Supporting Information� Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2011

One-Pot Functionalization of Graphene with Porphyrin throughCycloaddition Reactions

Xiaoyan Zhang,[a, b] Lili Hou,[a] Arjen Cnossen,[a] Anthony C. Coleman,[b]

Oleksii Ivashenko,[c] Petra Rudolf,[c] Bart J. van Wees,[b] Wesley R. Browne,[a] andBen L. Feringa*[a]

chem_201100980_sm_miscellaneous_information.pdf

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Fig S1. FTIR spectra of TPP-CHO (black) and PdTPP-CHO (red).

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Fig S2. Additional TEM images of graphene-TPP hybrid material and diffraction pattern

shown in figure 6a.

Fig S3. Additional TEM images of graphene-PdTPP hybrid material.

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Fig S4. UV/Vis absorption spectra of graphene-TPP (solid line) and TPP-CHO (dashed line) used to obtain the emission spectra shown in Figure 7 and of graphene-TPP after baseline correction (dotted line). The concentrations of porphyrin in both TPP-CHO and graphene-TPP were equivalent (0.7 µM) according to the intensity of the Soret band absorption.

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Fig S5. UV/Vis absorption spectra of graphene-PdTPP (solid line) and PdTPP-CHO (dashed line) used to obtain the emission spectra shown in Figure 7 and of graphene-PdTPP after baseline correction (dotted line). The concentrations of porphyrin in both TPP-CHO and graphene-TPP were equivalent (0.6 µM) according to the intensity of the Soret band absorption.

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Data: Data2_CModel: ExpDec1Equation: y = A1*exp(-x/t1) + y0Weighting: y No weighting Chi^2/DoF = 0.00002R^2 = 0.99955 y0 0.00041 ±0.00014A1 1.00779 ±0.00061t1 10.64901 ±0.01084

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1.0 Data: Data4_BModel: ExpDec2Equation: y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0Weighting: y No weighting Chi^2/DoF = 0.00006R^2 = 0.98073 y0 0.00323 ±0.00021A1 0.23688 ±0.00184t1 6.17338 ±0.06364A2 0.64057 ±0.00588t2 0.23361 ±0.00386

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time /ns Figure S6 Fluorescence lifetime decays for (Left) TPP-CHO and (right) graphene-TPP in DMF together with a mono and bi-exponential decay fitting, respectively. In the case of the graphene-TPP the lifetime of the shorter component was < 500 ps and the longer component was 6.2 ns. Fitting was performed using Microcal Origin 7.

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Data: Data4_BModel: ExpDec1Equation: y = A1*exp(-x/t1) + y0Weighting: y No weighting Chi^2/DoF = 0.0005R^2 = 0.97401 y0 0.06724 ±0.0007A1 0.53361 ±0.00099t1 43960.59117 ±221.24077

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Data: Data2_BModel: ExpDec2Equation: y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0Weighting: y No weighting Chi^2/DoF = 0.00026R^2 = 0.9899 y0 0.02668 ±0.00044A1 0.43264 ±0.00228t1 662.70098 ±4.77279A2 0.62454 ±0.00287t2 79.34149 ±0.72784

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Figure S7 Fluorescence lifetime decays for (Left) PdTPP-CHO and (right) graphene-PdTPP in DMF together with a mono and bi-exponential decay fitting, respectively. A free fit gave lifetimes of 44 µs for PdTPP-CHO, and 80 ns and 660 ns for the graphene-PdTPP sample. Fitting was performed using Microcal Origin 7.

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Fig S8. (left) UV/Vis absorption and (right) fluorescence (λexc 410 nm) spectra of solutions of TPP-CHO (thick solid line), graphene-TPP (thin dotted line) and a mixture of TPP-CHO and graphene (thin solid line). The absorption at 410 nm (attributable to the porphyrin component in each case was matched for comparison of the intensity of the emission spectra. The attenuation due to scattering by the

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graphene in the wavelength range of the fluorescence spectrum and at 410 nm is estimated to result in a 50% loss in emission intensity. Hence the decrease in emission intensity of the TPP-CHO in the presence of graphene is attributable to attenuation primarily not only dynamic quenching.

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Fig S9. (left) UV/Vis absorption and (right) phosphorescence (λexc 410 nm) spectra of solutions of graphene-PdTPP (red line) and a mixture of PdTPP-CHO with graphene (black line). The absorption at 410 nm (attributable to the porphyrin component in each case was matched for comparison of the intensity of the emission spectra. The attenuation due to scattering by the graphene in the wavelength range of the phosphorescence spectrum and at 410 nm is estimated to result in a ca. 40% loss in emission intensity. Hence the decrease in emission intensity of the PdTPP-CHO in the presence of graphene is attributable to attenuation primarily and not only dynamic quenching.

TPP-COOMe (87 mg, 0.129 mmol) was dissolved in freshly distilled CH2Cl2 (5 mL) at 0 ºC. LiAlH4 (0.3 mL of a 1.0 M solution in CH2Cl2, 0.3 mmol) was added dropwise. The mixture was allowed to warm to RT and stirred for 2 h, followed by the addition of MeOH (1 mL). The reaction mixture was partitioned between CH2Cl2 (30 mL) and sat. aqueous Rochelle salt solution (30 mL). The organic layer was separated, dried on Na2SO4 and concentrated. The residue was dissolved in THF (5 mL) and MnO2 (56 mg, 0.64 mmol) was added. The mixture was vigorously stirred at 40 ºC for 4 h and then filtered through a silica plug (CH2Cl2). The filtrate was concentrated and recrystallized (CH2Cl2/MeOH, layer addition) to give TPP-CHO (63 mg, 76%) as a purple solid. Spectroscopic data is in accordance with the following literature1. 1 O. Wennerström, H. Ericsson, I. Raston, S. Svensson, W. Pimlott, Tetrahedron Lett., 1989, 30, 1129-1132.

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1H NMR spectrum of TPP-CHO.