ELECTRONIC SUPPORTING INFORMATION. · 2011. 4. 7. · Page S3 of S53 Table S12. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for β-BrPhO-BsubPc

Page S1 of S53

A Role for π-Br Interactions in the Solid-State Molecular

Packing of Para-Halo-Phenoxy-Boronsubphthalocyanines.

Andrew S. Paton†, Alan J. Lough‡, and Timothy P. Bender†,‡,* † - Department of Chemical Engineering and Applied Chemistry, The University of Toronto, 200 College St., Toronto, Ontario, Canada, M5S 3E5 ‡ - Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, Canada, M5S 3H6 * - To whom all correspondence should be addressed: [email protected]

ELECTRONIC SUPPORTING INFORMATION.

Supplementary Material (ESI) for CrystEngCommThis journal is © The Royal Society of Chemistry 2011

Page S2 of S53

LIST OF TABLES AND FIGURES. Figure S1. Anisotropic displacement ellipsoid plot of ClPhO-BsubPc (compound 2b). Figure S2. Populated unit cell of ClPhO-BsubPc (compound 2b). Table S1. Crystal data and structure refinement for ClPhO-BsubPc (compound 2b). Table S2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for ClPhO-BsubPc (compound 2b). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. Table S3. Bond lengths [Å] and angles [°] for ClPhO-BsubPc (compound 2b). Table S4. Anisotropic displacement parameters (Å2x 103) for ClPhO-BsubPc (compound 2b). The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] Table S5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for ClPhO-BsubPc (compound 2b). Figure S3. Anisotropic displacement ellipsoid plot of α-BrPhO-BsubPc (compound 2c). Figure S4. Populated unit cell of α-BrPhO-BsubPc (compound 2c). Table S6. Crystal data and structure refinement for α-BrPhO-BsubPc (compound 2c). Table S7. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for α-BrPhO-BsubPc (compound 2c). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. Table S8. Bond lengths [Å] and angles [°] for α-BrPhO-BsubPc (compound 2c). Table S9. Anisotropic displacement parameters (Å2x 103) for α-BrPhO-BsubPc (compound 2c). The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] Table S10. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for α-BrPhO-BsubPc (compound 2c). Figure S5. Anisotropic displacement ellipsoid plot of β-BrPhO-BsubPc (compound 2c). Figure S6. Populated unit cell of β-BrPhO-BsubPc (compound 2c). Table S11. Crystal data and structure refinement for β-BrPhO-BsubPc (compound 2c).


Page S3 of S53

Table S12. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for β-BrPhO-BsubPc (compound 2c). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. Table S13. Bond lengths [Å] and angles [°] for β-BrPhO-BsubPc (compound 2c). Table S14. Anisotropic displacement parameters (Å2x 103) for β-BrPhO-BsubPc (compound 2c). The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] Table S15. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for β-BrPhO-BsubPc (compound 2c). Figure S7. Anisotropic displacement ellipsoid plot of IPhO-BsubPc (compound 2d). Figure S8. Populated unit cell of IPhO-BsubPc (compound 2d). Table S16. Crystal data and structure refinement for IPhO-BsubPc (compound 2d). Table S17. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)for IPhO-BsubPc (compound 2d). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. Table S18. Bond lengths [Å] and angles [°] for IPhO-BsubPc (compound 2d). Table S19. Anisotropic displacement parameters (Å2x 103) for IPhO-BsubPc (compound 2d). The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ] Table S20. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for IPhO-BsubPc (compound 2d). Figure S9: Electrostatic potential 3D mapped isosurface plot of FPhO-BsubPc (2a) generated using the 6-31G* basis set with the B3LYP DFT method. Areas of electron deficiency are colored blue; areas of electron excess are colored red. Figure S10: Electrostatic potential 3D mapped isosurface plot of ClPhO-BsubPc (2b) generated using the 6-31G* basis set with the B3LYP DFT method. Areas of electron deficiency are colored blue; areas of electron excess are colored red. Figure S11: Electrostatic potential 3D mapped isosurface plot of IPhO-BsubPc (2d) generated using the 6-6-311G* basis set with the B3LYP DFT method. Areas of electron deficiency are colored blue; areas of electron excess are colored red.


Page S4 of S53

EXPERIMENTAL.

Materials

4-Fluorophenol was purchased from TCI Company Ltd. (Portland, Oregon). 4-Chlorophenol,

4-bromophenol, and 4-iodophenol were obtained from Sigma Aldrich (Mississauga, Ontario,

Canada). All reagents were used as received. Other common solvents, reagents and standard

basic alumina (300 mesh) were purchased from Caledon Laboratories (Caledon, Ontario,

Canada) and used as received. Cl-BsubPc was synthesized according to a previously

described procedure. [1]

Methods

X-ray diffraction results were analyzed using PLATON 40M-version 250809 [2] for

bond angles and lengths, and crystal packing images were generated using Mercury version

2.2. [3] All data sets were collected using a Nonius KappaCCD diffractometer equipped with

an Oxford Cryostream variable temperature apparatus. Hydrogen positions were calculated.

All nuclear magnetic resonance (NMR) spectra were acquired on a Varian Mercury

400 MHz system in deuterated chloroform with 0.05% (v/v) tetramethylsilane (TMS) as a 1H

NMR reference purchased from Cambridge Isotope Laboratories and used as received. All

ultraviolet-visible (UV-Vis) spectroscopy was performed using PerkinElmer Lambda 25 in a

PerkinElmer quartz cuvette with 10.00 mm path length.

The progress of reactions was monitored using a Waters 2695 high pressure liquid

chromatography (HPLC) separation module with a Waters 2998 photodiode array. A Waters

150 mm reverse phase Sunfire® C18 5μm column was used with HPLC grade acetonitrile

(ACN, 1.2 mL/min isocratic) purchased from Caledon Laboratories as the eluent.

Molecular level computer modeling was performed at the density functional theory

level using the 6-31G* basis set with the B3LYP method in the SPARTAN ’06 V102

software package, except for that of IPhO-BsubPc, which was performed using the 6-311G*

basis set.

Crystal level computer modeling was performed as follows: the crystallographic

information files (.cif) were imported into Materials Studio version 5.0 (Accelrys Inc.) [4].

The aromatic pattern of the BsubPc ligand was recreated in the visualization window. Next,

using the DMol3 module [5,6] the electrostatic potential (ESP) surface was calculated at DFT

level (fine quality) employing the PW91 functional and DNP basis set. The ESP surface was

imported and applied to the crystal lattice, and the Forcite module was used to calculate the


Page S5 of S53

crystal lattice energies of the experimental structures at the molecular mechanics (MM) level.

The DREIDING forcefield[7] with Ewald summations for the van der Waal and electrostatic

intermolecular interactions was chosen since not only does it natively support all of the atom

types within the molecules, but it also has been shown to provide an accurate calculation for

the energy ranking of crystal structures.[8] Subsequently, the Forcite module was used to

perform a MM single point energy calculation on the structure.

REFERENCES.

[1] G.E. Morse, A.S. Paton, and T.P. Bender, Dalton Transactions, 2010, 39(16), 3915 –

3922.

[2] A.L. Spek, Acta Cryst., 2009, D65, 148-155.

[3] (a) I. J. Bruno, J. C. Cole, P. R. Edgington, M. K. Kessler, C. F. Macrae, P. McCabe, J.

Pearson and R. Taylor, Acta Cryst., 2002, B58, 389-397; (b) C. F. Macrae, P. R. Edgington,

P. McCabe, E. Pidcock, G. P. Shields, R. Taylor, M. Towler and J. van de Streek, J. Appl.

Cryst., 2006, 39, 453-457. (c) C.F. Macrae, I.J. Bruno, J.A. Chisholm, P.R. Edgington, P.

McCabe, E. Pidcock, L. Rodriguez-Monge, R. Taylor, J. van de Streek, and P.A. Wood, J.

Appl. Cryst., 2008, 41, 466-470.

[4] Accelrys Inc., Materials Studio, DMol3, Forcite., 9685 Scranton Road, San Diego, CA

92121-3752, USA. Accelrys (2001).

[5] B. Delley, J. Chem. Phys., 1990, 92, 508.

[6] B. Delley, J. Chem. Phys., 2000, 113, 7756.

[7] S.L. Mayo, B.D. Olafson, W.A. Goddard, J. Phys. Chem. 1990, 94, 8897−8909.

[8] (a) M. Svärd and Å.C. Rasmuson, Ind. Eng. Chem. Res., 2009, 48, 2899-2912; (b) K.-H.

Kim, D.H. Jung, D. Kim, A. Lee, K. Choi, Y. Kim, and S.-H. Choi, Dyes Pigments, 2011, 89,

37-43.


Page S6 of S53

Synthesis

4-Fluorophenoxyboronsubphthalocyanine (FPhO-BsubPc, 2a, previously reported: A.S.

Paton, G.E. Morse, A.J. Lough, and T.P. Bender, CrystEngComm, in press.)

4-Chlorophenoxyboronsubphthalocyanine (ClPhO-BsubPc, 2b).

Cl-BsubPc (1, 0.601 g, 0.0014 mol) was mixed with 4-chlorophenol (0.896 g, 0.0069 mol) in

toluene (10 mL) in a cylindrical vessel fitted with a reflux condenser and argon inlet. The

mixture was stirred and heated at reflux under a constant pressure of argon for 20 hours.

Reaction was determined complete via HPLC by the absence of 1. The solvent was removed

under rotary evaporation. The crude product was purified first by dissolving the product in

toluene (300 mL) and extracting with 3.0 M KOH solution in distilled water (3 x 300 mL).

After removal of the toluene, the product was then purified on a Kauffman column using

standard basic alumina (300 mesh) as the adsorbent and dichloromethane as the eluent. The

product elutes from the Kauffman column while the excess phenol remains adsorbed. The

dichloromethane was then removed under reduced pressure yielding a dark pink/magenta

powder. Compound 2b (yield 0.228 g, 31 %). δH(400 MHz; CDCl3; Me4Si) 5.32 (2H, d),

6.70 (2H, d), 7.91-7.93 (6H, m), 8.85-8.87 (6H, m); λmax(CHCl3)/nm 563. HRMS (EI) Calcd.

for [C30H16BN6OCl] ([M]+): m/z 522.1167, found 522.1180.

4-bromophenoxyboronsubphthalocyanine (BrPhO-BsubPc, 2c). 2c was synthesized as for

2b except 4-bromophenol (1.205 g, 0.0069 mol) was used in place of 4-fluorophenol,

yielding compound 2b (0.468 g, 59 %). δH(400 MHz; CDCl3; Me4Si) 5.27 (2H, d), 6.84 (2H,

d), 7.91-7.93 (6H, m), 8.85-8.87 (6H, m); λmax(CHCl3)/nm 563. HRMS (EI) Calcd. for

[C30H16BN6OBr] ([M]+): m/z 566.0662, found 566.0668.

4-iodophenoxyboronsubphthalocyanine (IPhO-BsubPc, 2d). 2d was synthesized as for 2b

except 4-iodophenol (1.531 g, 0.0069 mol) was used in place of 4-fluorophenol, yielding

compound 2d (0.540 g, 74 %). δH(400 MHz; CDCl3; Me4Si) 5.18 (2H, d), 7.01 (2H, d),

7.90-7.92 (6H, m), 8.85-8.87 (6H, m); λmax(CHCl3)/nm 563. HRMS (EI) Calcd. for

[C30H16BN6OI] ([M]+): m/z 614.0523, found 614.0530.


Page S7 of S53

Figure S1. Anisotropic displacement ellipsoid plot of ClPhO-BsubPc (compound 2b).

Figure S2. Populated unit cell of ClPhO-BsubPc (compound 2d).


Page S8 of S53

Table S1. Crystal data and structure refinement for ClPhO-BsubPc (compound 2d).

Identification code k1038

Empirical formula C30 H16 B Cl N6 O

Formula weight 522.75

Temperature 150(2) K Wavelength 0.71073 Å

Crystal system Triclinic

Space group P -1

Unit cell dimensions a = 10.0961(4) Å α= 86.562(2)°. b = 10.9362(4) Å β= 78.274(2)°.

c = 11.6798(3) Å γ = 67.4840(14)°.

Volume 1166.21(7) Å3

Z 2 Density (calculated) 1.489 Mg/m3

Absorption coefficient 0.204 mm-1

F(000) 536

Crystal size 0.20 x 0.14 x 0.13 mm3 Theta range for data collection 2.57 to 27.48°.

Index ranges -12<=h<=13, -14<=k<=14, -14<=l<=15

Reflections collected 10801

Independent reflections 5249 [R(int) = 0.0411] Completeness to theta = 25.24° 99.1 %

Absorption correction Semi-empirical from equivalents

Max. and min. transmission 0.978 and 0.876

Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 5249 / 0 / 352

Goodness-of-fit on F2 1.059

Final R indices [I>2sigma(I)] R1 = 0.0524, wR2 = 0.1304

R indices (all data) R1 = 0.0841, wR2 = 0.1548 Largest diff. peak and hole 0.370 and -0.406 e.Å-3


Page S9 of S53

Table S2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters

(Å2x 103) for ClPhO-BsubPc (compound 2d). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

___________________________________________________________________________

_

x y z U(eq) ___________________________________________________________________________

_

Cl(1) -4110(1) 9231(1) 7342(1) 41(1)

O(1) 1159(2) 5724(2) 9020(1) 26(1) N(1) 3638(2) 4056(2) 8660(1) 24(1)

N(2) 3256(2) 2026(2) 8766(1) 25(1)

N(3) 1963(2) 3805(2) 7631(1) 24(1)

N(4) 1643(2) 4934(2) 5834(2) 25(1) N(5) 2869(2) 5486(2) 7127(2) 24(1)

N(6) 4950(2) 5414(2) 7815(2) 28(1)

C(1) 4810(2) 4438(2) 8528(2) 25(1)

C(2) 5908(2) 3397(2) 9039(2) 25(1) C(3) 7321(3) 3231(2) 9117(2) 32(1)

C(4) 8194(3) 2046(2) 9528(2) 34(1)

C(5) 7675(3) 1036(2) 9850(2) 32(1)

C(6) 6287(2) 1165(2) 9758(2) 28(1) C(7) 5385(2) 2357(2) 9348(2) 24(1)

C(8) 3966(2) 2770(2) 9009(2) 24(1)

C(9) 2332(2) 2526(2) 8018(2) 24(1)

C(10) 1863(2) 1849(2) 7247(2) 25(1) C(11) 1977(2) 537(2) 7180(2) 27(1)

C(12) 1549(3) 164(2) 6252(2) 31(1)

C(13) 1047(3) 1053(2) 5382(2) 33(1)

C(14) 969(2) 2344(2) 5400(2) 29(1) C(15) 1360(2) 2748(2) 6343(2) 25(1)

C(16) 1545(2) 3962(2) 6570(2) 25(1)

C(17) 2382(2) 5635(2) 6097(2) 25(1)

C(18) 3091(2) 6423(2) 5370(2) 24(1) C(19) 2961(2) 6963(2) 4269(2) 27(1)

C(20) 3805(3) 7688(2) 3815(2) 31(1)


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C(21) 4814(3) 7816(2) 4407(2) 32(1)

C(22) 5006(2) 7235(2) 5480(2) 29(1) C(23) 4112(2) 6573(2) 5979(2) 25(1)

C(24) 4012(2) 5875(2) 7082(2) 25(1)

C(25) -66(2) 6544(2) 8604(2) 24(1)

C(26) -1188(2) 6113(2) 8598(2) 28(1) C(27) -2431(2) 6929(2) 8185(2) 29(1)

C(28) -2531(2) 8178(2) 7801(2) 29(1)

C(29) -1418(2) 8618(2) 7803(2) 28(1)

C(30) -175(2) 7792(2) 8201(2) 27(1) B(1) 2317(3) 4827(2) 8169(2) 23(1)

___________________________________________________________________________

_


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Table S3. Bond lengths [Å] and angles [°] for ClPhO-BsubPc (compound 2d).

_____________________________________________________ Cl(1)-C(28) 1.738(2)

O(1)-C(25) 1.383(3)

O(1)-B(1) 1.442(3)

N(1)-C(8) 1.372(3) N(1)-C(1) 1.377(3)

N(1)-B(1) 1.487(3)

N(2)-C(8) 1.346(3)

N(2)-C(9) 1.348(3) N(3)-C(16) 1.369(3)

N(3)-C(9) 1.376(3)

N(3)-B(1) 1.501(3)

N(4)-C(17) 1.341(3) N(4)-C(16) 1.348(3)

N(5)-C(24) 1.365(3)

N(5)-C(17) 1.368(3)

N(5)-B(1) 1.496(3) N(6)-C(24) 1.341(3)

N(6)-C(1) 1.347(3)

C(1)-C(2) 1.449(3)

C(2)-C(3) 1.389(3) C(2)-C(7) 1.427(3)

C(3)-C(4) 1.382(3)

C(4)-C(5) 1.396(3)

C(5)-C(6) 1.379(3) C(6)-C(7) 1.397(3)

C(7)-C(8) 1.459(3)

C(9)-C(10) 1.450(3)

C(10)-C(11) 1.400(3) C(10)-C(15) 1.432(3)

C(11)-C(12) 1.380(3)

C(12)-C(13) 1.396(3)

C(13)-C(14) 1.385(3) C(14)-C(15) 1.391(3)

C(15)-C(16) 1.456(3)


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C(17)-C(18) 1.454(3)

C(18)-C(19) 1.392(3) C(18)-C(23) 1.427(3)

C(19)-C(20) 1.386(3)

C(20)-C(21) 1.393(3)

C(21)-C(22) 1.386(3) C(22)-C(23) 1.383(3)

C(23)-C(24) 1.463(3)

C(25)-C(26) 1.385(3)

C(25)-C(30) 1.387(3) C(26)-C(27) 1.393(3)

C(27)-C(28) 1.384(3)

C(28)-C(29) 1.382(3)

C(29)-C(30) 1.389(3)

C(25)-O(1)-B(1) 115.79(15)

C(8)-N(1)-C(1) 112.75(18)

C(8)-N(1)-B(1) 123.18(18) C(1)-N(1)-B(1) 122.11(18)

C(8)-N(2)-C(9) 117.09(18)

C(16)-N(3)-C(9) 112.77(18)

C(16)-N(3)-B(1) 122.90(17) C(9)-N(3)-B(1) 122.88(17)

C(17)-N(4)-C(16) 116.69(17)

C(24)-N(5)-C(17) 113.69(17)

C(24)-N(5)-B(1) 122.54(17) C(17)-N(5)-B(1) 123.46(17)

C(24)-N(6)-C(1) 116.79(18)

N(6)-C(1)-N(1) 123.07(19)

N(6)-C(1)-C(2) 129.4(2) N(1)-C(1)-C(2) 105.74(18)

C(3)-C(2)-C(7) 120.7(2)

C(3)-C(2)-C(1) 131.2(2)

C(7)-C(2)-C(1) 107.56(18) C(4)-C(3)-C(2) 118.3(2)

C(3)-C(4)-C(5) 121.0(2)


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C(6)-C(5)-C(4) 121.9(2)

C(5)-C(6)-C(7) 118.1(2) C(6)-C(7)-C(2) 120.0(2)

C(6)-C(7)-C(8) 132.6(2)

C(2)-C(7)-C(8) 106.93(18)

N(2)-C(8)-N(1) 122.77(19) N(2)-C(8)-C(7) 129.4(2)

N(1)-C(8)-C(7) 105.75(18)

N(2)-C(9)-N(3) 122.35(19)

N(2)-C(9)-C(10) 129.8(2) N(3)-C(9)-C(10) 105.88(17)

C(11)-C(10)-C(15) 119.74(19)

C(11)-C(10)-C(9) 132.6(2)

C(15)-C(10)-C(9) 107.24(18) C(12)-C(11)-C(10) 118.3(2)

C(11)-C(12)-C(13) 121.5(2)

C(14)-C(13)-C(12) 121.7(2)

C(13)-C(14)-C(15) 117.7(2) C(14)-C(15)-C(10) 121.1(2)

C(14)-C(15)-C(16) 131.55(19)

C(10)-C(15)-C(16) 106.93(18)

N(4)-C(16)-N(3) 122.88(19) N(4)-C(16)-C(15) 129.54(19)

N(3)-C(16)-C(15) 105.97(17)

N(4)-C(17)-N(5) 122.14(18)

N(4)-C(17)-C(18) 131.10(18) N(5)-C(17)-C(18) 105.53(17)

C(19)-C(18)-C(23) 120.39(19)

C(19)-C(18)-C(17) 132.4(2)

C(23)-C(18)-C(17) 107.20(17) C(20)-C(19)-C(18) 117.9(2)

C(19)-C(20)-C(21) 121.4(2)

C(22)-C(21)-C(20) 121.5(2)

C(23)-C(22)-C(21) 117.9(2) C(22)-C(23)-C(18) 120.76(19)

C(22)-C(23)-C(24) 132.1(2)


Page S14 of S53

C(18)-C(23)-C(24) 107.13(18)

N(6)-C(24)-N(5) 122.33(19) N(6)-C(24)-C(23) 131.02(19)

N(5)-C(24)-C(23) 105.24(17)

O(1)-C(25)-C(26) 119.48(19)

O(1)-C(25)-C(30) 120.32(19) C(26)-C(25)-C(30) 120.2(2)

C(25)-C(26)-C(27) 120.2(2)

C(28)-C(27)-C(26) 118.9(2)

C(29)-C(28)-C(27) 121.4(2) C(29)-C(28)-Cl(1) 119.30(18)

C(27)-C(28)-Cl(1) 119.29(18)

C(28)-C(29)-C(30) 119.3(2)

C(25)-C(30)-C(29) 120.0(2) O(1)-B(1)-N(1) 112.52(17)

O(1)-B(1)-N(5) 114.48(18)

N(1)-B(1)-N(5) 104.39(17)

O(1)-B(1)-N(3) 116.42(18) N(1)-B(1)-N(3) 104.75(17)

N(5)-B(1)-N(3) 102.98(16)

_____________________________________________________________

Symmetry transformations used to generate equivalent atoms:


Page S15 of S53

Table S4. Anisotropic displacement parameters (Å2x 103) for ClPhO-BsubPc (compound

2d). The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ]

___________________________________________________________________________

_

U11 U22 U33 U23 U13 U12 ___________________________________________________________________________

_

Cl(1) 36(1) 33(1) 49(1) 5(1) -18(1) -4(1)

O(1) 29(1) 23(1) 27(1) 3(1) -9(1) -8(1) N(1) 27(1) 23(1) 24(1) 3(1) -8(1) -10(1)

N(2) 28(1) 23(1) 25(1) 2(1) -8(1) -10(1)

N(3) 26(1) 21(1) 27(1) 4(1) -9(1) -9(1)

N(4) 26(1) 20(1) 30(1) 2(1) -10(1) -7(1) N(5) 25(1) 19(1) 28(1) 3(1) -9(1) -8(1)

N(6) 31(1) 23(1) 32(1) 3(1) -12(1) -10(1)

C(1) 28(1) 23(1) 27(1) -2(1) -9(1) -10(1)

C(2) 30(1) 23(1) 24(1) 1(1) -11(1) -8(1) C(3) 33(1) 32(1) 35(1) 1(1) -14(1) -15(1)

C(4) 30(1) 36(1) 37(1) 1(1) -18(1) -10(1)

C(5) 34(1) 28(1) 30(1) 3(1) -15(1) -6(1)

C(6) 33(1) 24(1) 25(1) 3(1) -10(1) -9(1) C(7) 27(1) 24(1) 23(1) 1(1) -8(1) -9(1)

C(8) 26(1) 22(1) 23(1) 3(1) -8(1) -7(1)

C(9) 24(1) 23(1) 25(1) 4(1) -5(1) -9(1)

C(10) 22(1) 28(1) 28(1) 4(1) -6(1) -11(1) C(11) 30(1) 22(1) 30(1) 5(1) -8(1) -10(1)

C(12) 32(1) 26(1) 37(1) 1(1) -8(1) -12(1)

C(13) 36(1) 32(1) 35(1) -2(1) -11(1) -16(1)

C(14) 30(1) 29(1) 31(1) 5(1) -12(1) -12(1) C(15) 23(1) 23(1) 28(1) 4(1) -6(1) -9(1)

C(16) 23(1) 23(1) 27(1) 2(1) -8(1) -6(1)

C(17) 26(1) 20(1) 26(1) 3(1) -8(1) -6(1)

C(18) 28(1) 16(1) 27(1) 2(1) -5(1) -5(1) C(19) 28(1) 23(1) 28(1) -1(1) -5(1) -6(1)

C(20) 37(1) 27(1) 26(1) 4(1) -2(1) -10(1)


Page S16 of S53

C(21) 31(1) 25(1) 36(1) 4(1) 0(1) -9(1)

C(22) 25(1) 25(1) 36(1) 1(1) -5(1) -8(1) C(23) 26(1) 18(1) 28(1) 2(1) -5(1) -6(1)

C(24) 25(1) 20(1) 32(1) 1(1) -7(1) -9(1)

C(25) 25(1) 23(1) 20(1) 0(1) -5(1) -6(1)

C(26) 29(1) 24(1) 29(1) 4(1) -5(1) -10(1) C(27) 27(1) 31(1) 30(1) 2(1) -7(1) -12(1)

C(28) 30(1) 26(1) 27(1) 0(1) -9(1) -5(1)

C(29) 36(1) 18(1) 30(1) 2(1) -8(1) -10(1)

C(30) 30(1) 25(1) 28(1) 2(1) -7(1) -12(1) B(1) 23(1) 20(1) 25(1) 2(1) -8(1) -6(1)

___________________________________________________________________________

_


Page S17 of S53

Table S5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)

for ClPhO-BsubPc (compound 2d). ___________________________________________________________________________

_

x y z U(eq)

____________________________________________________________________________

H(3A) 7678 3916 8894 38

H(4A) 9162 1916 9592 41 H(5A) 8296 237 10140 38

H(6A) 5954 464 9968 33

H(11A) 2339 -80 7759 32

H(12A) 1597 -716 6205 37 H(13A) 752 764 4761 40

H(14A) 659 2933 4790 34

H(19A) 2313 6838 3842 33

H(20A) 3694 8107 3084 38 H(21A) 5382 8313 4067 39

H(22A) 5728 7289 5861 35

H(26A) -1110 5259 8876 33

H(27A) -3197 6633 8166 34 H(29A) -1503 9477 7534 33

H(30A) 602 8081 8198 32

___________________________________________________________________________

_


Page S18 of S53

Figure S3. Anisotropic displacement ellipsoid plot of α-BrPhO-BsubPc (compound 2c).

Figure S4. Populated unit cell of α-BrPhO-BsubPc (compound 2c).


Page S19 of S53

Table S6. Crystal data and structure refinement for α-BrPhO-BsubPc (compound 2c).

Identification code k1002 Empirical formula C30 H16 B Br N6 O


Temperature 150(2) K

Wavelength 0.71073 Å Crystal system Monoclinic

Space group P 21/n

Unit cell dimensions a = 15.7312(12) Å α= 90°.

b = 10.2246(9) Å β= 113.281(5)°. c = 16.4141(13) Å γ = 90°.

Volume 2425.2(3) Å3

Z 4

Density (calculated) 1.553 Mg/m3 Absorption coefficient 1.734 mm-1

F(000) 1144

Crystal size 0.38 x 0.15 x 0.04 mm3

Theta range for data collection 2.70 to 27.51°. Index ranges -20<=h<=19, -13<=k<=13, -21<=l<=21


Independent reflections 5448 [R(int) = 0.0961]

Completeness to theta = 25.00° 99.3 % Absorption correction Semi-empirical from equivalents


Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 5448 / 0 / 352 Goodness-of-fit on F2 1.026


R indices (all data) R1 = 0.1368, wR2 = 0.1690

Largest diff. peak and hole 0.732 and -1.060 e.Å-3


Page S20 of S53


(Å2x 103) for α-BrPhO-BsubPc (compound 2c). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ____________________________________________________________________________

x y z U(eq) ___________________________________________________________________________

_

Br(1) -1397(1) 204(1) 990(1) 64(1)

O(1) 1731(2) 479(3) 4599(2) 43(1) N(1) 2374(2) 1880(3) 5891(2) 33(1)

N(2) 3907(2) 1093(3) 6605(2) 36(1)

N(3) 3278(2) 1562(3) 5051(2) 34(1)

N(4) 3088(2) 3053(3) 3883(2) 36(1) N(5) 1939(2) 2885(3) 4486(2) 32(1)

N(6) 1247(2) 3579(3) 5467(2) 37(1)

C(1) 1796(3) 2736(4) 6069(3) 35(1)

C(2) 2114(3) 2737(4) 7035(3) 36(1) C(3) 1813(3) 3430(4) 7605(3) 43(1)

C(4) 2323(4) 3315(4) 8508(3) 49(1)

C(5) 3124(4) 2560(4) 8852(3) 52(1)

C(6) 3438(3) 1871(4) 8288(3) 46(1) C(7) 2927(3) 1973(4) 7385(3) 36(1)

C(8) 3109(3) 1519(4) 6631(3) 34(1)

C(9) 4000(3) 1207(4) 5828(3) 36(1)

C(10) 4832(3) 1363(4) 5668(3) 38(1) C(11) 5760(3) 1145(4) 6227(3) 45(1)

C(12) 6425(3) 1510(5) 5915(3) 51(1)

C(13) 6190(4) 2108(5) 5101(4) 52(1)

C(14) 5270(3) 2356(4) 4542(3) 45(1) C(15) 4582(3) 1957(4) 4826(3) 38(1)

C(16) 3586(3) 2179(4) 4477(3) 36(1)

C(17) 2297(3) 3466(4) 3937(3) 34(1)

C(18) 1807(3) 4696(4) 3661(3) 36(1) C(19) 1887(3) 5698(4) 3120(3) 40(1)

C(20) 1340(3) 6792(4) 3006(3) 43(1)


Page S21 of S53

C(21) 734(3) 6895(4) 3437(3) 46(1)

C(22) 670(3) 5943(4) 4001(3) 41(1) C(23) 1214(3) 4818(4) 4116(3) 35(1)

C(24) 1374(3) 3704(4) 4699(3) 34(1)

C(25) 1032(3) 462(4) 3778(3) 34(1)

C(26) 134(3) 284(4) 3705(3) 43(1) C(27) -591(3) 205(4) 2880(3) 44(1)

C(28) -401(3) 317(4) 2139(3) 43(1)

C(29) 474(3) 517(4) 2188(3) 44(1)

C(30) 1196(3) 595(5) 3013(3) 44(1) B(1) 2294(3) 1629(5) 4962(3) 35(1)

___________________________________________________________________________

_


Page S22 of S53

Table S8. Bond lengths [Å] and angles [°] for α-BrPhO-BsubPc (compound 2c).

_____________________________________________________ Br(1)-C(28) 1.922(4)

O(1)-C(25) 1.362(5)

O(1)-B(1) 1.451(6)

N(1)-C(8) 1.356(5) N(1)-C(1) 1.375(5)

N(1)-B(1) 1.503(6)

N(2)-C(9) 1.345(5)

N(2)-C(8) 1.345(5) N(3)-C(16) 1.371(5)

N(3)-C(9) 1.380(5)

N(3)-B(1) 1.497(6)

N(4)-C(16) 1.327(5) N(4)-C(17) 1.349(5)

N(5)-C(24) 1.364(5)

N(5)-C(17) 1.372(5)

N(5)-B(1) 1.492(6) N(6)-C(1) 1.338(5)

N(6)-C(24) 1.359(5)

C(1)-C(2) 1.462(6)

C(2)-C(3) 1.396(6) C(2)-C(7) 1.413(6)

C(3)-C(4) 1.384(6)

C(4)-C(5) 1.393(7)

C(5)-C(6) 1.399(6) C(6)-C(7) 1.383(6)

C(7)-C(8) 1.453(6)

C(9)-C(10) 1.442(6)

C(10)-C(11) 1.401(6) C(10)-C(15) 1.415(6)

C(11)-C(12) 1.385(6)

C(12)-C(13) 1.380(7)

C(13)-C(14) 1.396(7) C(14)-C(15) 1.399(6)

C(15)-C(16) 1.457(6)


Page S23 of S53

C(17)-C(18) 1.450(6)

C(18)-C(19) 1.394(6) C(18)-C(23) 1.412(6)

C(19)-C(20) 1.379(6)

C(20)-C(21) 1.396(6)

C(21)-C(22) 1.374(6) C(22)-C(23) 1.401(6)

C(23)-C(24) 1.445(6)

C(25)-C(26) 1.382(6)

C(25)-C(30) 1.384(6) C(26)-C(27) 1.386(6)

C(27)-C(28) 1.366(6)

C(28)-C(29) 1.362(6)

C(29)-C(30) 1.384(6)

C(25)-O(1)-B(1) 122.6(3)

C(8)-N(1)-C(1) 112.7(3)

C(8)-N(1)-B(1) 124.2(3) C(1)-N(1)-B(1) 121.9(4)

C(9)-N(2)-C(8) 117.0(4)

C(16)-N(3)-C(9) 111.8(3)

C(16)-N(3)-B(1) 123.0(4) C(9)-N(3)-B(1) 122.9(3)

C(16)-N(4)-C(17) 117.1(4)

C(24)-N(5)-C(17) 112.4(3)

C(24)-N(5)-B(1) 122.8(3) C(17)-N(5)-B(1) 123.4(3)

C(1)-N(6)-C(24) 117.2(3)

N(6)-C(1)-N(1) 122.8(4)

N(6)-C(1)-C(2) 130.1(4) N(1)-C(1)-C(2) 105.0(4)

C(3)-C(2)-C(7) 120.0(4)

C(3)-C(2)-C(1) 131.7(4)

C(7)-C(2)-C(1) 107.9(4) C(4)-C(3)-C(2) 117.9(4)

C(3)-C(4)-C(5) 122.0(4)


Page S24 of S53

C(4)-C(5)-C(6) 120.7(5)

C(7)-C(6)-C(5) 117.6(4) C(6)-C(7)-C(2) 121.8(4)

C(6)-C(7)-C(8) 131.5(4)

C(2)-C(7)-C(8) 106.4(4)

N(2)-C(8)-N(1) 122.5(4) N(2)-C(8)-C(7) 129.1(4)

N(1)-C(8)-C(7) 106.9(3)

N(2)-C(9)-N(3) 122.8(4)

N(2)-C(9)-C(10) 129.0(4) N(3)-C(9)-C(10) 106.1(3)

C(11)-C(10)-C(15) 121.6(4)

C(11)-C(10)-C(9) 130.4(4)

C(15)-C(10)-C(9) 107.6(4) C(12)-C(11)-C(10) 117.3(4)

C(13)-C(12)-C(11) 121.6(5)

C(12)-C(13)-C(14) 121.9(5)

C(13)-C(14)-C(15) 117.8(4) C(14)-C(15)-C(10) 119.8(4)

C(14)-C(15)-C(16) 132.6(4)

C(10)-C(15)-C(16) 107.0(4)

N(4)-C(16)-N(3) 123.2(4) N(4)-C(16)-C(15) 128.7(4)

N(3)-C(16)-C(15) 106.0(4)

N(4)-C(17)-N(5) 122.4(4)

N(4)-C(17)-C(18) 129.9(4) N(5)-C(17)-C(18) 106.0(3)

C(19)-C(18)-C(23) 121.1(4)

C(19)-C(18)-C(17) 131.7(4)

C(23)-C(18)-C(17) 107.0(4) C(20)-C(19)-C(18) 118.3(4)

C(19)-C(20)-C(21) 120.4(4)

C(22)-C(21)-C(20) 122.3(4)

C(21)-C(22)-C(23) 118.0(4) C(22)-C(23)-C(18) 119.8(4)

C(22)-C(23)-C(24) 132.4(4)


Page S25 of S53

C(18)-C(23)-C(24) 107.6(3)

N(6)-C(24)-N(5) 122.1(4) N(6)-C(24)-C(23) 129.7(4)

N(5)-C(24)-C(23) 105.9(3)

O(1)-C(25)-C(26) 119.0(4)

O(1)-C(25)-C(30) 122.0(4) C(26)-C(25)-C(30) 119.0(4)

C(25)-C(26)-C(27) 120.7(4)

C(28)-C(27)-C(26) 118.7(4)

C(29)-C(28)-C(27) 122.1(4) C(29)-C(28)-Br(1) 118.7(4)

C(27)-C(28)-Br(1) 119.3(3)

C(28)-C(29)-C(30) 119.1(4)

C(29)-C(30)-C(25) 120.4(4) O(1)-B(1)-N(5) 116.2(4)

O(1)-B(1)-N(3) 116.3(4)

N(5)-B(1)-N(3) 104.4(3)

O(1)-B(1)-N(1) 110.3(4) N(5)-B(1)-N(1) 104.4(3)

N(3)-B(1)-N(1) 103.9(4)

_____________________________________________________________



Page S26 of S53

Table S9. Anisotropic displacement parameters (Å2x 103) for α-BrPhO-BsubPc

(compound 2c). The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ]

___________________________________________________________________________

_

U11 U22 U33 U23 U13 U12 ___________________________________________________________________________

_

Br(1) 63(1) 44(1) 56(1) -4(1) -6(1) 7(1)

O(1) 52(2) 30(2) 37(2) 3(1) 7(2) -3(1) N(1) 42(2) 24(2) 34(2) 0(2) 17(2) 0(2)

N(2) 46(2) 29(2) 37(2) 3(2) 20(2) 3(2)

N(3) 41(2) 28(2) 35(2) -2(2) 17(2) 4(2)

N(4) 42(2) 36(2) 34(2) 0(2) 18(2) 6(2) N(5) 37(2) 29(2) 31(2) -1(2) 12(2) 2(2)

N(6) 41(2) 33(2) 38(2) -4(2) 16(2) -2(2)

C(1) 41(2) 33(2) 33(2) 0(2) 17(2) -4(2)

C(2) 45(3) 28(2) 39(2) 3(2) 21(2) -2(2) C(3) 56(3) 34(3) 43(3) 4(2) 24(2) 5(2)

C(4) 82(4) 32(3) 40(3) 4(2) 31(3) 6(2)

C(5) 83(4) 36(3) 38(3) 7(2) 25(3) 7(3)

C(6) 63(3) 31(3) 39(3) 7(2) 15(2) 4(2) C(7) 47(3) 27(2) 36(2) 3(2) 17(2) 0(2)

C(8) 46(3) 24(2) 34(2) 3(2) 18(2) 1(2)

C(9) 45(3) 23(2) 42(2) 2(2) 19(2) 7(2)

C(10) 45(3) 32(2) 39(2) 3(2) 19(2) 8(2) C(11) 53(3) 35(3) 45(3) 5(2) 16(2) 12(2)

C(12) 47(3) 42(3) 68(3) 5(3) 26(3) 8(2)

C(13) 50(3) 47(3) 67(3) 5(3) 32(3) 5(2)

C(14) 51(3) 41(3) 49(3) 1(2) 26(3) 4(2) C(15) 49(3) 28(2) 44(3) 1(2) 25(2) 7(2)

C(16) 46(3) 32(2) 34(2) -2(2) 19(2) 2(2)

C(17) 40(2) 32(2) 32(2) -6(2) 15(2) -4(2)

C(18) 42(2) 29(2) 34(2) -3(2) 10(2) 0(2) C(19) 44(3) 37(3) 36(2) 5(2) 13(2) -2(2)

C(20) 51(3) 29(2) 43(3) 4(2) 14(2) 0(2)


Page S27 of S53

C(21) 53(3) 26(2) 49(3) 1(2) 9(2) 8(2)

C(22) 46(3) 34(3) 41(2) -4(2) 14(2) 3(2) C(23) 37(2) 29(2) 35(2) -2(2) 12(2) 1(2)

C(24) 38(2) 30(2) 36(2) -4(2) 19(2) -3(2)

C(25) 44(3) 24(2) 36(2) -2(2) 17(2) 1(2)

C(26) 56(3) 30(2) 46(3) 1(2) 23(2) 4(2) C(27) 40(3) 32(2) 61(3) 0(2) 22(2) 3(2)

C(28) 44(3) 28(2) 45(3) 1(2) 6(2) 4(2)

C(29) 57(3) 40(3) 38(3) -7(2) 23(2) -5(2)

C(30) 40(3) 46(3) 45(3) -7(2) 16(2) -3(2) B(1) 42(3) 31(3) 35(3) 1(2) 18(2) 3(2)

___________________________________________________________________________

_


Page S28 of S53

Table S10. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for α-BrPhO-BsubPc (compound 2c). ___________________________________________________________________________

_

x y z U(eq)

H(3A) 1276 3963 7380 51

H(4A) 2121 3765 8906 59

H(5A) 3461 2513 9476 63

H(6A) 3982 1351 8518 55 H(11A) 5926 762 6797 54

H(12A) 7058 1345 6270 61

H(13A) 6667 2358 4916 62

H(14A) 5117 2781 3988 54 H(19A) 2308 5628 2837 48

H(20A) 1375 7481 2633 52

H(21A) 353 7649 3336 55

H(22A) 270 6045 4304 49 H(26A) 12 216 4226 51

H(27A) -1207 75 2830 52

H(29A) 587 602 1663 53

H(30A) 1808 741 3055 52 ___________________________________________________________________________

_


Page S29 of S53

Figure S5. Anisotropic displacement ellipsoid plot of β-BrPhO-BsubPc (compound 2c).

Figure S6. Populated unit cell of β-BrPhO-BsubPc (compound 2c).


Page S30 of S53

Table S11. Crystal data and structure refinement for β-BrPhO-BsubPc (compound 2c).

Identification code k10257

Empirical formula C30 H16 B Br N6 O



Wavelength 0.71073 Å

Crystal system Triclinic

Space group P -1

Unit cell dimensions a = 10.1389(4) Å α= 86.929(2)°.

b = 11.0056(4) Å β= 78.811(2)°.

c = 11.6749(5) Å γ = 68.0100(19)°.

Volume 1184.74(8) Å3

Z 2

Density (calculated) 1.590 Mg/m3

Absorption coefficient 1.775 mm-1

F(000) 572


Theta range for data collection 2.56 to 27.53°.

Index ranges -12<=h<=13, -14<=k<=14, -15<=l<=15



Completeness to theta = 27.53° 98.4 %

Absorption correction Semi-empirical from equivalents



Data / restraints / parameters 5379 / 0 / 352

Goodness-of-fit on F2 1.018





Page S31 of S53

Table S12. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)

for β-BrPhO-BsubPc (compound 2c). U(eq) is defined as one third of the trace of the

orthogonalized Uij tensor.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________ Br(1) -4166(1) 9274(1) 2309(1) 34(1)

O(1) 1184(2) 5700(2) 4035(1) 21(1)

N(1) 3634(2) 4052(2) 3679(2) 20(1)

N(2) 3239(2) 2045(2) 3782(2) 21(1)

N(3) 1946(2) 3798(2) 2652(2) 20(1)

N(4) 1622(2) 4910(2) 853(2) 21(1)

N(5) 2864(2) 5459(2) 2147(2) 20(1)

N(6) 4946(2) 5387(2) 2825(2) 23(1)

C(1) 4801(3) 4422(2) 3538(2) 22(1)

C(2) 5898(3) 3394(2) 4041(2) 22(1)

C(3) 7312(3) 3233(2) 4109(2) 27(1)

C(4) 8181(3) 2055(3) 4509(2) 29(1)

C(5) 7661(3) 1049(2) 4825(2) 27(1)

C(6) 6272(3) 1183(2) 4748(2) 25(1)

C(7) 5376(3) 2367(2) 4353(2) 21(1)

C(8) 3959(3) 2769(2) 4023(2) 20(1)

C(9) 2319(2) 2523(2) 3035(2) 19(1)

C(10) 1846(2) 1855(2) 2259(2) 21(1)

C(11) 1957(3) 556(2) 2196(2) 24(1)

C(12) 1546(3) 167(2) 1256(2) 28(1)

C(13) 1045(3) 1046(2) 382(2) 28(1)

C(14) 954(3) 2332(2) 412(2) 25(1)

C(15) 1349(2) 2736(2) 1359(2) 21(1)

C(16) 1524(3) 3948(2) 1590(2) 21(1)

C(17) 2361(2) 5607(2) 1119(2) 20(1)

C(18) 3075(3) 6388(2) 388(2) 21(1)

C(19) 2937(3) 6907(2) -713(2) 25(1)

C(20) 3800(3) 7600(2) -1178(2) 27(1)

C(21) 4835(3) 7710(2) -604(2) 28(1)

C(22) 5029(3) 7151(2) 470(2) 26(1)


Page S32 of S53

C(23) 4107(3) 6518(2) 986(2) 20(1)

C(24) 4007(3) 5839(2) 2089(2) 22(1)

C(25) -25(3) 6509(2) 3620(2) 20(1)

C(26) -121(3) 7744(2) 3221(2) 23(1)

C(27) -1350(3) 8562(2) 2822(2) 25(1)

C(28) -2467(3) 8133(2) 2813(2) 24(1)

C(29) -2374(3) 6891(2) 3190(2) 26(1)

C(30) -1150(3) 6089(2) 3603(2) 24(1)

B(1) 2317(3) 4811(3) 3184(2) 20(1)

________________________________________________________________________________


Page S33 of S53

Table S13. Bond lengths [Å] and angles [°] for β-BrPhO-BsubPc (compound 2c).

_____________________________________________________

Br(1)-C(28) 1.893(2)

O(1)-C(25) 1.376(3)

O(1)-B(1) 1.443(3)

N(1)-C(1) 1.368(3)

N(1)-C(8) 1.381(3)

N(1)-B(1) 1.492(3)

N(2)-C(8) 1.337(3)

N(2)-C(9) 1.344(3)

N(3)-C(16) 1.371(3)

N(3)-C(9) 1.383(3)

N(3)-B(1) 1.499(3)

N(4)-C(17) 1.338(3)

N(4)-C(16) 1.349(3)

N(5)-C(24) 1.361(3)

N(5)-C(17) 1.372(3)

N(5)-B(1) 1.492(3)

N(6)-C(24) 1.345(3)

N(6)-C(1) 1.348(3)

C(1)-C(2) 1.449(3)

C(2)-C(3) 1.395(3)

C(2)-C(7) 1.421(3)

C(3)-C(4) 1.383(3)

C(3)-H(3A) 0.9500

C(4)-C(5) 1.399(4)

C(4)-H(4A) 0.9500

C(5)-C(6) 1.381(4)

C(5)-H(5A) 0.9500

C(6)-C(7) 1.396(3)

C(6)-H(6A) 0.9500

C(7)-C(8) 1.459(3)

C(9)-C(10) 1.448(3)

C(10)-C(11) 1.396(3)

C(10)-C(15) 1.424(3)

C(11)-C(12) 1.386(4)


Page S34 of S53

C(11)-H(11A) 0.9500

C(12)-C(13) 1.401(3)

C(12)-H(12A) 0.9500

C(13)-C(14) 1.385(3)

C(13)-H(13A) 0.9500

C(14)-C(15) 1.392(4)

C(14)-H(14A) 0.9500

C(15)-C(16) 1.455(3)

C(17)-C(18) 1.462(3)

C(18)-C(19) 1.390(3)

C(18)-C(23) 1.417(3)

C(19)-C(20) 1.383(3)

C(19)-H(19A) 0.9500

C(20)-C(21) 1.393(4)

C(20)-H(20A) 0.9500

C(21)-C(22) 1.383(4)

C(21)-H(21A) 0.9500

C(22)-C(23) 1.394(3)

C(22)-H(22A) 0.9500

C(23)-C(24) 1.460(3)

C(25)-C(30) 1.386(3)

C(25)-C(26) 1.388(3)

C(26)-C(27) 1.386(3)

C(26)-H(26A) 0.9500

C(27)-C(28) 1.382(4)

C(27)-H(27A) 0.9500

C(28)-C(29) 1.388(3)

C(29)-C(30) 1.385(3)

C(29)-H(29A) 0.9500

C(30)-H(30A) 0.9500

C(25)-O(1)-B(1) 115.65(18)

C(1)-N(1)-C(8) 112.53(19)

C(1)-N(1)-B(1) 122.26(19)

C(8)-N(1)-B(1) 122.96(19)

C(8)-N(2)-C(9) 118.03(19)

C(16)-N(3)-C(9) 112.7(2)


Page S35 of S53

C(16)-N(3)-B(1) 122.78(19)

C(9)-N(3)-B(1) 122.89(19)

C(17)-N(4)-C(16) 116.61(19)

C(24)-N(5)-C(17) 113.4(2)

C(24)-N(5)-B(1) 123.1(2)

C(17)-N(5)-B(1) 123.14(19)

C(24)-N(6)-C(1) 116.5(2)

N(6)-C(1)-N(1) 123.3(2)

N(6)-C(1)-C(2) 128.9(2)

N(1)-C(1)-C(2) 106.06(19)

C(3)-C(2)-C(7) 120.8(2)

C(3)-C(2)-C(1) 131.1(2)

C(7)-C(2)-C(1) 107.5(2)

C(4)-C(3)-C(2) 118.1(2)

C(4)-C(3)-H(3A) 120.9

C(2)-C(3)-H(3A) 120.9

C(3)-C(4)-C(5) 120.9(2)

C(3)-C(4)-H(4A) 119.5

C(5)-C(4)-H(4A) 119.5

C(6)-C(5)-C(4) 121.8(2)

C(6)-C(5)-H(5A) 119.1

C(4)-C(5)-H(5A) 119.1

C(5)-C(6)-C(7) 118.1(2)

C(5)-C(6)-H(6A) 120.9

C(7)-C(6)-H(6A) 120.9

C(6)-C(7)-C(2) 120.2(2)

C(6)-C(7)-C(8) 132.2(2)

C(2)-C(7)-C(8) 107.11(19)

N(2)-C(8)-N(1) 122.4(2)

N(2)-C(8)-C(7) 130.1(2)

N(1)-C(8)-C(7) 105.44(19)

N(2)-C(9)-N(3) 122.0(2)

N(2)-C(9)-C(10) 130.6(2)

N(3)-C(9)-C(10) 105.49(19)

C(11)-C(10)-C(15) 120.0(2)

C(11)-C(10)-C(9) 131.8(2)


Page S36 of S53

C(15)-C(10)-C(9) 107.69(19)

C(12)-C(11)-C(10) 118.3(2)

C(12)-C(11)-H(11A) 120.8

C(10)-C(11)-H(11A) 120.8

C(11)-C(12)-C(13) 121.1(2)

C(11)-C(12)-H(12A) 119.4

C(13)-C(12)-H(12A) 119.4

C(14)-C(13)-C(12) 121.6(2)

C(14)-C(13)-H(13A) 119.2

C(12)-C(13)-H(13A) 119.2

C(13)-C(14)-C(15) 117.7(2)

C(13)-C(14)-H(14A) 121.2

C(15)-C(14)-H(14A) 121.2

C(14)-C(15)-C(10) 121.2(2)

C(14)-C(15)-C(16) 131.3(2)

C(10)-C(15)-C(16) 107.1(2)

N(4)-C(16)-N(3) 122.9(2)

N(4)-C(16)-C(15) 129.4(2)

N(3)-C(16)-C(15) 105.87(19)

N(4)-C(17)-N(5) 122.3(2)

N(4)-C(17)-C(18) 131.1(2)

N(5)-C(17)-C(18) 105.2(2)

C(19)-C(18)-C(23) 121.0(2)

C(19)-C(18)-C(17) 131.8(2)

C(23)-C(18)-C(17) 107.2(2)

C(20)-C(19)-C(18) 117.5(2)

C(20)-C(19)-H(19A) 121.3

C(18)-C(19)-H(19A) 121.3

C(19)-C(20)-C(21) 121.7(2)

C(19)-C(20)-H(20A) 119.2

C(21)-C(20)-H(20A) 119.2

C(22)-C(21)-C(20) 121.5(2)

C(22)-C(21)-H(21A) 119.2

C(20)-C(21)-H(21A) 119.2

C(21)-C(22)-C(23) 117.6(2)

C(21)-C(22)-H(22A) 121.2


Page S37 of S53

C(23)-C(22)-H(22A) 121.2

C(22)-C(23)-C(18) 120.6(2)

C(22)-C(23)-C(24) 132.0(2)

C(18)-C(23)-C(24) 107.36(19)

N(6)-C(24)-N(5) 122.1(2)

N(6)-C(24)-C(23) 130.9(2)

N(5)-C(24)-C(23) 105.6(2)

O(1)-C(25)-C(30) 119.95(19)

O(1)-C(25)-C(26) 120.2(2)

C(30)-C(25)-C(26) 119.9(2)

C(27)-C(26)-C(25) 120.0(2)

C(27)-C(26)-H(26A) 120.0

C(25)-C(26)-H(26A) 120.0

C(28)-C(27)-C(26) 119.6(2)

C(28)-C(27)-H(27A) 120.2

C(26)-C(27)-H(27A) 120.2

C(27)-C(28)-C(29) 121.0(2)

C(27)-C(28)-Br(1) 119.38(18)

C(29)-C(28)-Br(1) 119.57(19)

C(30)-C(29)-C(28) 118.9(2)

C(30)-C(29)-H(29A) 120.6

C(28)-C(29)-H(29A) 120.6

C(29)-C(30)-C(25) 120.7(2)

C(29)-C(30)-H(30A) 119.7

C(25)-C(30)-H(30A) 119.7

O(1)-B(1)-N(5) 114.52(19)

O(1)-B(1)-N(1) 112.2(2)

N(5)-B(1)-N(1) 104.20(19)

O(1)-B(1)-N(3) 116.3(2)

N(5)-B(1)-N(3) 103.3(2)

N(1)-B(1)-N(3) 104.99(19)

_____________________________________________________________



Page S38 of S53

Table S14. Anisotropic displacement parameters (Å2x 103) for β-BrPhO-BsubPc (compound 2c).

The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ]

______________________________________________________________________________

U11 U22 U33 U23 U13 U12

______________________________________________________________________________

Br(1) 29(1) 28(1) 42(1) 3(1) -14(1) -2(1)

O(1) 21(1) 20(1) 21(1) 0(1) -6(1) -5(1)

N(1) 19(1) 19(1) 20(1) 0(1) -6(1) -6(1)

N(2) 21(1) 20(1) 20(1) 1(1) -3(1) -6(1)

N(3) 19(1) 17(1) 23(1) 3(1) -5(1) -6(1)

N(4) 19(1) 18(1) 24(1) 2(1) -6(1) -4(1)

N(5) 20(1) 16(1) 23(1) 1(1) -4(1) -6(1)

N(6) 24(1) 18(1) 28(1) -1(1) -7(1) -8(1)

C(1) 23(1) 21(1) 23(1) -2(1) -6(1) -8(1)

C(2) 25(1) 24(1) 20(1) -1(1) -7(1) -9(1)

C(3) 28(1) 28(1) 29(2) 2(1) -10(1) -13(1)

C(4) 23(1) 34(1) 32(2) -1(1) -13(1) -9(1)

C(5) 30(2) 26(1) 24(1) 2(1) -12(1) -5(1)

C(6) 27(1) 25(1) 21(1) 1(1) -6(1) -8(1)

C(7) 25(1) 21(1) 18(1) -1(1) -6(1) -7(1)

C(8) 20(1) 19(1) 17(1) 3(1) -3(1) -6(1)

C(9) 16(1) 21(1) 19(1) 2(1) -2(1) -7(1)

C(10) 17(1) 22(1) 25(1) 1(1) -4(1) -8(1)

C(11) 23(1) 21(1) 26(1) 3(1) -5(1) -8(1)

C(12) 29(2) 23(1) 33(2) 1(1) -6(1) -11(1)

C(13) 30(2) 28(1) 29(2) -2(1) -7(1) -14(1)

C(14) 22(1) 28(1) 28(1) 4(1) -8(1) -11(1)

C(15) 16(1) 21(1) 25(1) 2(1) -3(1) -6(1)

C(16) 17(1) 22(1) 23(1) 0(1) -4(1) -5(1)

C(17) 18(1) 18(1) 22(1) 2(1) -3(1) -3(1)

C(18) 19(1) 16(1) 25(1) 0(1) -3(1) -3(1)

C(19) 26(1) 21(1) 26(1) 0(1) -4(1) -7(1)

C(20) 30(1) 26(1) 22(1) 2(1) -1(1) -9(1)

C(21) 29(2) 24(1) 29(2) 4(1) 3(1) -11(1)

C(22) 23(1) 21(1) 31(2) 0(1) -5(1) -7(1)

C(23) 20(1) 13(1) 26(1) 0(1) -5(1) -4(1)


Page S39 of S53

C(24) 21(1) 14(1) 30(1) -1(1) -5(1) -6(1)

C(25) 20(1) 19(1) 17(1) 1(1) -3(1) -3(1)

C(26) 24(1) 22(1) 24(1) -2(1) -4(1) -8(1)

C(27) 32(2) 19(1) 24(1) -1(1) -6(1) -9(1)

C(28) 22(1) 24(1) 22(1) -2(1) -5(1) -2(1)

C(29) 23(1) 27(1) 28(1) 0(1) -3(1) -11(1)

C(30) 26(1) 19(1) 24(1) 3(1) -3(1) -8(1)

B(1) 20(1) 18(1) 24(2) 2(1) -5(1) -8(1)

______________________________________________________________________________


Page S40 of S53

Table S15. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)

for β-BrPhO-BsubPc (compound 2c).

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

H(3A) 7668 3912 3887 32

H(4A) 9145 1927 4569 35

H(5A) 8281 252 5100 33

H(6A) 5936 489 4958 30

H(11A) 2306 -46 2782 28

H(12A) 1606 -711 1204 33

H(13A) 761 754 -246 33

H(14A) 633 2918 -192 30

H(19A) 2275 6790 -1131 30

H(20A) 3683 8013 -1908 32

H(21A) 5420 8179 -959 34

H(22A) 5764 7196 843 31

H(26A) 655 8030 3222 28

H(27A) -1424 9412 2556 30

H(29A) -3137 6596 3165 31

H(30A) -1081 5243 3876 28

________________________________________________________________________________


Page S41 of S53

Figure S7. Anisotropic displacement ellipsoid plot of IPhO-BsubPc (compound 2d).

Figure S8. Populated unit cell of IPhO-BsubPc (compound 2d).


Page S42 of S53

Table S16. Crystal data and structure refinement for IPhO-BsubPc (compound 2d).

Identification code k1057 Empirical formula C30 H16 B I N6 O



Wavelength 0.71073 Å Crystal system Triclinic

Space group P -1

Unit cell dimensions a = 10.1878(3) Å α= 87.1720(16)°.

b = 11.1594(4) Å β= 79.7950(17)°. c = 11.6949(4) Å γ = 68.6810(18)°.

Volume 1218.85(7) Å3

Z 2

Density (calculated) 1.674 Mg/m3 Absorption coefficient 1.352 mm-1

F(000) 608


Theta range for data collection 2.56 to 27.50°. Index ranges -12<=h<=13, -14<=k<=14, -14<=l<=15



Completeness to theta = 27.50° 98.8 % Absorption correction Semi-empirical from equivalents



Data / restraints / parameters 5543 / 0 / 352 Goodness-of-fit on F2 1.049





Page S43 of S53


(Å2x 103) for IPhO-BsubPc (compound 2d). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

___________________________________________________________________________

_

x y z U(eq) ___________________________________________________________________________

_

I(1) 9212(1) 665(1) 2795(1) 35(1)

O(1) 3790(2) 4329(2) 941(2) 23(1) N(1) 1379(2) 5955(2) 1283(2) 21(1)

N(2) 57(2) 4655(2) 2145(2) 24(1)

N(3) 2155(2) 4562(2) 2820(2) 21(1)

N(4) 3425(2) 5104(2) 4101(2) 22(1) N(5) 3086(2) 6196(2) 2309(2) 20(1)

N(6) 1806(2) 7921(2) 1186(2) 22(1)

C(1) 1069(3) 7209(2) 944(2) 21(1)

C(2) -351(3) 7624(3) 632(2) 22(1) C(3) -1240(3) 8798(3) 261(2) 27(1)

C(4) -2640(3) 8941(3) 207(3) 30(1)

C(5) -3153(3) 7948(3) 517(3) 32(1)

C(6) -2290(3) 6779(3) 883(2) 28(1) C(7) -875(3) 6611(3) 934(2) 24(1)

C(8) 214(3) 5591(3) 1423(2) 22(1)

C(9) 994(3) 4211(2) 2880(2) 23(1)

C(10) 885(3) 3573(2) 3988(2) 23(1) C(11) -80(3) 3013(3) 4527(3) 26(1)

C(12) 94(3) 2488(3) 5610(3) 30(1)

C(13) 1166(3) 2561(3) 6180(2) 30(1)

C(14) 2071(3) 3193(3) 5685(2) 27(1) C(15) 1945(3) 3677(2) 4580(2) 22(1)

C(16) 2668(3) 4424(2) 3839(2) 22(1)

C(17) 3518(3) 6051(2) 3365(2) 22(1)

C(18) 3707(3) 7240(3) 3600(2) 22(1) C(19) 4098(3) 7645(3) 4555(3) 27(1)

C(20) 4014(3) 8904(3) 4588(3) 31(1)


Page S44 of S53

C(21) 3525(3) 9771(3) 3707(3) 30(1)

C(22) 3110(3) 9385(3) 2766(3) 26(1) C(23) 3212(3) 8107(3) 2700(2) 22(1)

C(24) 2728(3) 7440(3) 1919(2) 22(1)

C(25) 4984(3) 3522(2) 1360(2) 22(1)

C(26) 6110(3) 3932(3) 1401(2) 24(1) C(27) 7312(3) 3125(3) 1827(2) 26(1)

C(28) 7373(3) 1913(3) 2209(2) 24(1)

C(29) 6250(3) 1495(3) 2178(2) 26(1)

C(30) 5050(3) 2313(3) 1756(2) 25(1) B(1) 2687(3) 5203(3) 1777(3) 21(1)

___________________________________________________________________________

_


Page S45 of S53

Table S18. Bond lengths [Å] and angles [°] for IPhO-BsubPc (compound 2d).

_____________________________________________________ I(1)-C(28) 2.094(3)

O(1)-C(25) 1.379(3)

O(1)-B(1) 1.441(3)

N(1)-C(8) 1.369(3) N(1)-C(1) 1.373(3)

N(1)-B(1) 1.491(4)

N(2)-C(9) 1.342(4)

N(2)-C(8) 1.348(3) N(3)-C(16) 1.365(3)

N(3)-C(9) 1.365(3)

N(3)-B(1) 1.501(4)

N(4)-C(16) 1.340(3) N(4)-C(17) 1.349(3)

N(5)-C(17) 1.367(3)

N(5)-C(24) 1.377(3)

N(5)-B(1) 1.505(4) N(6)-C(24) 1.334(3)

N(6)-C(1) 1.343(3)

C(1)-C(2) 1.458(4)

C(2)-C(3) 1.394(4) C(2)-C(7) 1.421(4)

C(3)-C(4) 1.389(4)

C(4)-C(5) 1.396(4)

C(5)-C(6) 1.379(4) C(6)-C(7) 1.396(4)

C(7)-C(8) 1.448(4)

C(9)-C(10) 1.454(4)

C(10)-C(11) 1.393(4) C(10)-C(15) 1.422(4)

C(11)-C(12) 1.381(4)

C(12)-C(13) 1.404(4)

C(13)-C(14) 1.388(4) C(14)-C(15) 1.385(4)

C(15)-C(16) 1.463(4)


Page S46 of S53

C(17)-C(18) 1.454(4)

C(18)-C(19) 1.396(4) C(18)-C(23) 1.425(4)

C(19)-C(20) 1.378(4)

C(20)-C(21) 1.407(4)

C(21)-C(22) 1.385(4) C(22)-C(23) 1.397(4)

C(23)-C(24) 1.457(4)

C(25)-C(30) 1.387(4)

C(25)-C(26) 1.389(4) C(26)-C(27) 1.389(4)

C(27)-C(28) 1.386(4)

C(28)-C(29) 1.390(4)

C(29)-C(30) 1.389(4)

C(25)-O(1)-B(1) 116.0(2)

C(8)-N(1)-C(1) 112.6(2)

C(8)-N(1)-B(1) 122.0(2) C(1)-N(1)-B(1) 123.1(2)

C(9)-N(2)-C(8) 116.6(2)

C(16)-N(3)-C(9) 113.7(2)

C(16)-N(3)-B(1) 123.2(2) C(9)-N(3)-B(1) 122.6(2)

C(16)-N(4)-C(17) 116.4(2)

C(17)-N(5)-C(24) 112.9(2)

C(17)-N(5)-B(1) 123.0(2) C(24)-N(5)-B(1) 122.4(2)

C(24)-N(6)-C(1) 117.7(2)

N(6)-C(1)-N(1) 122.5(2)

N(6)-C(1)-C(2) 129.4(2) N(1)-C(1)-C(2) 105.9(2)

C(3)-C(2)-C(7) 120.3(2)

C(3)-C(2)-C(1) 132.4(2)

C(7)-C(2)-C(1) 106.8(2) C(4)-C(3)-C(2) 118.0(3)

C(3)-C(4)-C(5) 121.4(3)


Page S47 of S53

C(6)-C(5)-C(4) 121.5(3)

C(5)-C(6)-C(7) 118.0(3) C(6)-C(7)-C(2) 120.8(2)

C(6)-C(7)-C(8) 130.9(2)

C(2)-C(7)-C(8) 107.7(2)

N(2)-C(8)-N(1) 123.5(2) N(2)-C(8)-C(7) 128.4(2)

N(1)-C(8)-C(7) 105.9(2)

N(2)-C(9)-N(3) 122.5(2)

N(2)-C(9)-C(10) 130.8(2) N(3)-C(9)-C(10) 105.3(2)

C(11)-C(10)-C(15) 120.4(2)

C(11)-C(10)-C(9) 131.8(3)

C(15)-C(10)-C(9) 107.7(2) C(12)-C(11)-C(10) 117.9(3)

C(11)-C(12)-C(13) 121.5(3)

C(14)-C(13)-C(12) 121.0(3)

C(15)-C(14)-C(13) 117.9(3) C(14)-C(15)-C(10) 121.1(2)

C(14)-C(15)-C(16) 132.0(3)

C(10)-C(15)-C(16) 106.7(2)

N(4)-C(16)-N(3) 122.6(2) N(4)-C(16)-C(15) 130.6(2)

N(3)-C(16)-C(15) 105.3(2)

N(4)-C(17)-N(5) 123.0(2)

N(4)-C(17)-C(18) 129.1(2) N(5)-C(17)-C(18) 106.1(2)

C(19)-C(18)-C(23) 121.0(2)

C(19)-C(18)-C(17) 131.5(2)

C(23)-C(18)-C(17) 107.0(2) C(20)-C(19)-C(18) 117.9(3)

C(19)-C(20)-C(21) 121.7(3)

C(22)-C(21)-C(20) 120.9(3)

C(21)-C(22)-C(23) 118.5(3) C(22)-C(23)-C(18) 120.0(2)

C(22)-C(23)-C(24) 132.1(2)


Page S48 of S53

C(18)-C(23)-C(24) 107.4(2)

N(6)-C(24)-N(5) 122.7(2) N(6)-C(24)-C(23) 129.6(2)

N(5)-C(24)-C(23) 105.5(2)

O(1)-C(25)-C(30) 120.0(2)

O(1)-C(25)-C(26) 119.8(2) C(30)-C(25)-C(26) 120.1(2)

C(27)-C(26)-C(25) 120.1(2)

C(28)-C(27)-C(26) 119.3(2)

C(27)-C(28)-C(29) 121.2(2) C(27)-C(28)-I(1) 119.5(2)

C(29)-C(28)-I(1) 119.24(19)

C(30)-C(29)-C(28) 119.0(2)

C(25)-C(30)-C(29) 120.3(2) O(1)-B(1)-N(1) 112.8(2)

O(1)-B(1)-N(3) 114.3(2)

N(1)-B(1)-N(3) 104.6(2)

O(1)-B(1)-N(5) 116.1(2) N(1)-B(1)-N(5) 104.9(2)

N(3)-B(1)-N(5) 102.9(2)

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Page S49 of S53

Table S19. Anisotropic displacement parameters (Å2x 103) for IPhO-BsubPc (compound

2d). The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12 ]

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U11 U22 U33 U23 U13 U12 ___________________________________________________________________________

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I(1) 31(1) 27(1) 42(1) 1(1) -14(1) -1(1)

O(1) 24(1) 22(1) 21(1) 0(1) -6(1) -4(1) N(1) 23(1) 19(1) 20(1) 1(1) -6(1) -6(1)

N(2) 26(1) 22(1) 25(1) 0(1) -8(1) -8(1)

N(3) 22(1) 18(1) 23(1) 1(1) -6(1) -6(1)

N(4) 21(1) 22(1) 24(1) 2(1) -5(1) -6(1) N(5) 20(1) 18(1) 21(1) 2(1) -5(1) -6(1)

N(6) 23(1) 20(1) 22(1) 2(1) -2(1) -6(1)

C(1) 22(1) 21(1) 19(1) 1(1) -3(1) -7(1)

C(2) 25(1) 24(1) 18(1) -1(1) -8(1) -7(1) C(3) 32(2) 24(1) 22(1) 0(1) -7(1) -7(1)

C(4) 31(2) 30(2) 26(2) 2(1) -13(1) -4(1)

C(5) 25(1) 40(2) 33(2) 0(1) -14(1) -9(1)

C(6) 30(1) 32(2) 28(2) 1(1) -12(1) -14(1) C(7) 29(1) 23(1) 22(1) 0(1) -10(1) -9(1)

C(8) 24(1) 22(1) 22(1) -2(1) -6(1) -8(1)

C(9) 25(1) 18(1) 27(1) -2(1) -6(1) -6(1)

C(10) 24(1) 17(1) 27(1) -1(1) -4(1) -5(1) C(11) 26(1) 22(1) 30(2) 0(1) -3(1) -8(1)

C(12) 32(2) 23(1) 31(2) 2(1) 4(1) -9(1)

C(13) 36(2) 27(2) 22(1) 4(1) 0(1) -9(1)

C(14) 31(1) 22(1) 26(2) 0(1) -6(1) -7(1) C(15) 22(1) 18(1) 24(1) 0(1) -5(1) -4(1)

C(16) 19(1) 20(1) 23(1) 2(1) -5(1) -3(1)

C(17) 16(1) 21(1) 26(1) 1(1) -5(1) -3(1)

C(18) 19(1) 23(1) 24(1) 1(1) -4(1) -7(1) C(19) 26(1) 30(2) 27(2) 1(1) -9(1) -12(1)

C(20) 34(2) 33(2) 32(2) 0(1) -10(1) -18(1)


Page S50 of S53

C(21) 33(2) 26(1) 35(2) -2(1) -8(1) -14(1)

C(22) 25(1) 24(1) 30(2) 4(1) -6(1) -11(1) C(23) 16(1) 25(1) 23(1) 0(1) -2(1) -8(1)

C(24) 19(1) 27(1) 22(1) -2(1) 0(1) -11(1)

C(25) 22(1) 23(1) 16(1) -2(1) -3(1) -4(1)

C(26) 28(1) 20(1) 25(1) 0(1) -2(1) -9(1) C(27) 23(1) 26(1) 26(2) 0(1) -3(1) -8(1)

C(28) 25(1) 20(1) 23(1) -1(1) -5(1) -1(1)

C(29) 30(1) 17(1) 28(2) 0(1) -4(1) -6(1)

C(30) 29(1) 23(1) 25(1) -1(1) -6(1) -12(1) B(1) 23(1) 19(1) 19(2) 1(1) -6(1) -7(1)

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Page S51 of S53

Table S20. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3) for IPhO-BsubPc (compound 2d). ___________________________________________________________________________

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x y z U(eq)

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H(3A) -898 9479 51 32

H(4A) -3262 9733 -46 36 H(5A) -4119 8080 475 38

H(6A) -2648 6108 1095 34

H(11A) -833 2994 4161 32

H(12A) -527 2068 5977 36 H(13A) 1274 2171 6915 35

H(14A) 2755 3291 6092 32

H(19A) 4412 7072 5162 32

H(20A) 4293 9194 5223 37 H(21A) 3480 10633 3758 36

H(22A) 2764 9977 2180 31

H(26A) 6058 4764 1138 29

H(27A) 8085 3401 1857 31 H(29A) 6303 662 2440 31

H(30A) 4270 2043 1738 30

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Page S52 of S53

Figure S9: Electrostatic potential 3D mapped isosurface plot of FPhO-BsubPc (2a) generated using the 6-31G* basis set with the B3LYP DFT method. Areas of electron deficiency are colored blue areas of electron excess are colored red.

Figure S10: Electrostatic potential 3D mapped isosurface plot of ClPhO-BsubPc (2b) generated using the 6-31G* basis set with the B3LYP DFT method. Areas of electron deficiency are colored blue areas of electron excess are colored red.


Page S53 of S53

Figure S11: Electrostatic potential 3D mapped isosurface plot of IPhO-BsubPc generated using the 6-6-311G* basis set with the B3LYP DFT method. Areas of electron deficiency are colored blue areas of electron excess are colored red.


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ELECTRONIC SUPPORTING INFORMATION. · 2011. 4. 7. · Page S3 of S53 Table S12. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for β-BrPhO-BsubPc