Supporting Information: Pi Extended Ethynyl 21,23 Dithiaporphyrins: A Synthesis and Comparative Study of Electrochemical, Optical and Self Assembling Properties Ashley D. Bromby; Samantha N. Keller; Kevin J. A. Bozek; Vance E. Williams; Todd C. Sutherland* *Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary Alberta, Canada Fax: 01 403 289 9488;Tel: 01 403 220 7559;E mail: todd.sutherland@ucalgary.ca Contents: Compound characterization 1 H and 13 C NMR 1 Scheme S1: Synthesis of ethynyl precursors 1a/b 12 Figure S1: Differential pulse voltammograms for dithiaporphyrins 3a and 3b 13 Figure S2: Frontier molecular orbitals of dithiaporphyrins 3a, 3b and N 2 S 2 TPOC 12 14 Table S1: Oscillator strengths and peak widths at full height half maximum for compounds 3a and 3b 14 Figure S3: DSC thermogram of dithiaporphyrin 3b 15 Figure S4: Powder XRD of porphyrin 3a 15 Figure S5: Powder XRD of blank capillary tube 16 Cartesian coordinates of DFT optimized [B3LYP 6 31G+(d)] structures of reduced model ethynyl dithiaporphyrins 3a and 3b 16
1 1 Bromo 4 (dodecyloxy)benzene 4a 2.00 2.05 2.10 2.10 2.40 16.16 3.33 1 Bromo 4 (dodecyloxy)benzene 4a 158.41 132.32 116.45 112.69 68.41 32.08 29.82 29.79 29.75 29.72 29.53 29.51 29.33 26.15 22.85 14.27
2 4 Dodecyloxy[(trimethylsilyl)ethynyl]benzene 5a 2.00 2.08 2.17 2.33 2.22 16.30 3.44 9.16 8 7 6 5 4 ppm 3 2 1 0 4 Dodecyloxy[(trimethylsilyl)ethynyl]benzene 5a 159.51 133.58 115.14 114.48 105.48 92.40 68.19 32.07 29.81 29.79 29.74 29.71 29.53 29.50 29.33 26.15 22.84 14.27 0.23
3 4 Dodecyloxyethynylbenzene 1a 8 7 6 5 4 ppm 3 2 1 0 4 Dodecyloxyethynylbenzene 1a 170 150 130 110 90 80 ppm 70 60 50 40 30 20 10 0
4 2,5 Bis[(4 dodecyloxyethynylphenyl)hydroxymethyl]thiophene 2a 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 ppm 3.0 2.5 2.0 1.5 1.0 0.5 0.0 2,5 Bis[(4 dodecyloxyethynylphenyl)hydroxymethyl]thiophene 2a 170 150 130 110 90 80 ppm 70 60 50 40 30 20 10 0
5 5, 10, 15, 20 Tetra(4 dodecyloxyethynylphenyl) 21, 23 dithiaporphyrin 3a 5, 10, 15, 20 Tetra(4 dodecyloxyethynylphenyl) 21, 23 dithiaporphyrin 3a
6 4 Bromododecanoylbenzene 1 Bromo 4 dodecylbenzene 4b
7 1 Bromo 4 dodecylbenzene 4b 4 Dodecyl[(trimethylsilyl)ethynyl]benzene 5b
8 4 Dodecyl[(trimethylsilyl)ethynyl]benzene 5b 4 Dodecylethynylbenzene 1b
9 4 Dodecylethynylbenzene 1b 2,5 Bis[(4 dodecylethynylphenyl)hydroxymethyl]thiophene 2b
10 2,5 Bis[(4 dodecylethynylphenyl)hydroxymethyl]thiophene 2b 5, 10, 15, 20 Tetra(4 dodecylethynylphenyl) 21, 23 dithiaporphyrin 3b
11 5, 10, 15, 20 Tetra(4 dodecylethynylphenyl) 21, 23 dithiaporphyrin 3b 2, 5 thiophenedicarboxaldehyde 2, 5 thiophenedicarboxaldehyde
12 Br BrC 12 H 25 OH K 2 CO 3,KI 90% O Br OC 12 H 25 4a SiMe 3 Me 3 Si OC 12 H 25 Br Cl C 11 H 23 AlCl 3 40% Br 58% C 11 H 23 O H 2 N NH 2 KOH Pd(PPh 3 ) 2 Cl 2 5a, 62% CuI, PPh 3 NEt Me C 3 3 Si 12 H 25 5b, 48% Br C 12 H 25 4b Scheme S1: Synthesis of ethynyl precursors 1a/b.
13 Figure S1: Differential pulse voltammograms for dithiaporphyrins 3a (left) and 3b (right) at 100 mv s 1.
14 Figure S2: Frontier molecular orbitals of dithiaporphyrins 3a, 3b and N 2 S 2 TPOC 12 using DFT methods at the B3LYP/6 31G(+)d level. Note: Orbital pictures are LUMO+1, LUMO, HOMO and HOMO 1 from top to bottom and the HOMO 2 orbital is not shown. Table S2: Oscillator strengths and peak widths at full height half maximum for compounds 3a and 3b. Compound Soret QIV QIII QII QI 3a 0.72 (1226)* 0.10 (1461) 0.20 (835) 0.003 (586) 0.03 (562) 0.14 (527)* 3b 0.96 (1095) 0.09 (1294) 0.21 (777) 0.002 (439) 0.03 (495) N 2 S 2 TPOC 12 1.53 (776) 0.09 (686) 0.08 (883) 0.005 (584) 0.03 (551) Note: Peak widths are reported in parentheses at full width half maximum in cm 1. Spectra of 3a and 3b were recorded in methylene chloride and N 2 S 2 TPOC 12 was recorded in toluene.*indicates oscillator strengths of both Soret bands.
15 Figure S3: DSC thermogram of dithiaporphyrin 3b at 5 C/min. Figure S4: Powder XRD of porphyrin 3a taken at left) room temperature right) 260 C. Inset shows smaller intensity peaks.
16 Figure S5: Powder XRD of blank capillary tube. Cartesian coordinates of DFT optimized [B3LYP 6 31G+(d)] structures of reduced model ethynyl dithiaporphyrins Reduced model of 3a: Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0 1.258496 2.748767 0.000001 2 6 0 0.691858 4.048831 0.000001 3 6 0 0.691858 4.048831 0.000001 4 6 0 1.258496 2.748767 0.000001 5 16 0 0.000000 1.533738 0.000000 6 6 0 2.645304 2.423095 0.000003 7 6 0 3.143475 1.087500 0.000001 8 6 0 4.546125 0.681431 0.000000 9 6 0 4.546125 0.681431 0.000000 10 6 0 3.143475 1.087500 0.000001 11 7 0 2.335789 0.000000 0.000000 12 6 0 2.645304 2.423095 0.000003 13 6 0 1.258496 2.748767 0.000001 14 6 0 0.691858 4.048831 0.000001 15 6 0 0.691858 4.048831 0.000001 16 6 0 1.258496 2.748767 0.000001
17 17 16 0 0.000000 1.533738 0.000000 18 6 0 2.645304 2.423095 0.000003 19 6 0 3.143475 1.087500 0.000001 20 6 0 4.546125 0.681431 0.000000 21 6 0 4.546125 0.681431 0.000000 22 6 0 3.143475 1.087500 0.000001 23 7 0 2.335789 0.000000 0.000000 24 1 0 1.301534 4.945263 0.000002 25 1 0 1.301534 4.945263 0.000002 26 1 0 5.398627 1.347796 0.000001 27 1 0 5.398627 1.347796 0.000001 28 1 0 1.301534 4.945263 0.000002 29 1 0 1.301534 4.945263 0.000002 30 1 0 5.398627 1.347796 0.000001 31 1 0 5.398627 1.347796 0.000001 32 6 0 2.645304 2.423095 0.000003 33 6 0 3.581276 3.490788 0.000004 34 6 0 3.581276 3.490788 0.000004 35 6 0 3.581276 3.490788 0.000004 36 6 0 3.581276 3.490788 0.000004 37 6 0 4.384860 4.409261 0.000004 38 6 0 4.384860 4.409261 0.000004 39 6 0 4.384860 4.409261 0.000004 40 6 0 4.384860 4.409261 0.000004 41 6 0 5.327989 5.473281 0.000004 42 6 0 6.711837 5.214223 0.000001 43 6 0 4.905064 6.823634 0.000007 44 6 0 7.644569 6.251469 0.000002 45 1 0 7.058890 4.185149 0.000001 46 6 0 5.825871 7.859410 0.000007 47 1 0 3.842342 7.047145 0.000010 48 6 0 7.203971 7.582729 0.000004 49 6 0 5.327989 5.473281 0.000004 50 6 0 6.711837 5.214223 0.000001 51 6 0 4.905064 6.823634 0.000007 52 6 0 7.644569 6.251469 0.000002 53 1 0 7.058890 4.185149 0.000001 54 6 0 5.825871 7.859410 0.000007 55 1 0 3.842342 7.047145 0.000010 56 6 0 7.203971 7.582729 0.000004 57 6 0 5.327989 5.473281 0.000004 58 6 0 4.905064 6.823634 0.000007 59 6 0 6.711837 5.214223 0.000001 60 6 0 5.825871 7.859410 0.000007
18 61 1 0 3.842342 7.047145 0.000010 62 6 0 7.644569 6.251469 0.000002 63 1 0 7.058890 4.185149 0.000001 64 6 0 7.203971 7.582729 0.000004 65 6 0 5.327989 5.473281 0.000004 66 6 0 6.711837 5.214223 0.000001 67 6 0 4.905064 6.823634 0.000007 68 6 0 7.644569 6.251469 0.000002 69 1 0 7.058890 4.185149 0.000001 70 6 0 5.825871 7.859410 0.000007 71 1 0 3.842342 7.047145 0.000010 72 6 0 7.203971 7.582729 0.000004 73 1 0 8.701767 6.011304 0.000000 74 1 0 5.503360 8.896284 0.000010 75 1 0 5.503360 8.896284 0.000010 76 1 0 8.701767 6.011304 0.000000 77 1 0 8.701767 6.011304 0.000000 78 1 0 5.503360 8.896284 0.000010 79 1 0 5.503360 8.896284 0.000010 80 1 0 8.701767 6.011304 0.000000 81 8 0 8.026197 8.670155 0.000005 82 8 0 8.026197 8.670155 0.000005 83 8 0 8.026197 8.670155 0.000005 84 8 0 8.026197 8.670155 0.000005 85 6 0 9.434210 8.464171 0.000003 86 1 0 9.756496 7.920167 0.897223 87 1 0 9.878078 9.460919 0.000005 88 1 0 9.756494 7.920170 0.897219 89 6 0 9.434210 8.464171 0.000003 90 1 0 9.756496 7.920167 0.897223 91 1 0 9.878078 9.460919 0.000005 92 1 0 9.756494 7.920170 0.897219 93 6 0 9.434210 8.464171 0.000003 94 1 0 9.756496 7.920167 0.897223 95 1 0 9.878078 9.460919 0.000005 96 1 0 9.756494 7.920170 0.897219 97 6 0 9.434210 8.464171 0.000003 98 1 0 9.756496 7.920167 0.897223 99 1 0 9.878078 9.460919 0.000005 100 1 0 9.756494 7.920170 0.897219 Energy = 3362.20570766 a.u.
19 Reduced model of 3b: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 1 6 0 2.748573 1.258256 0.000000 2 6 0 4.049043 0.691740 0.000000 3 6 0 4.049043 0.691740 0.000000 4 6 0 2.748573 1.258256 0.000000 5 16 0 1.533587 0.000000 0.000000 6 6 0 2.422477 2.644607 0.000000 7 6 0 1.087257 3.142919 0.000000 8 6 0 0.681221 4.546134 0.000000 9 6 0 0.681221 4.546134 0.000000 10 6 0 1.087257 3.142919 0.000000 11 7 0 0.000000 2.335092 0.000000 12 6 0 2.422477 2.644607 0.000000 13 6 0 2.748573 1.258256 0.000000 14 6 0 4.049043 0.691740 0.000000 15 6 0 4.049043 0.691740 0.000000 16 6 0 2.748573 1.258256 0.000000 17 16 0 1.533587 0.000000 0.000000 18 6 0 2.422477 2.644607 0.000000 19 6 0 1.087257 3.142919 0.000000 20 6 0 0.681221 4.546134 0.000000 21 6 0 0.681221 4.546134 0.000000 22 6 0 1.087257 3.142919 0.000000 23 7 0 0.000000 2.335092 0.000000 24 1 0 4.945284 1.301639 0.000000 25 1 0 4.945284 1.301639 0.000000 26 1 0 1.347613 5.398532 0.000000 27 1 0 1.347613 5.398532 0.000000 28 1 0 4.945284 1.301639 0.000000 29 1 0 4.945284 1.301639 0.000000 30 1 0 1.347613 5.398532 0.000000 31 1 0 1.347613 5.398532 0.000000 32 6 0 2.422477 2.644607 0.000000 33 6 0 3.490071 3.581460 0.000000 34 6 0 3.490071 3.581460 0.000000 35 6 0 3.490071 3.581460 0.000000 36 6 0 3.490071 3.581460 0.000000 37 6 0 4.407600 4.385537 0.000000 38 6 0 4.407600 4.385537 0.000000
20 39 6 0 4.407600 4.385537 0.000000 40 6 0 4.407600 4.385537 0.000000 41 6 0 5.468600 5.334013 0.000000 42 6 0 5.199992 6.717764 0.000000 43 6 0 6.817219 4.915438 0.000000 44 6 0 6.243060 7.641855 0.000000 45 1 0 4.169061 7.059507 0.000000 46 6 0 7.847494 5.849618 0.000000 47 1 0 7.043788 3.853132 0.000000 48 6 0 7.583500 7.230010 0.000000 49 6 0 5.468600 5.334013 0.000000 50 6 0 5.199992 6.717764 0.000000 51 6 0 6.817219 4.915438 0.000000 52 6 0 6.243060 7.641855 0.000000 53 1 0 4.169061 7.059507 0.000000 54 6 0 7.847494 5.849618 0.000000 55 1 0 7.043788 3.853132 0.000000 56 6 0 7.583500 7.230010 0.000000 57 6 0 5.468600 5.334013 0.000000 58 6 0 6.817219 4.915438 0.000000 59 6 0 5.199992 6.717764 0.000000 60 6 0 7.847494 5.849618 0.000000 61 1 0 7.043788 3.853132 0.000000 62 6 0 6.243060 7.641855 0.000000 63 1 0 4.169061 7.059507 0.000000 64 6 0 7.583500 7.230010 0.000000 65 6 0 5.468600 5.334013 0.000000 66 6 0 5.199992 6.717764 0.000000 67 6 0 6.817219 4.915438 0.000000 68 6 0 6.243060 7.641855 0.000000 69 1 0 4.169061 7.059507 0.000000 70 6 0 7.847494 5.849618 0.000000 71 1 0 7.043788 3.853132 0.000000 72 6 0 7.583500 7.230010 0.000000 73 1 0 6.010308 8.704496 0.000000 74 1 0 8.879008 5.502642 0.000000 75 1 0 8.879008 5.502642 0.000000 76 1 0 6.010308 8.704496 0.000000 77 1 0 6.010308 8.704496 0.000000 78 1 0 8.879008 5.502642 0.000000 79 1 0 8.879008 5.502642 0.000000 80 1 0 6.010308 8.704496 0.000000 81 6 0 8.714804 8.231146 0.000000 82 1 0 9.355514 8.108621 0.882682
21 83 1 0 9.355514 8.108621 0.882682 84 1 0 8.339232 9.259518 0.000000 85 6 0 8.714804 8.231146 0.000000 86 1 0 9.355514 8.108621 0.882682 87 1 0 9.355514 8.108621 0.882682 88 1 0 8.339232 9.259518 0.000000 89 6 0 8.714804 8.231146 0.000000 90 1 0 9.355514 8.108621 0.882682 91 1 0 9.355514 8.108621 0.882682 92 1 0 8.339232 9.259518 0.000000 93 6 0 8.714804 8.231146 0.000000 94 1 0 9.355514 8.108621 0.882682 95 1 0 9.355514 8.108621 0.882682 96 1 0 8.339232 9.259518 0.000000 Energy = 3061.37103444 a.u.