-,2,3-triazol-4-yl)-2-nitrophenyl)diazenyl)-,-diethylaniline (Compound 7) 2 In a 00 ml round-bottom flask containing a stir bar, g,-diethyl-4-((4-ethynyl-2- nitrophenyl)diazenyl)aniline (Compound 4, 0.29 mmol, eq.), 4 mg CuBr (0.29 mmol, eq.),

18 4 mg sodium ascorbate (0.8 mmol, 2 eq.) and 60 µl PMDTA (0.29 mmol, eq.) were dissolved in 20 ml DMF. After the reactants were dissolved, 90 mg 2-azido-anthracene (0.87 mmol, 3 eq.) was added and the solution was left to stir 6 hours. The red DMF solution was concentrated to ~0 ml, added to a separatory funnel with 60 ml water and extracted twice with 0 ml ethyl acetate. The red organic extractions were combined and washed in sequence with 80 ml water, 80 ml saturated H 4 Cl, and 80 ml brine. The organic phase was dried with magnesium sulfate, filtered, and evaporated. The crude product was purified by silica gel chromatography, 0 to 00% ethyl acetate in hexane. Yield: 0.02 g, 8%. H MR (400 MHz, chloroform-d) ppm 8. (d, J=0. Hz, H), 8.0 (s, H), 8.40 (s, 2 H), (m, 2 H), 8.06 (d, J=9.38 Hz, 2 H), (m, 2 H), (m, 3 H), (m, 2 H), (m, 2 H), (m, 4 H),.2.3 (m, 6 H). _6_2_AGH_-77F0-8.ESP M0(m) M07(m) 34, M06(m) ormalized Intensity M0(m) M08(m) M09(d) M02(d) 4, M(s) M0(m) M2(s) ,38 M03(m) Chemical Shift (ppm) Due to insufficient solubility, a C MR spectrum was unattainable. HR-MS (APCI, 4 kv): m/z Calculated for C 32 H [M+H] + : ; found: Calculated for C 32 H [M] - : 4.222; found:

19 Synthesis of 2-(ethyl(phenyl)amino)ethylmethacrylate (Compound 8a) In a L round-bottom flask containing a stir bar, 00 ml CH 2 Cl 2 was set to cool in an ice bath. nce cool, 7.9 g of -ethyl aniline ethanol (08.4 mmol, eq.) was added and dissolved, followed by the addition of 0 ml triethylamine, forming a clear blue solution. In a dropping funnel above the reaction flask, 6.8 ml methacryloyl chloride (73 mmol,.6 eq.) was dissolved in 200 ml CH 2 Cl 2 and added dropwise to the cooled reaction flask. Within an hour, the solution started turning red. After 3 hours the reaction mixture was concentrated to 200 ml and washed with 200 ml water four times. The organic phase was transferred to a 00 ml round bottom flask and stirred with 00 ml wt% ah for one hour, to remove unreacted methacryloyl chloride. The mixture was transferred to a separatory funnel and the aqueous phase discarded. The red organic phase was washed with two portions of 00 ml water and then 00 ml brine, dried with MgS 4, filtered, and evaporated. The pure monomer was separated from starting material by running through a short silica plug with CH 2 Cl 2. Yield: 22. g, 86%. H MR (300 MHz, chloroform-d) ppm (m, 2 H), (m, 3 H), 6. (s, H),.8 (s, H), 4.32 (t, J=6.4 Hz, 2 H), 3.6 (t, J=6.4 Hz, 2 H), 3.43 (q, J=7.03 Hz, 2 H),.9 (s, 3 H),.9 (t, J=7.03 Hz, 3 H).

20 _6 AGH_0-99B.ESP ormalized Intensity ,3 6,2, Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm 6., 29.4, 2.8, 6.,.9, 88.7, 62., 48.7, 4.2, 30.9, 8.3, _2_27_AGH_9-73F_CARB.ESP ormalized Intensity Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C 4 H 20 2 [M+H] + : ; found;

21 Synthesis of 2-(ethyl(4-((2-nitro-4- ((trimethylsilyl)ethynyl)phenyl)diazenyl)phenyl)amino)ethylmethacrylate (Compound 8b) 2 Si In a 00 ml round-bottom flask containing a stir bar, 20 ml acetone and 0 ml water was set to cool in an ice bath. nce the solvent temperature was below C,.692 g of 2-nitro- 4-((trimethylsilyl)ethynyl)aniline (Compound 4a, 7.2 mmol, eq.) was added and dissolved, forming a deep red solution, after which 0.4 g of sodium nitrite (.8 mmol, 0.8 eq.) and 2 ml 2 M HCl (24 mmol, 3.3 eq.) was added. This solution was stirred for 30 minutes to form the reactive diazonium intermediate, after which.3 g of 2-(ethyl(phenyl)amino)ethylmethacrylate was added (Compound 8a,.78 mmol, 0.8 eq.). The solution rapidly turned red and was left to react for 2 hours after which the acetone was removed under reduced pressure and the aqueous solution was extracted with 00 ml ethyl acetate. The organic phase was washed twice with 0 ml water then 0 ml brine, dried with MgS 4, filtered, and evaporated. The crude product was purified by silica gel chromatography, 0 to 60% ethyl acetate in hexane. The azo product coelutes with unreacted 2-nitro-4-((trimethylsilyl)ethynyl)aniline which was removed by dissolving the crude in 00 ml THF with a trace of DMAP and adding an excess of di-tert-butyl dicarbonate until the reaction was complete by TLC. The solvent was removed and the product purified on a short silica column, 0 to 60% ethyl acetate in hexane. Yield:.0 g, 36%. H MR (300 MHz, chloroform-d) ppm (m, 3 H), (m, 2 H), 6.82 (d, J=9.38 Hz, 2 H), 6.09 (s, H),.9 (s, H), 4.37 (t, J=.90 Hz, 2 H), 3.73 (t, J=6. Hz, 2 H), 3.4 (q, J=7.03 Hz, 2 H),.93 (s, 3 H),.26 (t, J=8.20 Hz, 3 H), 0.26 (s, 9 H).

22 _6_6_AGH_0-0PURE.ESP M0(s,28,,29) 0.27 ormalized Intensity Si ,0,4,, M0(m), M(m) M09(d) M08(s) M07(s) M04(q) M06(t) M0(t) M02(t) 3 M03(s) Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm 67.3,.3, 47.2, 44.8, 44.0,.6, 27., 26.6, 26.3, 23.8, 8.3,., 02., 98.6, 6.7, 48.8, 4.6, 27.7, 8.3, 2.3, -0.2.

23 AGH_-C2F4_CARB_0.ESP Si ormalized Intensity Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C 2 H Si [M+H] + : ; found: Calculated for C 2 H Si [M] - : ; found: Synthesis of 2-(ethyl(4-((4-ethynyl-2- nitrophenyl)diazenyl)phenyl)amino)ethylmethacrylate (Compound 8) 2 In a 00 ml round-bottom flask containing a stir bar, 2.4 g 2-(ethyl(4-((2-nitro-4- ((trimethylsilyl)ethynyl)phenyl)diazenyl)phenyl)amino)ethylmethacrylate (Compound 8b, 4.0 mmol, eq.) was dissolved in 40 ml THF. To the deep red solution, 4. ml M tetra-nbutylammonium fluoride (4. mmol,.02 eq.) was added dropwise over 0 minutes. nce the reaction was complete, as judged by thin layer chromatography, the THF solution was transferred to a separatory funnel with 200 ml water and 200 ml ethyl acetate. The organic

24 phase was washed with 00 ml water, then 00 ml brine, dried with MgS 4, filtered, and evaporated. The crude product was purified by silica gel chromatography, 0 to 0% ethyl acetate in hexane. Yield:.66 g, 8%. H MR (300 MHz, chloroform-d) ppm 7.92 (s, H), 7.8 (d, J=9.38 Hz, 2 H), (m, 3 H), 6.80 (d, J=9.38 Hz, 2 H), 6.0 (s, H),.9 (d, J=.76 Hz, H), 4.36 (t, J=6. Hz, 2 H), 3.72 (t, J=6. Hz, 2 H), 3.4 (q, J=7.03 Hz, H), 3.27 (s, H),.93 (s, 3 H),.2 (t, J=7.03 Hz, 3 H). _6_7_AGH_0-2.ESP M0(t) ormalized Intensity ,0 M0(m) M(d),6 3 M2(s) M09(d) M08(s) 30, 30M07(d) M04(q) 26 M0(t) M06(t) M03(s) M02(s) Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm 67.3,.4, 47.2, 4.3, 44.0,.8,.8, 27.3, 26.7, 26.3, 22.7, 8.,., 8.4, 80.7, 6.7, 48.8, 4.7, 8.3, 2.3.

25 _7_4_AGH_0-2CARB.ESP ormalized Intensity Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C 22 H [M+H] + : ; found: Synthesis of 2-(ethyl(4-((2-nitro-4-(-phenyl-H-,2,3-triazol-4- yl)phenyl)diazenyl)phenyl)amino)ethylmethacrylate (Compound 9) 2 To a 00 ml round-bottom flask containing a stir bar and 30 ml DMF, 0.3 g 2-(ethyl(4- ((4-ethynyl-2-nitrophenyl)diazenyl)phenyl)amino)ethylmethacrylate (Compound 8, 0.74 mmol, eq.), 06 mg CuBr (0.74 mmol, eq.), 293 mg sodium ascorbate (.48 mmol, 2 eq.) and 4 µl

26 PMDTA (0.74 mmol, eq.) were added. After the reactants were dissolved, 300 mg phenyl azide (2 mmol, 3 eq.) was added and the solution was left to stir 6 hours. The red solution was added to a separatory funnel with 200 ml water and extracted twice with 0 ml ethyl acetate. The red organic extractions were combined and washed with 80 ml water, 80 ml saturated H 4 Cl, and 80 ml brine. The organic phase was dried with a 2 S 4, filtered, and evaporated. The crude product was purified by silica gel chromatography, 0 to 00% ethyl acetate in hexane. Yield: 60 mg, 4%. H MR (400 MHz, chloroform-d) ppm 8.34 (d, J=.9 Hz, H), 8.33 (s, H), 8.8 (dd, J=8.40,.76 Hz, H), (m, H), (m, 2 H), 7.49 (d, J=7.42 Hz, H), 6.79 (d, J=8.99 Hz, 2 H), 6. (s, H),.60 (s, H), 4.37 (t, J=6.2 Hz, 2 H), 3.72 (t, J=6.2 Hz, 2 H), 3.4 (q, J=7.03 Hz, 2 H),.94 (s, 3 H),.2 (t, J=7.03 Hz, 3 H). _6_0_AGH_0-9F4-2.ESP 38 M02(s) ormalized Intensity ,9,8,,8 0 M(m) 7 M2(dd) M0(m) 23,27 M08(d) 24, M07(s) M06(s) M03(q) M0(t) 3 3 M04(t) M0(t) Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm 67.3,.2, 47.9, 4., 44.0, 6.8,.8,.0, 29.9, 29.4, 29., 26., 26.3, 20.8, 20.6, 9., 8.,., 6.7, 48.8, 4.7, 8.4, 2.3.

27 _6_2_AGH_0-9F4-2CARB.ESP ormalized Intensity Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C 28 H [M+H] + : ; found: Synthesis of 2-(ethyl(4-((4-(-(naphthalen--yl)-H-,2,3-triazol-4-yl)-2- nitrophenyl)diazenyl)phenyl)amino)ethylmethacrylate (Compound 0) 2 To a 00 ml round-bottom flask containing a stir bar and 30 ml DMF, 0.3 g 2-(ethyl(4- ((4-ethynyl-2-nitrophenyl)diazenyl)phenyl)amino)ethylmethacrylate (Compound 8, 0.74 mmol, eq.), 06 mg CuBr (0.74 mmol, eq.), 293 mg sodium ascorbate (.48 mmol, 2 eq.) and 4 µl

28 PMDTA (0.74 mmol, eq.) were added. After the reactants were dissolved, 376 mg -azido naphthalene (2 mmol, 3 eq.) was added and the solution was left to stir 6 hours. The red solution was added to a separatory funnel with 200 ml water and extracted twice with 0 ml ethyl acetate. The red organic extractions were combined and washed with 80 ml water, 80 ml saturated H 4 Cl, and 80 ml brine. The organic phase was dried with a 2 S 4, filtered, and evaporated. The crude product was purified by silica gel chromatography, 0 to 00% ethyl acetate in hexane. Yield: 40 mg, 33%. H MR (400 MHz, chloroform-d) ppm 8.38 (d, J=.6 Hz, H), 8.28 (s, H), 8.23 (dd, J=8.60,.9 Hz, H), 8.07 (d, J=7.82 Hz, H), (m, H), 7.88 (dd, J=8.79,.67 Hz, 3 H), (m, H), 6.8 (d, J=9.38 Hz, 2 H), 6. (s, H),.60 (s, H), 4.37 (t, J=6.06 Hz, 2 H), 3.73 (t, J=6.06 Hz, 2 H), 3.4 (q, J=7.03 Hz, 2 H),.94 (s, 3 H),.26 (t, J=7.03 Hz, 3 H)..0 _6_2_AGH_0-43F3-7.ESP M(m) ormalized Intensity M(dd) 2 2,,4,22,27, M2(dd) M(m) 8,0 9 M0(d) DMF 28, M09(s) 6. M08(s) M07(t) M0(q) 3 M06(t) M02(s) DMF DMF M0(t) Chemical Shift (ppm) C MR (300 MHz, chloroform-d) ppm 67.3,.2, 4., 44.0,.9, 4.2,., 0.8, 29., 28.4, 28., 27.3, 26., 26.3, 2.0, 23.6, 23., 22.2, 20.9, 9.2,., 6.7, 48.8, 4.6, 8.4, 2.3.

29 _6_2_AGH_0-43F3-7CARB.ESP ormalized Intensity Chemical Shift (ppm) HR-MS (APCI, 4 kv): m/z Calculated for C 32 H [M+H] + : ; found: Synthesis of 2-((4-((4-(-(anthracen-2-yl)-H-,2,3-triazol-4-yl)-2- nitrophenyl)diazenyl)phenyl)(ethyl)amino)ethylmethacrylate (Compound ) 2 To a 00 ml round-bottom flask containing a stir bar and 30 ml DMF, 0.3 g 2-(ethyl(4- ((4-ethynyl-2-nitrophenyl)diazenyl)phenyl)amino)ethylmethacrylate (Compound 8, 0.74 mmol,

30 eq.), 06 mg CuBr (0.74 mmol, eq.), 293 mg sodium ascorbate (.48 mmol, 2 eq.) and 4 µl PMDTA (0.74 mmol, eq.) were added. After the reactants were dissolved, 487 mg 2-azido anthracene (2 mmol, 3 eq.) was added and the solution was left to stir 6 hours. The red solution was added to a separatory funnel with 200 ml water and extracted twice with 0 ml ethyl acetate. The red organic extractions were combined and washed with 80 ml water, 80 ml saturated H 4 Cl, and 80 ml brine. The organic phase was dried with a 2 S 4, filtered, and evaporated. The crude product was purified by silica gel chromatography, 0 to 00% ethyl acetate in hexane. Yield: 80 mg, 39%. H MR (300 MHz, chloroform-d) ppm 8.2 (d, J=7.62 Hz, H), 8.47 (s, H), 8.37 (s, 2 H), 8.20 (d, J=0.26 Hz, 2 H), (m, 3 H), (m, 4 H), 7.3 (d, J=7.33 Hz, 2 H), 6.79 (d, J=9.96 Hz, 2 H), 6. (s, H),.60 (s, H), 4.36 (t, J=.7 Hz, 2 H), 3.7 (t, J=6.30 Hz, 2 H), 3.2 (q, J=7.00 Hz, 2 H),.94 (s, 3 H),.4.3 (m, 3 H). _6_20_AGH_-7F4-9_7-2.ESP 46 M02(s) ormalized Intensity M2(d) M(d) M(s) M4(s) 8.37 M0(m) M(m) M09(d) M08(d) 34, M07(s) 6. M06(s).60 M03(q) M04(t) M0(t) M0(m) Chemical Shift (ppm) Due to insufficient solubility, a C MR spectrum was unattainable.

31 HR-MS (APCI, 4 kv): m/z Calculated for C 36 H [M+H] + : ; found: Synthesis of poly(9) Compound 2 n 2 In a 2 ml custom-made rota-flo polymerization flask with stir bar, 60 mg 2-(ethyl(4-((2- nitro-4-(-phenyl-h-,2,3-triazol-4-yl)phenyl)diazenyl)phenyl)amino)ethylmethacrylate (Compound 9, 0.3 mmol, equiv), was dissolved in 6 ml dry THF. This was followed by the addition of mg of freshly recrystallized AIB (0.03 mmol, 0. eq.). xygen was removed by four freeze-pump-thaw-backfill cycles in liquid nitrogen with an argon backfill. After deoxygenation, the flask was placed in an oil bath at 80 C for 36 hours. The flask was then cooled to room temperature and the contents rinsed to a round bottom flask to be concentrated to ~ ml. This solution was flocculated into ~300 ml methanol. After stirring for 6 hours, the flocculated polymer was filtered on a fine frit. Yield: 0 mg, 3%. Mw: 3; Mn: 2277; PDI:.6. Synthesis of poly(0) Compound n 2

32 In a 2 ml custom-made rota-flo polymerization flask with stir bar, 9 mg 2-(ethyl(4-((4- (-(naphthalen--yl)-h-,2,3-triazol-4-yl)-2- nitrophenyl)diazenyl)phenyl)amino)ethylmethacrylate (Compound 0, 0.3 mmol, equiv), was dissolved in 6 ml dry THF. This was followed by the addition of mg of freshly recrystallized AIB (0.03 mmol, 0. eq.). xygen was removed by four freeze-pump-thaw-backfill cycles in liquid nitrogen with an argon backfill. After deoxygenation, the flask was placed in an oil bath at 80 C for 36 hours. The flask was then cooled to room temperature and the contents rinsed to a round bottom flask to be concentrated to ~ ml. This solution was flocculated into ~300 ml methanol. After stirring for 6 hours, the flocculated polymer was filtered on a fine frit. Yield: 36 mg, 26%. Mw: 248; Mn: 227; PDI:.09.

33 Synthesis of poly() Compound 4 n 2 In a 2 ml custom-made rota-flo polymerization flask with stir bar, 80 mg 2-((4-((4-(- (anthracen--yl)-h-,2,3-triazol-4-yl)-2- nitrophenyl)diazenyl)phenyl)(ethyl)amino)ethylmethacrylate (Compound, 0.3 mmol, equiv), was dissolved in 6 ml dry THF. This was followed by the addition of mg of freshly recrystallized AIB (0.03 mmol, 0. eq.). xygen was removed by four freeze-pump-thawbackfill cycles in liquid nitrogen with an argon backfill. After deoxygenation, the flask was placed in an oil bath at 80 C for 36 hours. The flask was then cooled to room temperature and the contents rinsed to a round bottom flask to be concentrated to ~ ml. This solution was flocculated into ~300 ml methanol. After stirring for 6 hours, the flocculated polymer was filtered on a fine frit. Precipitation failed to adequately separate the polymer from starting material. The crude material was dissolved in CH 2 Cl 2 and loaded onto a silica plug, ethyl acetate was added to remove the monomer from the plug, once the eluent was clear, THF was added to remove the polymer. The THF portion was concentrated to ~2 ml, flocculated in 00 ml hexanes, and filtered on a fine frit. Yield: 22 mg, 2%. Mw: 2600; Mn: 94; PDI:.33.

34 Synthesis of polymer a, poly(8a) n In a 00 ml custom-made rota-flo polymerization flask with stir bar 6.0 g 2- (ethyl(phenyl)amino)ethylmethacrylate (Compound 8, 2.8 mmol, equiv) was dissolved in 60 ml dry THF. This was followed by 300 mg of freshly recrystallized AIB (.8 mmol, 0.07 eq.). xygen was removed by four freeze-pump-thaw-backfill cycles in liquid nitrogen with an argon backfill. After deoxygenation, the flask was placed in an oil bath at 80 C for 6 hours. The flask was then cooled to room temperature and the contents transferred to a round bottom flask and concentrated to ~40 ml. This solution was flocculated into L petroleum ether. After stirring for 30 minutes, the flocculated polymer was filtered on a Buchner funnel. Yield: 3 g, 0%. Mw: 8802; Mn: 383; PDI: 2.3. Synthesis of polymer 2 m -m In a L round-bottom flask containing a stir bar, 400 ml of DMF was set to cool in an ice bath. nce cool, 3.3 g poly(8a) (Compound a, 4. mmol, eq.) was added. In a separate 00 ml round-bottom flask containing a stir bar, 23 ml of acetone and 4 ml of water were added and cooled in an ice bath. nce the acetone/water solvent temperature was below C, 8 mg of 2-nitro-4-( ethynyl)aniline (0.38 mmol, 0.03 eq.) was added and dissolved, resulting in a

35 yellow solution, followed by adding 9 mg of sodium nitrite (0.28 mmol, 0.02 eq.) and ml 2 M HCl (2 mmol, 0.4 eq.). This solution was stirred for 30 minutes, forming the reactive diazonium intermediate, after which it was added dropwise to the stirring polymer in DMF solution. The solution rapidly turned orange/red and was left to react for 2 hours after which the solvent was removed under reduced pressure, the polymer was dissolved in 40 ml THF, and flocculated into. L petroleum ether. The crude polymer was redissolved in 30 ml DMF and flocculated in L of rapidly stirring water. Yield:.6 g, 48%. Mw: 0,8; Mn: 442; PDI: 2.3. Synthesis of polymer b 2 m -m In a ml round-bottom flask containing a stir bar, ml DMF, 00 mg poly(8-co-8a) (Compound, 0.2 mmol, eq.), 3 mg CuBr (0.2 mmol, eq.), 98 mg sodium ascorbate (0. mmol, 2 eq.) and µl PMDTA (0.2 mmol, eq.) were combined. The mixture was set to stir for 6 hours, after which the red DMF solution was concentrated to ~ ml and flocculated into 20 ml water. The precipitate was filtered and rinsed generously with water, then dried for 6 hours in a vacuum oven at 3 C. The dry orange filter cake was dissolved in THF, filtered through a fine frit filter and rinsed with THF. The THF filtrate was concentrated to ~ ml, flocculated into 20 ml hexanes, and filtered. Yield: 88 mg, 88%. Synthesis of polymer 6

36 2 m -m In a 00 ml round-bottom flask containing a stir bar, 30 ml DMF, 0.3 g poly(8-co-8a) (Compound,. mmol, eq.), 8 mg CuBr (. mmol, eq.), 436 mg sodium ascorbate (2.2 mmol, 2 eq.) and 230 µl PMDTA (. mmol, eq.) were combined. After the reactants dissolved, 42 mg phenyl azide (. mmol, eq.) was added and the solution was left to stir 6 hours. The red DMF solution was concentrated to ~ ml and flocculated into 20 ml water, filtered and rinsed generously with water, then dried for 6 hours in a vacuum oven at 3 C. The dry orange filter cake was dissolved in THF, filtered through a fine frit filter and rinsed with THF. The THF filtrate was concentrated to ~ ml, flocculated into 20 ml hexanes, and filtered. Yield: 28 mg, 73%. Mw: 9772; Mn: 4828; PDI: 2.02.

37 Synthesis of polymer 7 2 m -m In a 00 ml round-bottom flask containing a stir bar, 30 ml DMF, 0.3 g poly(8-co-8a) (Compound,. mmol, eq.), 8 mg CuBr (. mmol, eq.), 436 mg sodium ascorbate (2.2 mmol, 2 eq.) and 230 µl PMDTA (. mmol, eq.) were combined. After the reactants dissolved, 86 mg -azido naphthalene (. mmol, eq.) was added and the solution was left to stir for 6 hours. The red DMF solution was concentrated to ~ ml and flocculated into 20 ml water, filtered and rinsed generously with water, then dried for 6 hours in a vacuum oven at 3 C. The dry orange filter cake was dissolved in THF, filtered through a fine frit filter and rinsed with THF. The THF filtrate was concentrated to ~ ml, flocculated into 20 ml hexanes, and filtered. Yield: 244 mg, 8%. Mw: 0,392; Mn: 4670; PDI: 2.22.

38 Synthesis of polymer 8 2 m -m In a 00 ml round-bottom flask containing a stir bar, 30 ml DMF, 0.3 g poly(8-co-8a) (Compound,. mmol, eq.), 8 mg CuBr (. mmol, eq.), 436 mg sodium ascorbate (2.2 mmol, 2 eq.) and 230 µl PMDTA (. mmol, eq.) were combined. After the reactants dissolved, 29 mg 2-azido anthracene (. mmol, eq.) was added and the solution was left to stir for 6 hours. The red DMF solution was concentrated to ~ ml and flocculated into 20 ml water, filtered and rinsed generously with water, then dried for 6 hours in a vacuum oven at 3 C. The dry orange filter cake was dissolved in THF, filtered through a fine frit filter and rinsed with THF. The THF filtrate was concentrated to ~ ml, flocculated into 20 ml hexanes, and filtered. Yield: 28 mg, 86%. Mw: 93; Mn: 468; PDI: 2.0.

39 ptical Characterization of Materials All small molecules and polymers were optically characterized in dry spectral grade THF on a Cary Bio 300 UV/vis spectrophotometer to measure the absorbance spectra and λ max values. For the pump-probe laser setup, a Melles Griot Series 43 argon-ion laser was employed. The pump beam was 34 mw/cm 2 with a pump cycle of between and 0 seconds to induce isomerization and ensure sample relaxation back to the trans state. The pump irradiation time (~ ms) was fast enough to avoid heating the sample, so the kinetic measurements can be considered to have been acquired at room temperature. The probe beam was chopped mechanically at 40 Hz, attenuated to between 0.2 to 3.6 mw/cm 2 (as needed) and passed through the sample into a photodiode detector, where the intensity was recorded as a function of time. Figure S. UV-vis absorbance of diethylaniline DR (2) and ortho-dr (3) dyes in THF.

40 Figure S2. atural log of the intensity measured from the decay of the cis state of the small molecules 4 7 in THF.

41 Figure S4. Kinetic decay of the cis state of the 4 monomers 8 in THF. Figure S. atural log of the intensity measured from the kinetic decay of the cis state of monomers 8 in THF.

42 Figure S6. UV-vis spectra of clickable and clicked monomers 8 in THF.

43 Figure S7. Kinetic decay of the cis state of homopolymers, 2 4 in THF. Figure S8. atural log of the intensity measured from the kinetic decay of the cis state of homopolymers 2 4 in THF.

44 Figure S9. UV-vis spectra of the three homopolymers of clicked phenyl 2, napthyl, and anthracyl 4. All show identical λ max to their monomer counterparts at 466 nm. Figure S0. atural log of the intensity measured from the kinetic decay of the cis state in the copolymers 8 in THF.

45 Figure S. UV-vis spectra of unclicked and clicked copolymers 8 in THF, including expanded view of the azobenzene absorbance peak.

46 Figure S2. atural log of the intensity measured from the kinetic decay of the cis state of copolymers 8 in THF.

47 Figure S. Top down AFM view of an SRG written into a thin film of polymer.

48 Figure S4. UV/vis traces of isomerization extent in films of polymer 2,, 8 spun cast on glass from THF solution, demonstrating an isomerization extent of % under irradiation from a 488 nm Ar+ laser at a power of 0 mw/cm 2. The sharp feature at 488nm is due to scattering from the laser light.

49 Figure S. Pump-probe laser set-up to determine kinetics of cis-trans thermal reconversion.

50 Table. Extinction coefficients of all dyes measured in this study Compound ε (M - cm - ) 2,280 3, ,430 32, , , , , ,320 42, ,00 26,770 4,660.37* b.7* 6.* 7.32* 8.8* * Extinction coefficient measured as (g - cm - L).

51 Table 2. Molecular weight of all polymers used in this study as measured against a polystyrene standard in tetrahydrofuran. Compound Mw (g/mol) 2 3,60 2, ,600 0,80 6 9, , ,30

52 References. K. G. Yager and C. J. Barrett, J. Chem. Phys., 2004, 20,