Polyethylenes Bearing a Terminal Porphyrin Group

Transcription

1 Polyethylees Bearig a Termial Porphyri Group Miriam M. Uterlass, a Edgar Espiosa, a Ferade Boisso, b Frack D Agosto,*,a Christophe Boisso,*,a Katsuhiko Ariga, c,d Iva Khalakha, c,e Richard Charvet, c Joatha P. Hill c,d a Uiversité de Lyo, Uiv. Lyo, CPE Lyo, CNRS UMR 565 Laboratoire de Chimie Catalyse Polymères et Procédés (CP), LCPP team, Bat 308F, 43 Bd du ovembre 98, F-6966 Villeurbae, Frace. Fax: (+33) ; Tel: (+33) ; dagosto@lcpp.cpe.fr; boisso@lcpp.cpe.fr b Service commu de RMN du Réseau des Polyméristes Lyoais, CNRS/UMR53, INSA de Lyo, IMP, 0 aveue Albert Eistei 696 Villeurbae Cedex, Frace. c WPI-Ceter for Materials Naoarchitectoics, Natioal Istitute of Materials Sciece (NIMS), Namiki -, Tsukuba, Ibaraki, , Japa. d JST-CREST, Namiki -, Tsukuba, Japa. e Departmet of Surface ad Plasma Sciece, Faculty of Mathematics ad Physics, Charles Uiversity, V Hole_sovi_ck_ach, Praha 8, Czech Republic. SUPPORTING INFORMATION MATERIALS Toluee was distilled over sodium/bezopheoe. Butyloctylmagesium (0% solutio i heptae, Crompto), dimethylformamide (DMF, Sigma-Aldrich, 99.8%), d 8 - toluee (euriso-top, H O<0.0%, 99.5% D), copper(i) bromide (Aldrich, 98%), N,N,N,N,N - petamethyleediethyleetriamie (Aldrich, 99%) were used as received. ANALYTICAL TECHNIQUES High-resolutio liquid NMR spectroscopy was carried out with a Bruker DRX 400 spectrometer operatig at 400 MHz for H ad MHz for 3 C. Spectra were obtaied with a 5-mm QNP or a PSEX 0-mm probe at 363K. Polymer samples were examied as 0-5 %(w/v) solutios. A mixture of tetrachloroethylee (TCE) ad perdeuterobezee (C 6 D 6 ) (/ v/v) was used as solvet. Chemical shift values ( ) are give i ppm i referece to iteral tetramethylsilae (TMS). A coaxial tube cotaiig D O was also used for some specific samples with TMS as referece ad experimet were i this case performed at 353K. High temperature SEC aalyses were performed usig a Waters Alliace GPCV 000 chromatograph equipped with three colums ( Styragel HT6E ad Styragel HT). Samples ( mg.ml - ) were eluted with trichlorobezee with a flow rate of ml.mi - at 50 C. Olie detectio was performed by refractometry ad viscosimetric measuremets usig Waters equipmets.

2 MALDI-TOF mass spectrometry aalyses were recorded i the liear ad the reflectro mode usig a Applied Biosystems Voyager DE-STR equipmet usig a itroge laser (wavelegth 337 m) ad a acceleratig voltage of 0 kv. The positive ios were detected i all cases. The spectra were the sum of 00 shots, ad a exteral mass calibratio was used (mixture of peptides stadards, Sequazyme kit). The samples were deposited o a stailess steel target ad dried. Samples were prepared by dissolvig the polymer i freshly distilled tetrahydrofura (THF) at a cocetratio of 0 g.l -. The matrix was used without further purificatio ad dissolved i distilled THF (0 g.l - ). The samples were prepared by mixig a solutio of polymer i THF (0 mg.ml - ), a solutio of matrix i THF (0 mg.ml - ), with a volumetric ratio i the ratio /0 (Vsample/Vmatrix). ml of the resultig mixture was placed oto the sample plate ad the solvet was evaporated at room temperature. FT-IR aalyses were carried out i a Nicolet 460 FT-IR spectrometer at room temperature over 3 scas (sesibility rage cm - ). UV-Vis spectroscopy (reflectace mode) was carried out usig a Perki Elmer PE950 (sesibility rage m). Scaig electro microscopy (SEM) images were obtaied usig a Hitachi S4800 Field Effect SEM operatig at a acceleratig voltage of 5kV. Samples for SEM were dropped oto a passified silico substrate dried i vacuo the coated with platium (~ 4 m) usig a Hitachi 030 Io Sputterer. Atomic force microscopy (AFM) images were obtaied usig a Seiko Istrumets SPA400-SPI4000 equipped with a calibrated 0- m xy-sca rage ad a 0 m z- sca rage PZT-scaer. All AFM images were take i dyamic force mode at optimal force. Samples for AFM were dropped oto a passified silico substrate ad dried i vacuo prior to measuremet. Rectagular shaped silico catilevers (Tip radius: ~0 m; SI-DF0; Seiko Istrumets Ic.), with sprig costat of N/m ad resoace frequecy of khz, were used for imagig i air. Powder X-ray diffractio data was collected from freshly crystallised (toluee) samples usig a Rigaku RINT 000 diffractometer ad Cu K( ) radiatio ( = Å). Samples were spread o a specially prepared glass plate. METHODS

3 Sythesis of (C 5 Me 5 ) NdCl Li(OEt ). The eodymocee based catalyst was sythesized followig coditios depicted i the literature. Polymerizatio procedure. Ethylee polymerizatio was carried out i toluee i a 500 ml reactor coectig to a ethylee reservoir equipped with a pressure sesor. The reactor was charged with a mixture of the chloroeodymocee complex (C 5 Me 5 ) NdCl Li(OEt ) ) ( mol.l - ), ad butyloctylmagesium (BOMg) i a 400 ml toluee solutio. The molar ratio Mg/Nd was adjusted with respect to the targeted molar mass (Mg/Nd = 00). The solutio was rapidly set to the polymerizatio temperature (80 C) ad the to a ethylee pressure of 3 bar. The cosumptio rate of ethylee was measured from the observed drop of pressure i the reservoir. The molar ratio ethylee to BOMg was cotrolled accordig to this measure i order to reach the targeted molar mass. A o fuctioal polyethylee (PE) was prepared accordig to this procedure for referece sake (M = 670 g/mol, PDI =.) Sythesis of iodie ed-fuctioalized polyethylee (PE-I) Oce ethylee polymerizatio is assumed to have reached completio, the reactor is degassed with argo before 50 ml of freshly distilled THF is itroduced. After coolig to room temperature by exteral water circulatio, the suspesio obtaied is the flushed ito a -litre three-ecked flask uder argo atmosphere. Iodie solutio (4 eq. I /Mg, i 50 ml THF) is added drop wise for 0 mi at 0 C uder vigorous magetic stirrig, ad the reactor is allowed to come back to room temperature for two hours. The the mixture is poured ito a large amout of methaol ad collected by filtratio. After washig 3 times with 00 ml methaol, the precipitate is dried uder reduced pressure for 0 hours. A fie white powder was the recovered (Fuctioality = 96.8%) accordig to H NMR aalysis. 3 I T. Do Tilley, T. ; Aderse, R.A. Iorg. Chem. 98, 0,

4 H NMR 400 MHz (TCE/C 6 D 6, 363K, ppm) δ 0.95 (H, t, J = 7 Hz);.30 (H, br);.7 (H3, qt, J = 7Hz);.0 (H5, m); 3.00 (H4, t, J = 7 Hz), 4.90 (H7, m); 4.96 (H7, m); 5.77 (H6, m).

5 Sythesis of azide ed-fuctioalized polyethylee (PE-N 3 ), PE-I, NaN 3 (. eq/pe-i) ad 50 ml DMF are mixed together i a 00 ml threeecked flask, ad the suspesio obtaied is the heated up 50 C i DMF. The mixture is observed to remai biphasic, with a molte polyethylee phase floatig i the DMF. After 4 h, the suspesio is cooled to room temperature. Polyethylee graules formed are crushed before washig with methaol ad dryig as previously described. Fuctioality = 90% as determied by H NMR N H NMR 400 MHz (TCE/C 6 D 6, 363K, ppm) δ 0.95 (H, t, J = 7 Hz);.30 (H, br);.47 (H3, J = 7 Hz);.0 (H5, m); 3.04 (H4, t, J = 7 Hz); 4.90 (H7, m); 4.96 (H7, m); 5.77 (H6, m). Sythesis of 4-bromobezaldehyde (7.4 g, 0.04 mol), 3-methyl--buty-3-ol (5.8 ml, 0.06 mol), CuI (0.46 g,.4 mmol) ad Pd(PPh 3 ) 4 (.4 g,. mmol) were take i dry toluee (75 ml) uder N atmosphere. After 3 freeze-pump-thaw cycles, diisopropylamie (5.7 ml) was added o the froze mixture which was agai submitted to 3 freeze-pumpthaw cycles. After stirrig at RT uder N atmosphere for 4 h, dichloromethae was added ad the orgaic phase washed with water (x3), dried with Na SO 4 ad cocetrated. Upo silica gel colum chromatography (CH Cl /hexae, 0/), the desired compoud was isolated as a viscous yellow pale oil which solidified o stadig upo to give a white solid (A). Yield: 7.9 g (97 %).

6 O OH A H NMR (CDCl 3 ) d:.64 (s, 6H, CH 3 ),.4 (s, H, OH), 7.56 (d, J = 8 Hz, H, Ar), 7.8 (d, J = 8 Hz, H, Ar), 0.00 (s, H, C To a mixture of A (6.6 g, mol) ad bezaldehyde (6.8 ml, mol) i refluxig propioic acid (500 ml) was added pyrrole (6.9 ml, 0. mol). After refluxig i air for 3 h, the mixture was cooled dow ad propioic acid removed by vacuum distillatio. Upo silica gel chromatography (CH Cl /hexae, 0/), the target compoud was isolated as a shiy purple solid (B). Yield:.53 g (8.8 %). NH N OH N HN B H NMR (CDCl 3 ) d: -.7 (s, H, NH),.8 (s, 6H, CH 3 ), 7.78 (m, 8H, Ar), 7.86 (m, 3H, Ar), 8.5 (m, 8H, Ar), 8.9 (m, 8H, b-h).

7 A mixture of B (.3 g,.87 mmol) ad KOH (80 mg, 5 mmol) i -isopropaol (00 ml) was refluxed uder N for 6 h. The mixture was the cooled dow ad cocetrated. Upo silica gel colum chromatography (CH Cl /hexae, /), the target compoud was isolated as a purple solid. Yield:. g (90 %). NH N N HN H NMR (CDCl 3 ) d: -.7 (s, H, NH), 3.7 (s, H, acetylee), 7.80 (m, 8H, Ar), 7.9 (m, 3H, Ar), 8.4 (m, 8H, Ar), 8.89 (m, 8H, b-h). 3 C NMR (CDCl 3 ) d: 78.5, 83.90, 00.73, 9.7, 0.55, 0.66,.83, 6.93, 7.98, 30.9, 30.73, 34.70, 34.78, 4.6, 4.3, Sythesis of PE-Por 0.085g of PE-N 3 (00 g.mol -, PDI =., Fuctioality = 90%) were dissolved i.5ml of toluee at 0 C. Simultaeously two flasks cotaiig 83mg of CuBr, 5.9mg of PMDETA ad 54.mg of, were prepared ad heated up to 0 C, too. I flask: CuBr ad PMDETA i ml of toluee, i flask: i ml of toluee. Whe heated up to reactio temperature, the cotet of flask has bee ijected ito flask. This mixture was kept stirrig for miute at 0 C ad the added drop wise to the PE-N 3 solutio. The reactio mixture was kept stirrig 40mi at 0 C ad the allowed to slowly cool back to RT. The purple crystallie product has bee precipitated with methaol (900mL), filtered ad dried overight at 40 C uder reduced pressure. 0.0g of PE-Por were obtaied.

8 Correspodig FTIR, H ad 3 C NMR, MALDI-ToF mass spectrometry aalyses are give below. Figure S: IR spectrum of PE-N 3 (red) ad PE-Por (blue).

9 H H Cu H H ppm * * ppm H N N N Cu Figure S: H NMR aalysis (400MHz, C 6 D 6 /TCE:/ v/v, 8 scas) of PE-Por. Assigmets of the resoaces betwee 5 ad 6 ppm to eyes compouds. *: solvet impurities.

10 A * * ppm NAM EXP PRO Dat Tim INS PRO PUL TD SOL NS DS SWH FID AQ RG DW DE TE D0 D IN === NUC P PL PL SFO ND0 TD SFO FID SW FM SI SF WDW SSB LB GB PC SI MC SF WDW SSB LB GB ppm

11 B * * ppm ppm Figure S3: 50 MHz H correlatio spectroscopy (COSY) of PE-Por i C 6 D 6 /TCE=: at 90 C, 6 scas. A. Correlatio betwee proto ad the protos of the mai chai. B. Correlatio betwee the proto i positio to the eye ad the protos of the mai chai. *: solvet impurities.

12 Electroic Supplemetary Material (ESI) for Chemical Commuicatios a ppm Zoe a: N Cu 6 6 Aromatic Cq b Aromatic CH Aromatic CH NAME EEPEPorb EXPNO 4 PROCNO Date_ Time 0.9 INSTRUM spect PROBHD 0 mm PASEX 3 PULPROG zgpg70_cc TD SOLVENT C6D6 NS 644 DS 8 SWH FIDRES AQ RG 050 DW.600 DE 0.00 TE D D L3 TD0 ======== CHANNEL f ==== NUC 3C P 4.0 PL -.50 PLW SFO ======== CHANNEL f ==== CPDPRG bi_waltz65_64pl NUC H PCPD PL PL 4.06 PL PL PL PLW PLW PL3W PL30W PL3W SFO SI 3768 SF WDW EM SSB 0 LB.00 GB 0 PC NAME.40 EEPEPorb EXPNO 4 PROCNO Date_ Time 0.9 INSTRUM spect PROBHD 0 mm PASEX 3 PULPROG zgpg70_cc TD SOLVENT C6D6 NS 644 DS 8 SWH FIDRES AQ RG 050 DW.600 DE 0.00 TE D D L3 TD0 ======== CHANNEL f === NUC 3C P 4.0 PL -.50 PLW SFO ======== CHANNEL f === CPDPRG bi_waltz65_64p NUC H PCPD PL PL 4.06 PL PL PL PLW PLW PL3W PL30W PL3W SFO SI 3768 SF WDW EM SSB 0 LB.00 GB 0 PC ppm

13 Electroic Supplemetary Material (ESI) for Chemical Commuicatios S S 3S 4S Zoe b: N Cu NAME EEPEPorb EXPNO 4 PROCNO Date_ Time 0.9 INSTRUM spect PROBHD 0 mm PASEX 3 PULPROG zgpg70_cc TD SOLVENT C6D6 NS 644 DS 8 SWH Hz FIDRES Hz AQ sec RG 050 DW.600 usec DE 0.00 usec TE K D sec D sec L3 TD0 ======== CHANNEL f ======== NUC 3C P 4.0 usec PL -.50 db PLW W SFO MHz 3S 4S, S S ======== CHANNEL f ======== CPDPRG bi_waltz65_64pl NUC H PCPD usec PL db PL 4.06 db PL db PL db PL db PLW W PLW W PL3W W PL30W W PL3W W SFO MHz SI 3768 SF MHz WDW EM SSB 0 LB.00 Hz GB 0 PC ppm Figure S4: 3 C spectrum of PE-Por (00MHz, 644 scas i C 6 D 6 /TCE=: (v/v) at 90 C) ad correspodig elargmets o zoes a ad b. Triazolic carbos chemical shifts were based o our previous cycloadditio reactios ivolvig PE-N 3. I additio, remaiig assigmets are based o additioal DEPT aalyses (Figure S5).

14 ppm Figure S5: DEPT 35 aalyses of of PE-Por betwee 0 ad 60 ppm.

15 e c d PE-Por b a Figure S6: Solid state UV-NIR spectroscopy of PE-Por, ad

16 % Itesity Electroic Supplemetary Material (ESI) for Chemical Commuicatios Voyager Spec # MC=>BC=>NR(.00)[BP = 699., 99] Mass (m/z ) Figure S7: MALDI-ToF mass spectrometry aalysis of PE-Por

17 Figure S8: Powder X-ray diffractio data of PE ad PE-Por