The design of new photochromic polymers incorporating covalently or ionically linked spiropyran/polyoxometalate hybrids

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1 Electronic Supplementry Mteril (ESI) for Journl of Mterils Chemistry C. This journl is The Royl Society of Chemistry 2017 The design of new photochromic polymers incorporting covlently or ioniclly linked spiropyrn/polyoxometlte hybrids Irene Bzzn, Ptrici Bolle, b Olivier Oms, * Hnène Slmi, c Ndine Aubry-Brroc, c Anne Dolbecq, Hélène Serier-Brult, b Rémi Desspt, *b Philippe Roger, *c nd Pierre Milne Institut Lvoisier de Versilles, UMR 8180, Université Pris-Scly, Université de Versilles Sint-Quentin en Yvelines, 45 Avenue des Etts-Unis, Versilles cedex (Frnce). b Institut des Mtériux Jen Rouxel (IMN), Université de Nntes, CNRS, 2 rue de l Houssinière, BP 32229, Nntes cedex 3, Frnce. c Institut de Chimie Moléculire et des Mtériux d Orsy (ICMMO), UMR 8182, Université Pris Sud, CNRS, Université Pris-Scly, Orsy, Frnce. Supplementry Figures nd Tble: Figure S1 : 13 C NMR spectrum of (TBA) 3 [SP-POM-MA]. Figure S2 : 1 H NMR spectrum of (TBA) 3 [SP-POM-MA]. Figure S3 : ATR-IR spectr of (TBA) 3 [SP-POM-NH 2 ] nd (TBA) 3 [SP-POM-MA]. Figure S4 : ESI/MS spectrum of (TBA) 3 [SP-POM-MA]. Figure S5 : 1 H NMR spectrum of poly(sp-pom-ma-co-ma). Figure S6 : ATR-IR spectr of PMMA nd poly(sp-pom-ma-co-ma). Figure S7 : SEC HPLC volume of elution of poly(sp-pom-ma-co-ma). Figure S8 : XPS nlysis of PMMA nd poly(sp-pom-ma-co-ma). Figure S9 : ATR-IR spectr of polydmaema nd polydmaema +. Figure S10 : 1 H NMR spectrum of polydmaema. Figure S11: SEC HPLC volume of elution of polydmaema.

2 Figure S12 : 1 H NMR spectrum of polydmaema +. Figure S13 : 1 H NMR spectrum of poly(sp-pom-sp-dmaema + ). Figure S14 : XPS nlysis of polydmaema +. Figure S15 : ATR-IR spectr of polydmaema + nd poly(sp-pom-sp-dmaema + ). Figure S16 : Kubelk-Munk trnsformed reflectivity vs wvelength of poly(sp-pom-maco-ma) nd poly(sp-pom-sp-dmaema + ). Figure S17 : Photochromic effect of poly(sp-pom-ma-co-ma) nd temporl evolution of its photogenerted bsorption. Tble S1 : Photochromic kinetic prmeters t room temperture of poly(sp-pom-ma-co- MA) nd SP-POM-NH 2 -mix-pmma.

3 Experimentl section NMR spectr were recorded t 298 K on Bruker Advnce 300 spectrometer operting t 300 MHz for 1 H nd 50 MHz for 13 C nuclei. Chemicl shifts re expressed in prts per million (ppm) downfield from internl TMS. The following bbrevitions re used: s, singlet; d, doublet; t, triplet; m, multiplet. Infrred spectr (ATR) were recorded on n IRFT Nicolet 6700 pprtus. Reltive intensities re given fter the wvenumber s vs = very strong, s = strong, m = medium, w = wek, sh = shoulder, br = brod. Elementl nlyses were performed by the Service de Micronlyse of CNRS, Gif-sur-Yvette, Frnce. TGA experiments were performed with Seiko TG/DTA 320 thermogrvimetric blnce (2 C/min, under N 2 tmosphere). Electrospry ioniztion (ESI) mss spectr were recorded on Xevo QTof WATERS (qudrupoletime-of-flight) instrument. The temperture of the source block ws set to 120 C, nd the desolvtion temperture to 200 C. A cpillry voltge of 1 kv ws used in the negtive scn mode, nd the cone voltge ws set to 10 V to control the extent of frgmenttion of the identified species. Mss clibrtion ws performed using solution of sodium formte in wter:cetonitrile (2:8) from m/z 50 to Smple solutions 50 µmol/l in cetonitrile were injected vi syringe pump directly connected to the ESI source t flow rte of 20 μl/min. XPS mesurements were performed on K-Alph spectrometer from ThermoFisher, equipped with monochromted X-ry Source (Al K lph, ev). For ll mesurements spot size of 400 μm ws employed. The hemisphericl nlyzer ws operted in CAE (Constnt Anlyzer Energy) mode, with pss energy of 200 ev nd step of 1 ev for the cquisition of surveys spectr, nd pss energy of 50 ev nd step of 0.1 ev for the cquisition of high resolution spectr. A dul bem flood gun ws used to neutrlize the chrge build-up. The spectr obtined were treted by mens of the Avntge softwre provided by ThermoFisher. A Shirley type bckground subtrction ws used nd the pek res were normlized using the Scofield sensitivity fctors in the clcultion of elementl compositions. The binding energies were clibrted ginst the C1s binding energy set t

4 284.8 ev. The peks were nlyzed using mixed Gussin-Lorentzin curves (70% of Gussin chrcter). Diffuse reflectnce spectr were collected t room temperture on finely ground smple with Cry 5G spectrometer (Vrin) equipped with 60 mm dimeter integrting sphere nd computer control using the Scn softwre. Diffuse reflectnce ws mesured from 250 to 1550 nm with 2 nm step using Hlon powder (from Vrin) s reference (100% reflectnce). The reflectnce dt were treted by Kubelk-Munk trnsformtion 1 to obtin the corresponding bsorption dt. The photocolortion nd fding kinetics were quntified by monitoring the temporl evolution of the photogenerted bsorption Abs 580 (t) defined s Abs 580 (t) = -log(r 580 (t)/r 580 (0)), where R 580 (t) nd R 580 (0) re the reflectivities t the time t nd t t = 0, respectively. For the colortion kinetics, the smples were irrdited with Fisher Bioblock lbosi UV lmp (λ ex = 365 nm, P = 6W) t distnce of 50 mm. Abs 580 (t) vs. t plots hve been fitted ccording to biexponentil rte lw Abs 580 (t) = (A 1 + A 2 ) - A 1 exp(-k c 1t) - A 2 exp(-k c 2t), with k c 1 nd k c 2 the extrcted colortion rte constnts. For the bleching processes, the smples were first irrdited under 365 nm-uv excittion until the photoinduced bsorptions rech sturtion. Then, the compounds were put under Thorlbs LED Arry light sources (590 nm W/cm 2 ) t distnce of 100 mm. The bleching kinetics were determined t room temperture by monitoring the temporl decys of Abs 580 (t) of smples once irrdited. Abs 580 (t) vs. t plots hve been fitted ccording to biexponentil rte lw Abs 580 (t) = (A 0 - A 1 - A 2 ) + A 1 exp(-k f 1t) + A 2 exp(-k f 2t), with k f 1 nd k f 2 the extrcted fding rte constnts. 1 Kubelk, P.; Munk, F. Z. Techn. Physik, 1931, 12, 593.

5 * * ppm Figure S1: 13 C NMR spectrum in CD 3 CN of (TBA) 3 [SP-POM-MA]. (*refer to the signls of two different mide functions present in the unsymmetricl hybrid POM). ppm * * ppm Figure S2: 1 H NMR spectrum in CD 3 CN of (TBA) 3 [SP-POM-MA] (*refer to the signls of the vinylic protons of the MA group)

6 Wvenumbers (cm-1) Figure S3 : ATR-IR spectr of (TBA) 3 [SP-POM-NH 2 ] (red line) nd (TBA) 3 [SP-POM-MA] (blue line)

7 ES/MS spectrum of (TBA) 3 [SP-POM-MA] Top: Experimentl spectrum, bottom: simulted spectrum (relted to [M+TBA] 2- signl) Top: Experimentl spectrum, bottom: simulted spectrum (relted to [M+H] 2- signl) Composition Formul Clculted Observed [M+TBA] 2- MnMo 6 O 29 C 49 H 74 N [M+H] 2- MnMo 6 O 29 C 33 H 39 N Figure S4: ESI/MS spectrum of (TBA) 3 [SP-POM-MA].

8 Protons relted to the end groups of the polymer chin Figure S5 : 1 H NMR spectrum in CDCl 3 of poly(sp-pom-ma-co-ma). * Figure S6 : ATR-IR spectr of PMMA (red line) nd poly(sp-pom-ma-co-ma) (blue line) copolymer. (*refers to Mo-O-Mo vibrtion bnd)

9 () Elution Volume (ml) (b) 0.0E E E E E E E+05 MW (g/mol) Figure S7: SEC HPLC () volume of elution nd (b) molr weight distribution in THF eluent of PMMA (blck line) nd poly(sp-pom-ma-co-ma) (green line).

10 Counts / s Counts / s Corbs/s 1.80E E+05 O 1s 1.40E+05 C 1s 1.20E+05 () 1.00E E+04 Auger C Auger O 6.00E E E E Binding Energy (ev) E E+05 O 1s 1.20E+05 C 1s 1.00E+05 (b) 8.00E+04 Auger C Auger O 6.00E E+04 N 1s+Mo3p 2.00E+04 Mo 3d Si2s Si2p 0.00E Binding Energy (ev) E E+04 C1s C-C sp3 1.50E+04 C1s C-O (c) C1s 1.00E+04 C1s O-C=O 5.00E E Binding Energy (ev) Figure S8 : Survey spectr of XPS nlysis for: () PMMA nd (b) poly(sp-pom-ma-co- MA); (c) zoom for C1s energies pttern of poly(sp-pom-ma-co-ma): recovered spectrum (blck line) nd enveloped spectrum (red line).

11 Wvenumbers (cm-1) Figure S9 : ATR-IR spectr of polydmaema (red line) nd polydmaema + (blue line). Figure S10 : 1 H NMR spectrum in CD 3 CN of polydmaema.

12 () Elution volume (ml) (b) 0.00E E E E+04 MW (g/mol) Figure S11 : SEC HPLC () volume of elution nd (b) molr weight distribution in THF eluent of polydmaema. Figure S12 : 1 H NMR spectrum in D 2 O of polydmaema +.

13 Counts / s Counts / s Counts / s Figure S13 : 1 H NMR spectrum in D 2 O of poly(sp-pom-sp-dmaema + ). 1.20E+05 () C 1s 1.00E+05 O 1s 8.00E E+04 Auger C Auger O N1s Br3p Br3p 4.00E+04 Br3s 2.00E E Binding Energy (ev) (b) C1s 1.80E E E E E E E E E E C1s C-C sp3 C1s C-O C1s O-C=O Binding Energy (ev) 280 (c) N1s 7.00E E E E E E E E E N1s R 3-N+ N1s N-C Binding Energy (ev) Figure S14: () Survey spectrum of XPS nlysis for polydmaema + ; zoom for (b) C1s nd (c) N1s energies pttern (in blck recovered spectrum, in red enveloped spectrum).

14 /S /S Wvenumbers (cm-1) Figure S15: ATR-IR spectr of polydmaema + (red line) nd poly(sp-pom-sp- DMAEMA + ) (blue line) () * (b) Wvelength (nm) * Figure S16: Kubelk-Munk trnsformed reflectivity vs wvelength of () (TBA) 3 [SP-POM- NH 2 ] (red line), PMMA (blue line), nd poly(sp-pom-ma-co-ma) (blck line), (b) (TBA) 3 [SP-POM-SP] (red line), polydmaema + (blue line) nd poly(sp-pom-sp- DMAEMA + ) (blck line). The bsorption bnd of the merocynine coloured form is noted by n sterisk.

15 () (b) Figure S17. () Photogrphs of the powder of poly(sp-pom-ma-co-ma) t different time during the colortion process under 365-nm UV irrdition t room temperture. (b) Temporl evolution of the photogenerted bsorption of poly(sp-pom-ma-co-ma) fter 0, 0.166, 0.333, 0.5, 1, 2, 3, 4, nd 5 min of 365 nm-uv irrdition. Tble S1. Photochromic kinetic prmeters t room temperture of poly(sp-pom-ma-co- MA), nd SP-POM-NH 2 -mix-pmma. Compound Photocolortion process A 1 A 2 k c (s -1 ) b k c (s -1 ) b t 1/2 (min) c R 2 d poly(sp-pom-ma-co-ma) SP-POM-NH 2-mix-PMMA Compound Therml fding process in the drk A 0 A 1 A 2 k f (s -1 ) b k f (s -1 ) b t 1/2 (min) c R 2 d poly(sp-pom-ma-co-ma) SP-POM-NH 2-mix-PMMA Compound Fding process under visible-light irrdition ( ex = 590 nm) A 0 A 1 A 2 k f (s -1 ) b k f (s -1 ) b t 1/2 (min) c R 2 d poly(sp-pom-ma-co-ma) SP-POM-NH 2-mix-PMMA The Abs 580 (t) vs t plots were fitted s Abs 580 (t) = (A 1 +A 2 ) - A 1 exp( k c 1t) - A 2 exp( k c 2t) for the colortion process nd s Abs 580 (t) = (A 0 A 1 A 2 ) + A 1 exp( k f 1t) + A 2 exp( k f 2t) for the fding ones. b Colortion (k c ) nd fding (k f ) rte constnts. c For the colortion process, the hlf-life time t 1/2 is defined s the UV irrdition time required for Abs 580 (t) to rech hlf of its mximum vlue. For the fding ones, t 1/2 is defined s the irrdition time required for Abs 580 (0) to rech the A 0 A 1 A 2 )/2 vlue. d Regression coefficient for the Abs 580 (t) vs t plots.