SUPPORTING INFORMATION SUPPORTING INFORMATION

SUPPORTING INFORMATION

Self-assembled monolayers of subphthalocyanines on gold substrates.

David González-Rodríguez,

M. Victoria Martínez-Díaz,

Julia Abel,

Andras Perl,

Jurriaan Huskens

*

,

Luis Echegoyen*

and Tomás Torres*

a

Universidad Autónoma de Madrid, Departamento de Química Orgánica (C-I), Facultad de Ciencias, Cantoblanco,

28049-Madrid, Spain.

b

Department of Chemistry, Clemson University, Clemson, South Carolina 29634, USA

c

Molecular Nanofabrication group, MESA+ Institute for Nanotechnology, University of Twente, PO Box 217, Enschede,

The Netherlands.

SUPPORTING INFORMATION

Supporting Information Available

:

Pages S2-S3

: Experimental Section. General Methods.

Pages S4-S13

: Synthetic procedures, characterization data, and selected

H and

C NMR spectra for

all new SubPcs products.

Pages S14-S19

: Figures S1-S5 and Table S1.

EXPERIMENTAL SECTION General Methods.

Synthesis and compound characterization. Melting points (Mp) were determined in a Büchi 504392-S

equipment and are uncorrected. UV/Vis spectra were recorded with a Hewlett-Packard 8453 instrument. IR spectra were recorded on a Bruker Vector 22 spectrophotometer. LSI-MS and HRMS spectra were determined on a VG AutoSpec apparatus and MALDI-TOF-MS spectra were obtained from a BRUKER REFLEX III instrument equipped with a nitrogen laser operating at 337 nm. Dithranol (1,8,9-anthracenetriol) was found to be the most convenient matrix for these measurements. In general, the most intense peak corresponds to the mixture of the [M]+ ion (often mixed with the [M+H]+ ion), followed by the [M-axial group]+ ion. The observation of this last ion in MS experiments (i.e. the loss of the axial group generating the SubPcB+ cation), together with the [M-axial group+OH]+ _{ion (i.e. SubPcOH}+_{), is very frequent for SubPcs, specially in FAB-MS. NMR spectra were}

recorded with a BRUKER AC-300 (300 MHz) or a Bruker DRX-500 instrument (500 MHz) instrument. The temperature was actively controlled at 298 K, unless indicated otherwise. Chemical shifts are measured in ppm relative to tetramethylsilane (TMS). Carbon chemical shifts are measured downfield from TMS using the resonance of the deuterated solvent as the internal standard. The assignment of the NMR signals was supported by analysis of HMQC spectra (500 MHz; not shown). Elemental analyses were performed with a Perkin-Elmer 2400 CHN equipment. Column chromatography was carried out on silica gel Merck-60 (230-400 mesh, 60 Å), and TLC on aluminum sheets precoated with silica gel 60 F254 (E. Merck). Chemicals were purchased from

commercial suppliers and used without further purification. The synthesis and characterization of 4-iodophthalonitrile i and SubPcs 4H,[ii] 4F,[ii] and 7[iii] (C3 isomer) (see Schemes S1 and S2) has been described

elsewhere. The synthesis and characterization of SubPcs 3H, 3F, 1H, 1F, 6, 5, and 2 (see Schemes S1 and S2)

is described below.

Molecular modeling. The structure of all compounds was build using the Hyperchem 8.0.3 software package

(Hypercube, Inc.) for Windows and the geometry was optimized using PM3 semiempirical calculations. Semiempirical (AM1 or PM3) calculations have proven to be a very reliable method for the geometry optimization of SubPcs and C60, yielding structural parameters that match those obtained by X-ray diffraction studies.[iv] For

the sake of simplicity, the tert-octyl group in the axial phenoxy ligand was substituted by a methyl group in these models.

Electrochemistry. The cyclic voltammetry (CV) experiments of the SubPcs in solution was performed on a

windows-driven BAS 100W electrochemical analyzer (Bioanalytical Systems, West Lafayette, IN). Scan rate was 100 mV s-1 unless otherwise specified. All experiments were performed in THF (transferred under vacuum). Tetrabutylammonium hexafluorophosphate (n-Bu4NPF6) purchased from Fluka (>99 %) was recrystallized twice

from ethanol, dried in vacuum overnight prior to use and employed as the supporting electrolyte in 0.1 M concentration. A Glassy Carbon electrode (3 mm diameter) was used as the working electrode, a platinum mesh as the counter electrode, and a Ag/AgNO3 (0.01 M)/MeCN as the reference electrode, with ferrocene added as

an internal reference. All values quoted are vs ferrocene. All solutions were approximately 0.2 mM (transferring the solvent under vacuum prevents accurate determination) and ferrocene was approximately 1 mM in each case. The CVs were actually performed under Ar as in each case it was necessary to polish the working electrode with commercial Alpha Micropolish@ Alumina No. 1C (Aldrich) (particle size of 1.0 micron). The gold substrates for the cyclic voltammetric and impedance experiments were prepared by annealing the tip of a gold

wire (99.999%, 0.5 mm diameter, Alfa Ashe) in a gas–oxygen flame. Subsequently, the hot gold bead was cooled down in deionized water (Barnstead Nanopure, 18 MΩ). The quality of the electrode surface was checked by

observing the reversible redox response of Ru(NH3)6 in aqueous KCl. Electrodes not exhibiting the reversible

response of the redox couple with peak to peak separation 60 mV were discarded. The geometric area of the electrode (typically 0.2–0.4 cm2) was calculated by cycling (prior to SAM adsorption) in 0.1 M KCl / 1 mM Ru(NH3)6Cl3 at various scan rates and plotting the peak cathodic current against the square root of the scan rate

in V/s (from the Randles-Sevč_ik Equation). Surface coverages were then calculated from the charge passed during the first reduction of the fresh SAMs divided by F x surface area. In a typical experiment, a monolayer was grown by dipping a freshly prepared gold bead electrode in a 1-5 mM deaerated CH3CN or THF solution of the

subphthalocyanine for 12-24 h. The substrates were removed, rinsed with the appropriate solvent, and dried in a stream of Ar. Impedance and cyclic voltammetric measurements were performed using a three-electrode cell comprising a gold bead as the working electrode, a coiled platinum wire as the counter electrode, and an Ag/AgCl (from Bioanalytical Systems, West Lafayette, IN) as the reference electrode. Both electrochemical experiments were carried out with a Bioanalytical Systems 100-W electrochemical workstation interfaced with a personal computer. Impedance measurements were performed at the formal potential of the redox couple, and readings were taken at ten discrete frequencies per decade. The frequency range used was 1 KHz to 0.1 Hz with an alternating current (AC) amplitude of 5 mV. Impedance analysis was carried out using the commercially available program EQUIVALENT CIRCUIT written by B.A. Boukamp (University of Twente, The Netherlands), which determines the parameters of the assumed equivalent circuit by a nonlinear least squares fit. All experiments were carried out at room temperature. In agreement with the CV results, these electrochemical experiments seemed to destroy the SAMs. In fact, cycling the electrode after these tests resulted in a clear stripping peak on the first scan and no redox response at all on subsequent cycles (Figure S3).

Contact angle goniometry and XPS. Monolayers were prepared on silicon substrates covered with a 20 nm

gold layer. The substrates were cleaned in piranha solution, rinsed with water, dried, and used immediately. Monolayers were formed by exposing the substrates to a 0.04 g/L solution of the absorbate molecule in acetonitrile overnight. Contact angles were measured on a Krüss G10 contact angle setup equipped with a CCD camera. Advancing (θa) and receding (θr) contact angles were determined automatically during growth and

reduction of a clean water droplet by the droplet shape analysis routine. XPS measurements were performed on a Quantum Scanning X-ray Multiprobe instrument from Physical Electronics, equipped with a monochromatic Al Kα X-ray source producing approximately 25 W of X-ray power. Spectra were referenced to the main C1s peak

set at 284.0 eV. A surface area of 1000 µm x 300 µm was scanned with an X-ray beam about 10 µm wide. AFM. “Molecular ruler” experiments. A PDMS stamp was inked with a drop of octadecanethiol (ODT) solution

(1.4 10-4 _{M in ethanol) and the solvent was evaporated with a continuous stream of nitrogen. The printing was}

achieved by keeping the stamp and gold in conformal contact for 1 min. Then, the sample was immersed in clear acetonitrile (in case of the blank), or in the solution of the SubPc for two hours. Afterwards, the sample was rinsed with clear acetonitrile and dried with nitrogen. In all cases the circles are the areas printed with ODT. AFM analyses were carried out with a Nanoscope III (Veeco/Digital Instruments, Santa Barbara, CA) multimode atomic force microscope equipped with a J-scanner, in contact mode by using Si3N4 cantilevers (Nanoprobes,

lateral forces in the friction force images, the sample was scanned at 90º with respect to the axis of the cantilever. AFM imaging was performed at ambient conditions.

Synthesis O S S CN CN N N N N N N BCl BCl3 p-xylene toluene OH OH R R R R R R R R R R R R R R R R N N N N N N R R R R R R R R R R R R B O OH HO O S S DCC / DMAP CH2Cl2 N N N N N N R R R R R R R R R R R R B O O 1H R = H 1F R = F 3H R = H 3F R = F 4H R = H 4F R = F

Scheme S1. Synthetic route to SubPcs 1H and 1F. These products were prepared from the correponding

chloroSubPcs 4H and 4F by axial substitution of the chlorine atom with hydroquinone, to yield 3H and 3F,

followed by an esterification reaction between the remaining phenol group and thiooctic acid.

CN CN I N N N N N N BCl BCl3 p-xylene toluene N N N N N N B O B HO O O Pd(PPh3)4 CsF / DME N N N N N N B O OH 2 5 6 7 O S S I I I I I I HO OH HO N N N N N N B O O O S S O O S S O HO O S S DCC / DMAP CH2Cl2

Scheme S2. Synthetic route to SubPc 2. After axial substitution of the C3-isomer of 7 with tert-octylphenol,

triiodo-SubPc 6 was subjected to a Suzuki reaction with (2-hydroxyphenyl)pinacol boronate and the product 5

Synthetic procedure for SubPc 3H: In a 25-mL round-bottomed flask, equipped with a condenser and a magnetic stirrer, the hydroquinone (275 mg; 2.5 mmol) and the chloro-SubPc 4H (0.5 mmol) were refluxed in

toluene (2 mL) for 7 h. The reaction mixture was cooled down to room temperature, the solvent was evaporated and the solid residue obtained was washed with a 4:1 mixture of methanol/water and subjected to column chromatography on silica gel using a 5:1 mixture of toluene/THF as eluent. Compound 3H was further purified

washing with hexane.

22 23 24 25 8 9 1 3 2 4 4a 5 6 7 10 11 11a 12 13 7a 14 14a 15 16 17 18 18a 19 20 21 21a N N N N N NB O OH 3H

Pink solid; Yield: 80%.

Mp > 250ºC.

1

H-NMR (300 MHz, CDCl3): δ (ppm) = 8.85-8.75 (AA’BB’ system, 6H; H-1, H-4, H-8, H-11, H-15, H-18),

7.90-7.80 (AA’BB’ system, 6H; H-2, H-3, H-9, H-10, H-16, H-17), 6.23 (AA’XX’ system, 2H; H-24), 5.24 (AA’XX’ system, 2H; H-23), 5.20 (s (broad), 1H; OH).

13

C-NMR (75.5 MHz, CDCl3): δ (ppm) = 152.1 (1C; C-25), 151.0 (6C; C-5, C-7, C-12, C-14, C-19, C-21), 145.0

(1C; C-22), 130.6 (6C; C-4a, C-7a, C-11a, C-14a, C-18a, C-21a), 129.5 (6C; C-2, C-3, C-9, C-10, C-16, C-17), 122.3 (6C; C-1, C-4, C-8, C-11, C-15, C-18), 120.0 (2C; C-24), 116.3 (2C; C-23).

MS (LSI-MS, m-NBA): m/z = 504 [M]+ (30%).

HRLSI-MS (C30H17N6O2B) [M]+: Calculated: 504.1506.

Found: 504.1497.

UV-vis (CHCl3): λmax (nm) (log ε (dm3 mol-1 cm-1)) = 563 (4.5), 528 (sh), 310 (4.2), 267 (4.2).

FT-IR (KBr), ν (cm-1): 3443, 3105 (OH), 1435, 1387, 1290, 1238, 1197, 1105, 1067 (B-O), 983, 766, 709.

Synthetic procedure for SubPc 3F: In a 10-mL round-bottomed flask, equipped with a magnetic stirrer and rubber seal, the hydroquinone (550 mg; 5 mmol) and the chloro-SubPc 4F (0.5 mmol) were placed. The mixture

was heated to the melting point of the phenol and stirred at that temperature for 10 min. The reaction mixture was cooled down to room temperature, and the excess of the phenol was eliminated washing the solid residue with a 3:1 mixture of methanol/water. The solid obtained was subjected to column chromatography on silica gel using a 10:1 mixture of toluene/THF as eluent. Compound 3F was further purified washing with hexane.

8 9 22 23 24 25 1 3 2 4 4a 5 6 7 10 11 11a 12 13 7a 14 14a 15 16 17 18 18a 19 20 21 21a N N N N N NB O F F F F F F F F F F F F OH 3F

Mp > 250ºC.

1

H-NMR (300 MHz, CDCl3): δ (ppm) = 6.21 (AA’XX’ system, 2H; H-24), 5.20 (AA’XX’ system, 2H; H-23), 4.5 (s

(broad), 1H; OH).

13

C-NMR (75.5 MHz, CDCl3): δ (ppm) = 150.7 (1C; C-25), 148.2 (6C; C-5, C-7, C-12, C-14, C-19, C-21), 144.5

(1C; C-22), 144.7-143.7 (m, 6C; C-F), 141.2-140.3 (m, 6C; C-F), 119.6 (2C; C-23), 115.9 (2C; C-24), 115.1-114.6 (m, 6C; C-4a, C-7a, C-11a, C-14a, C-18a, C-21a).

MS (LSI-MS, m-NBA): m/z = 721 [M+H]+ (45%).

HRLSI-MS (C30H5N6O2F12B) [M]+: Calculated: 720.0375.

Found: 720.0403.

UV-vis (CHCl3): λmax (nm) (log ε (dm3 mol-1 cm-1)) = 571 (4.5), 533 (sh), 309 (4.1), 273 (4.1).

FT-IR (KBr), ν (cm-1): 3618, 3389 (O-H), 2957, 1532, 1491, 1258, 1218, 1164, 1108, 957, 714, 593, 566.

Synthetic procedure forSubPc 6: In a 25-mL round-bottomed flask, equipped with a condenser and a magnetic stirrer, the 4-tert-octylphenol (516 mg; 2.5 mmol) and the chloro-SubPc 7 (0.5 mmol; C3 isomer) were refluxed in

toluene (3 mL) for 10 h. The reaction mixture was cooled down to room temperature, the solvent was evaporated and the solid residue obtained was washed with a 4:1 mixture of methanol/water and subjected to column chromatography on silica gel using toluene as the eluent. Compound 6 was further purified washing with cold

methanol. 6 8 9 1 3 2 4 4a 5 6 7 10 11 11a 12 13 7a 14 14a 15 16 17 18 18a 19 20 21 21a 22 23 24 25 N N N N N N B O I I I

Magenta solid; Yield: 88%.

Mp > 250ºC. 1 H-NMR (300 MHz, CDCl3): δ (ppm) = 9.20 (d, Jm = 1.5 Hz, 3H; H-1, H-8, H-15), 8.52 (d, Jo = 8.2 Hz, 3H; H-4, H-11, H-18), 8.13 (dd, Jo = 8.2 Hz, Jm = 1.5 Hz, 3H; H-3, H-10, H-17), 6.77 (AA’XX’ system, 2H; H-24), 5.41 (AA’XX’ system, 2H; H-23), 1.49 (s, 2H; CH2), 1.26 (s, 6H; C(CH3)2), 0.54 (s, 9H; C(CH3)3). 13 C-NMR (75.5 MHz, CDCl3): δ (ppm) = 149.6 (1C; C-22), 151.2, 150.3 (6C; C-5, C-7, C-12, C-14, C-19, C-21),

143.2 (1C; C-25), 138.9 (3C; C-3, C-10, C-17), 132.1, 129.6 (6C; C-4a, C-7a, C-11a, C-14a, C-18a, C-21a), 131.0 (3C; 1, 8, 15), 126.3 (2C; 24), 123.3 (3C; 4, 11, 18), 118.0 (2C; 23), 95.9 (3C; 2, C-9, C-16), 56.8 (1C; CH2), 37.7 (2C; C(CH3)2), 32.1, 30.1 (2C; C(CH3)2, C(CH3)3), 31.3 (3C; C(CH3)3).

MS (LSI-MS, m-NBA): m/z = 978 [M]+ (40%), 773 [M-axial group]+ (75%). HRLSI-MS (C38H30N6OBI3) [M]+: Calculated: 977.9708.

Found: 977.9717.

UV-vis (CHCl3): λmax (nm) (log ε (dm3 mol-1 cm-1)) = 573 (4.5), 527 (sh), 339 (4.0), 315 (4.1), 277 (4.2).

FT-IR (KBr), ν (cm-1): 2924, 2872, 2853, 1523, 1485, 1428, 1340, 1250, 1175, 1057 (B-O), 1035, 806, 746, 703.

Synthetic procedure for SubPc 5: A magnetically stirred mixture of triiodoSubPc 6 (0.2 mmol),

(2-hydroxyphenyl)pinacol boronate (145 mg, 0.66 mmol), Pd(PPh3)4 (34 mg, 0.03 mmol) and powdered CsF (272

mg, 1.8 mmol) in DME (10 mL) was heated to reflux for 6 h. The solvent was evaporated and CH2Cl2 (30 mL) was

added. The solution was washed twice with water (10 mL) and dried over Na2SO4. The drying agent was filtered

and the solvent was removed, yielding a dark purple solid that was subjected to column chromatography on silica gel using a 10:1 mixture of toluene/THF. Compound 5 was then washed with hexane for further purification.

22 23 24 25 8 9 1 3 2 4 4a 5 6 7 10 11 11a 12 13 7a 14 14a 15 16 17 18 18a 19 20 21 21a N N N N N N B O OH HO HO 26 27 28 29 30 31 5

Dark purple solid; Yield: 90%.

Mp > 250ºC.

1

H-NMR (300 MHz, Acetone-d6): δ (ppm) = 8.57 (d, Jm = 1.2 Hz, 3H; H-1, H-8, H-15), 8.3 (s (broad), 3H; OH),

8.28 (d, Jo = 8.2 Hz, 3H; H-4, H-11, H-18), 7.64 (dd, Jo = 8.2 Hz, Jm = 1.2 Hz, 3H; H-3, H-10, H-17), 6.92

(AA’XX’ system, 2H; H-30), 6.63 (dd, Jo = 8.8 Hz, Jo’ = 8.2 Hz, 3H; H-25), 6.52 (d, Jo’’ = 7.6 Hz, 3H; H-23), 6.37

(dd, Jo’ = 8.2 Hz, Jo’’ = 7.6 Hz, 3H; H-24), 6.28 (d, Jo = 8.8 Hz, 3H; H-26), 4.91 (AA’XX’ system, 2H; H-29), 1.43

(s, 2H; CH2), 0.99 (s, 6H; C(CH3)2), 0.59 (s, 9H; C(CH3)3).

13

C-NMR (75.5 MHz, Acetone-d6): δ (ppm) = 155.2 (3C; C-27), 152.6, 152.4 (6C; C-5, C-7, C-12, C-14, C-19,

C-21), 151.6 (1C; C-28), 143.1 (1C; C-31), 141.6 (3C; C-2, C-9, C-16), 132.8 (C-22), 132.0, 131.8 (6C; C-23, 25), 130.2, 130.1 (6C; 7a, 14a, 21a, 3, 10, 17), 128.5 (3C; 4a, 11a, 18a), 127.3 (2C; C-30), 123.3 (3C; C-4, C-11, C-18), 122.2 (3C; C-1, C-8, C-15), 121.1 (3C; C-24), 119.3 (2C; C-29), 117.1 (3C; C-26), 57.5 (1C; CH2), 38.2 (2C; C(CH3)2), 32.7, 31.8 (2C; C(CH3)2, C(CH3)3), 32.0 (3C; C(CH3)3).

MS (LSI-MS, m-NBA): m/z = 876 [M]+ (55%).

HRLSI-MS (C56H45N6O4B) [M]+: Calculated: 876.3595.

Found: 876.36515.

UV-vis (CHCl3): λmax (nm) (log ε (dm3 mol-1 cm-1)) = 576 (4.5), 536 (sh), 338 (4.4), 259 (4.5).

FT-IR (KBr), ν (cm-1): 3449 (O-H), 3039, 2987, 2856 (C-H), 1593, 1478, 1306, 1247, 1110, 1049 (B-O), 944,

865, 801, 756, 689.

General synthetic procedure for SubPcs 1H, 1F and 2: The corresponding SubPc (3H (for 1H), 3F (for 1F) or 5

(for 2)) (0.1 mmol), dicyclohexylcarbodiimide (31 mg, 0.15 mmol (for 3H and 4F); 93 mg, 0.45 mmol (for 5)) and

thioctic acid (25 mg, 0.12 mmol (for 3H and 3F); 75 mg, 0.36 mmol (for 5)) were dissolved in 3 mL of dry CH2Cl2

under argon atmosphere. The solution was cooled to 0ºC in an ice bath and a solution of 4-dimethylaminopyridine (6 mg, 0.05 mmol (for 3H and 3F); 18 mg, 0.15 mmol (for 5)) in dry CH2Cl2 (1 mL) was added dropwise. The

mixture was stirred for 1 h at 0ºC and then for 3 h at room temperature. In the case of 1F, decomposition was

insoluble urea by-product and the filtrate was washed with water (3 x 15 mL), dried over MgSO4, filtered and

evaporated. The residue was subjected to column chromatography using a 20:1 mixture of toluene/THF (1H), a

30:1 mixture of toluene/THF (1F), or a 10:1 mixture of toluene/THF (2). Further purification involved washing with

cold hexane for 1H and 1F. SubPc 1H 22 23 24 25 8 9 1 3 2 4 4a 5 6 7 10 11 11a 12 13 7a 14 14a 15 16 17 18 18a 19 20 21 21a N N N N N N B O O O S S 1H

Magenta solid. Yield: 80%.

Mp > 250ºC.

1

H-NMR (300 MHz, CDCl3): δ (ppm) = 8.88-8.75 (AA’BB’ system, 6H; H-1, H-4, H-8, H-11, H-15, H-18),

7.90-7.78 (AA’BB’ system, 6H; H-2, H-3, H-9, H-10, H-16, H-17), 6.48 (AA’XX’ system, 2H; H-24), 5.38 (AA’XX’ system, 2H; H-23), 3.51 (q, J = 7 Hz, 1H; CH), 3.2-3.0, 2.5-2.3, 2.0-1.8, 1.75-1.55, 1.55-1.35 (5xm, 12H; CH2).

13

C-NMR (75.5 MHz, CDCl3): δ (ppm) = 171.8 (1C; C=O), 151.2 (6C; C-5, C-7, C-12, C-14, C-19, C-21), 150.0

(1C; C-22), 144.6 (1C; C-25), 130.9 (6C; C-4a, C-7a, C-11a, C-14a, C-18a, C-21a), 129.8 (6C; C-2, C-3, C-9, C-10, C-16, C-17), 122.2 (6C; C-1, C-4, C-8, C-11, C-15, C-18), 121.6 (2C; C-24), 119.4 (2C; C-23), 56.2 (1C; CH), 40.1, 38.4, 34.5, 33.9, 28.6, 24.5 (6C; CH2). ppm 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0

MS (LSI-MS, m-NBA): m/z = 692 [M]+ (20%).

HRLSI-MS (C38H29N6O3S2B) [M]+: Calculated: 692.1836.

Found: 692.1839.

UV-vis (CHCl3): λmax (nm) (log ε (dm3 mol-1 cm-1)) = 563 (4.5), 530 (sh), 309 (4.2), 268 (4.2).

FT-IR (KBr), ν (cm-1): 2917, 2856, 1732 (C=O), 1598, 1432, 1387, 1291, 1240, 1197, 1105, 1062 (B-O), 983,

766, 709. SubPc 1F 8 9 22 23 24 25 1 3 2 4 4a 5 6 7 10 11 11a 12 13 7a 14 14a 15 16 17 18 18a 19 20 21 21a N N N N N N B O F F F F F F F F F F F F O O S S 1F

Dark magenta solid. Yield: 56%.

Mp > 250ºC.

1

H-NMR (300 MHz, CDCl3): δ (ppm) = 6.46 (AA’XX’ system, 2H; H-24), 5.31 (AA’XX’ system, 2H; H-23), 3.54

13

C-NMR (75.5 MHz, CDCl3): δ (ppm) = 171.7 (1C; C=O), 150.1 (1C; C-22), 148.2 (6C; C-5, C-7, C-12, C-14,

C-19, C-21), 144.6-143.5 (m, 6C; C-F), 144.5 (1C; C-25), 141.1-140.1 (m, 6C; C-F), 121.6 (2C; C-24), 119.5 (2C; C-23), 115.1-114.6 (m, 6C; C-4a, C-7a, C-11a, C-14a, C-18a, C-21a), 56.2 (1C; CH), 40.0, 38.3, 34.3, 33.9, 28.5, 24.3 (6C; CH2).

MS (LSI-MS, m-NBA): m/z = 908 [M]+ (45%).

HRLSI-MS (C38H17N6O3F12S2B) [M]+: Calculated: 908,0705.

Found: 908,0701.

UV-vis (CHCl3): λmax (nm) (log ε (dm3 mol-1 cm-1)) = 571 (4.6), 533 (sh), 309 (4.2, 273 (4.2).

SubpPc 2 ppm 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0

2 22 23 24 25 8 9 1 3 2 4 4a 5 6 7 10 11 11a 12 13 7a 14 14a 15 16 17 18 18a 19 20 21 21a 26 27 28 29 30 31 N N N N N N B O O O O S S O O O S S S S

Magenta solid. Yield: 69%.

Mp > 250ºC.

1

H-NMR (300 MHz, CDCl3): δ (ppm) = 8.92 (d, Jm = 1.2 Hz, 3H; H-1, H-8, H-15), 8.82 (d, Jo = 8.2 Hz, 3H; H-4,

H-11, H-18), 7.99 (dd, Jo = 8.2 Hz, Jm = 1.2 Hz, 3H; H-3, H-10, H-17), 7.70-7.60 (3H; H-23), 7.53-7.47 (m, 6H;

H-24, H-25), 7.23 (d, Jo = 8.8 Hz, 3H; H-26), 6.77 (AA’XX’ system, 2H; H-30), 5.34 (AA’XX’ system, 2H; H-29),

3.3-3.1 (3H; CH), 3.0-2.8, 2.8-2.45, 2.45-2.35, 1.95-1.75, 1.5-1.4 (5xm, 36H; CH2), 1.50 (s, 2H; CH2 (axial

group), 1.14 (s, 6H; C(CH3)2), 0.58 (s, 9H; C(CH3)3).

13

C-NMR (75.5 MHz, CDCl3): δ (ppm) = 171.7 (C=O), 151.6, 151.5, 151.4 (6C; 5, 7, 12, 14, 19,

C-21), 150.0 (1C; C-28), 147.9 (3C; C-27), 142.7 (1C; C-31), 139.5 (3C; C-2, C-9, C-16), 134.3 (3C; C-22), 131.3, 130.8, 129.9, 129.3 (15C; C-7a, C-14a, C-21a, C-4a, C-11a, C-18a, C-3, C-10, C-17, C-23, C-25), 126.6 (2C; C-30), 123.2, 122.6, 121.8 (12C; C-1, C-8, C-15, C-4, C-11, C-18, C-24, C-26), 118.0 (2C; C-29), ppm 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0

57.0 (1C; CH2 (axial group)), 55.7 (3C; CH), 39.7, 38.1, 38.0, 34.3, 34.1, 34.0, 28.4, 28.3, 24.3 (18C; CH2),

37.7 (2C; C(CH3)2), 32.2, 31.5 (2C; C(CH3)2, C(CH3)3), 31.6 (3C; C(CH3)3).

MS (LSI-MS, m-NBA): m/z = 1443 [M+H]+ (5%).

HRLSI-MS (C80H81N6O7S6B) [M]+: Calculated: 1440.4584.

Found: 1440.4568.

UV-vis (CHCl3): λmax (nm) (log ε (dm3 mol-1 cm-1)) = 575 (4.6), 536 (sh), 324 (4.2), 272 (4.3), 242 (4.4).

FT-IR (KBr), ν (cm-1): 2987, 2917, 2856, 1732 (C=O), 1593, 1478, 1310, 1247, 1110, 1049 (B-O), 944, 865,

Figure S1. Solution electrochemistry of SubPcs 1H, 1F and 2. Cyclic voltammograms in THF [SubPc] ~ 0.2 mM.

SubPc 1H displays a reversible signal for the first reduction, just over 530 mV more cathodic when compared

to 1F, being the most difficult to reduce of the three SubPcs. The second reduction is just under 500 mV more

negative and is not reversible, even when the cathodic limit is set to just beyond this second signal. The third reduction is approximately 50 mV more difficult in 1H than in 1F, and is highly irreversible in both cases. The

fourth reduction gives a very small signal and again displays approximately 50 mV difference between the two SubPcs and is highly irreversible.

In the case of the equivalent fluorinated 1F the first two reductions are reversible when scanning to just

beyond the second wave, scanning to more cathodic limits reduces the reversibility of these signals, presumably due to decomposition or absorption. The first reduction of the SubPc ring is approximately 0.5 V easier than for the non-fluorinated compounds, as expected. The second reduction is also clearly reversible. 1F also displays a

fifth signal at –2.879 V just before the solvent edge that is larger than the signal for the fourth reduction and has no equivalent in the CV of 1H.

The oxidation potentials vary as expected, with the fluorine substituents making 1F more difficult to oxidize by

60 mV, though despite being more difficult the process is much more reversible than for 1H.

The oxidation of 2 is only slightly easier than that of 1H (by about 30 mV) and is also quasi-reversible. In

contrast, none of the reductions of 2 are reversible. The peak to peak value of the first reduction is small, however

the anodic part of the signal is small and broad regardless of the cathodic limit. For the other three reductions the cathodic wave is small and no return anodic signals can be distinguished.

1000

0

-1000

-2000

-3000

0.0

2.0x10

4.0x10

C

u

rr

e

n

t /

A

Potential (mV)

vs

Ferrocene

1H

1F

2

Peak potentials 1H 1F 2 EpC 0.659 0.603 EpA 0.651* 0.710 0.617 EpC -1.555 -1.030 -1.481 EpA -1.509 -0.970 -1.419 EpC -2.155 -1.670 -1.775* EpA -2.027 -1.608 EpC -2.413* -2.360* -2.300* EpA EpC -2.667 -2.615* -2.585* EpA -2.475 EpC -2.879*

Half wave potentials

1H 0.651* (EpA) -1.532 (46) -2.091 (128) -2.413* (EpC) -2.571 (192) 1F 0.684 (51) -1.000 (60) -1.639 (62) -2.360* (EpC) -2.615* _(Ep

C)

-2.879* (EpC) 2 0.610 (15) -1.450 (62) -1.775* (EpC) -2.300* (EpC) -2.585*(EpC)

Table S1. Solution electrochemistry of SubPcs 1H, 1F and 2. Peak potentials and half-wave potentials (all data in

Figure S2. Cyclic voltammograms of SAMs formed from compound 1H and 2 on gold electrodes. For 1H, the

effect of repeated cycling on the current intensity is shown.

-0.5 -1.0 -1.5 -2.0 -4.0x10-6 -2.0x10-6 0.0 2.0x10-6 4.0x10-6 6.0x10-6 8.0x10-6 1.0x10-5 C u rr e n t / A Potential (mV) vsferrocene 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4 -1.6 -1.8 -4.0x10-6 -2.0x10-6 0.0 2.0x10-6 4.0x10-6 6.0x10-6 8.0x10-6 1.0x10-5

1H

2

Figure S3. a) Impedance experiment for compound 2. b) Impedance experiment for compound 1F. c) Cyclic

voltammogram obtained after the impedance measurement of 2.

0 20000 40000 60000 0 5000 10000 15000 20000 Z' / Ohms 0.0 -0.5 -1.0 -1.5 -1.2x10-5 -1.0x10-5 -8.0x10-6 -6.0x10-6 -4.0x10-6 -2.0x10-6 0.0 2.0x10-6 4.0x10-6 6.0x10-6 8.0x10-6 1.0x10-5 1.2x10-5 1.4x10-5 1.6x10-5

a

c

b

Figure S4. Height cross sections and contact-mode AFM height images of a gold surface patterned with ODT

and immersed into pure acetonitrile (blank), or SubPc 1H, 1F, and 2 solutions in acetonitrile (0.035 mg/ml). Any

value is an average of the points on a cross-line within the marked area.

1H

1F

2

blank

H

e

ig

h

t

/

n

m

Width /

µ

µ

µ

µ

m

H

e

ig

h

t

/

n

m

H

e

ig

h

t

/

n

m

H

e

ig

h

t

/

n

m

Figure S5. S2p region of the XPS spectrum and S2p peak fit data of the SAM of compound 2 on 20 nm evaporated

gold. 45 % of the sulphur atoms are bound to the surface, that is, nearly 3 out of 6 atoms per molecule of 2.

N N N N N NB O O O O S S O O O S S S S 2

Band Energy (eV) FWHM % Area

Sp2 3/2bound 161.42 1.26 30.44

Sp2 1/2bound 162.12 1.26 15.22

Sp2 3/2unbound 163.19 1.26 36.23

References (S.I.)

[i] M. S. Marcuccio, et al. Can. J. Chem.1985, 63, 3057. [ii] C. G. Claessens, et al. Eur. J. Org. Chem.2003, 2547-2551.

[iii] D. González-Rodríguez, et al. Eur. J. Org. Chem.2009, 1871–1879.

[iv] a) V. R. Ferro et al. J. Porphyrins Phthalocyanines2000, 4, 611-620; b) R. S. Iglesias et al. J. Org. Chem.

2007, 72, 2967-2977; c) S. Samdal et al. J. Phys. Chem. A 2007, 111, 4542-4550. d) D. González-Rodríguez, et al. Angew.Chem. Int. Ed. 2009, 48, 8032-8036.