Supplementary Material (A)

Transcription

1 Supplementary Material (A) Spirooxazine photochromic performance. 16 Asorance 1. T 1/ = 1 s T / = 110 s T 1/ = 9 s T / = 0 s Time (seconds) a, Coloration and fade speeds otained with PEG oligomer. and in standard polymer (Tg =10 ºC, 1: 9G:nouryset 110) Asorance T 1/ = s T / = 6 s T 1/ = s T / = 1 s Time (seconds) 000, Coloration and fade speeds dye- PDMS oligomer conjugate with a different point of attachment on the spirooxazine. and in standard polymer (Tg =10 ºC, 1: 9G:nouryset 110). 00 ature Pulishing Group

2 Supplementary Material (B) MR spectroscopic oservation of dye-oligomer associations. Experimental. Spectra were recorded on Bruker DMX 00 and DMX 600 spectrometers fitted with 1 H- 1 P-BB TBI-Z and 1 H- 1 C- 1 TXI XYZ proes respectively. Temperature control was maintained using a standard Bruker variale temperature unit employing a liquid nitrogen evaporator to achieve the temperatures of 19 and K. Standard gradient DQF-CSY, HSQC and HMBC experiments were acquired for resonance assignment purposes. RESY type two-dimensional experiments were used to elucidate through space interactions. The mixing time in the RESY experiments was maintained at 00ms at 19K and 0ms at K. For quantitative work involving extraction of internuclear distances, a compensated RESY experiment was employed as descried previously (Griesinger, C. & Ernst, R. R. J. Mag. Res. ( ) 7, (1987)). UV Irradiation using a Mercury ARC Lamp The irradiation setup has een descried previously (Geftakis, S. &Ball. G. E. Direct servation of a Transition Metal Alkane Complex, CpRe(C) (cyclopentane), Using MR Spectroscopy. J. Am. Chem. Soc., 10, (1998)). Irradiation was achieved using a 100W riel research arc lamp, coupled via condenser to an optical fire. Focus and mirror were optimised and 00 0mW of power at nm was otained at the sample end of the optical fire, a 7m long, 100micron core, nonsolarizing UV transmitting fire (Ceramoptec P/ SMA1P/UV100/1600- S/7.0M) Experimental Setup In a typical experiment,, (10mg) (for example) was dissolved in d 6 -acetone (0.7g) to create a 1.9 mm solution at room temperature. The free oligomer samples (where spirooxazine and oligomer were separate), the mass of oth and oligomer reflected the molar ratios present in the attached oligomer samples 1 and. Samples were frozen in liquid nitrogen within their septa sealed MR tues and placed under a vacuum. The sample was then isolated and allowed to thaw in an effort to remove entrained oxygen within the sample which could interfere y causing oxidation whilst under UV irradiation. itrogen was then pumped into the head space aove the solution prior to MR analysis. The fire optic was placed through the septa at approximately 1mm aove the surface of the solution. The MR proe containing sample was then cooled to 19K for. A higher temperature of K was required for 1 to prevent precipitation. Spectra were collected efore, during and after photoirradiation of the sample. 00 ature Pulishing Group

3 Supplementary Material (C) MR spectroscopic oservation of dye-oligomer associations. Compound 1. Spirooxazine and PDMS interactions in solution. H 1 H etc a, Summary of PDMS oligomer key interactions with 1 merocyanine form of the spirooxazine. enlarged RE etween mid methylenes on PDMS chain and H at position 1. H , RESY D MR experiment. Interaction of alkyl spacer of PDMS oligomer with indole H of coloured form of spirooxazine (1). Aromatic hydrogens H Interactions of dimethylsiloxane hydrogens Interactions of mid-methylenes of alkyl spacer c, Compensated RESY D experiment (0 ms). The general interaction of the oligomer with H and aromatic hydrogens of coloured form of spirooxazine (1) indicating the localization of the oligomer. These interactions were not visile in the control experiment where spirooxazine and PDMS were not attached to each other. Cross peaks due to unconverted colourless form are also present due to incomplete conversion, in particular intense peaks from H8 and/or H9 to H and H laelled with. 00 ature Pulishing Group

4 Supplementary Material (D) MR spectroscopic oservation of dye-oligomer associations. Compound. Spirooxazine and PEG interactions in solution. Strong RE Weaker RE a, Summary of PEG chain interactions with merocyanine form. RE I c RE II Irradiate enhancement # # , Specific PEG chain interactions with gem dimethyl groups of merocyanine form. Top spectrum is a slice through the protons laelled from the RESY experiment. Middle spectrum is a synthesised spectrum with clear form of spirooxazine sutracted. Bottom spectrum is the original spectrum of oth clear (spirooxazine) and coloured (merocyanine) form of. c, Specific PEG chain interactions with aromatic hydrogens on indole and naphthyl parts of merocyanine form. Top spectrum is the same slice as from the RESY experiment. Middle spectrum is a synthesised spectrum with clear form of spirooxazine sutracted. Bottom spectrum is the original spectrum of oth clear (spirooxazine) and coloured (merocyanine) form of. The first PEG unit interaction with the opposite side of the spirooxazine is readily identifiale ecause of its asymmetrical chemical environment. Due chemical similarity of all the other PEG units in the oligomer, it is not possile to unamiguously assign other PEG interactions with the spirooxazine to specific locations in the chain. The polar nature oth of the PEG oligomer and the coloured from of the spirooxazine make it likely the rest of the PEG oligomer will e localised around the dye. 00 ature Pulishing Group

5 Supplementary Material (E) Synthesis of 9 -(PDMS(8)-undecoyl)-1,,-trimethylspiro[indoline-, - [H]naphtha[,1-][1,] oxazine] Hydroxy-1,,-trimethylspiro[indoline-, -[H]naphtha[,1-][1,]oxazine] (1g,.9 mmoles) and triethylamine (0.9 ml, 6 mg, 6. mmoles) were added together in dichloromethane (0 ml) and then poly(dimethylsiloxane) monocaroxydecoyl chloride terminated (.0 g,.8 mmol) in dichloromethane was added dropwise to the solution at room temperature under argon protection. The reaction was monitored y tlc (DCM or ether:hexane 1:1) and was completed after a few hours. The reaction was worked up y washing with water, rine (plus a little of very dilute HCl to reak the emulsion), and dried (MgS ) efore evaporation to a dark liquid. The oil was chromatographed on silica with ether:hexane (1:) to give.1 g ( %) of pale rown green oil as the desired product. A second slower fraction (00 mg) was otained that was spectroscopically similar to the product except it had a vinyl (terminal) group and had much less DMS content. 1 H MR (acetone-d6)(shown elow) δ = 9 (d, J = 1.8 Hz, - Me), 0.10 (d, J = 1.8 Hz, -Me), 0.1 (d, J = 1.8 Hz, -Me), 0.1 (s, -Me), 0.6 (mult., H, alkyl), 0.90 (mult., H, alkyl), (mult, H, 9,10-H, alkyl, CH-CH), 1.0 (mult, H, c -H), 1.80 (pent., J = 7. Hz), H, -H),.68 (t, J = 7. Hz, H, a -H),.77 (s, H, 8-H), 6.6 (d, J = 7.8 Hz, 7-H), 6.87 (t, J = 7. Hz, -H), 7.0 (d, J = 8. Hz, -H), 7.1 (d, J = 7. Hz, -H), 7.19 (apparent t, H, 6 & 8 -H), 7.80 (d, J = 9.Hz, 6 -H), 7.8 (s, H), 7.86 (d, J = 8.6Hz, 7 -H), 8. (d, J =. Hz, 10 -H). MS (FAB), M+ 168 (100%) (corresponds to 11 DMS units in oligomer), 11.9 (90%)(corresponds to 8 DMS units in oligomer), 191. (8%)(corresponds to 1 DMS units in oligomer, 9.6 (corresponds to DMS units in oligomer), 181. (corresponds to 17 DMS units in oligomer). Peaks for all other oligomer lengths etween -19 DMS units were also oserved in a small ell curve distriution centred around 1 DMS units (1 MDS 0% of M+ with other peaks eing smaller) ,10 ' 10' 8 ' 6' a c 8' 7' ' -Me 10' 7' 6' 6,8' ' 7 8 9,10 acetone-d dcm a c aliphatic ature Pulishing Group