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Supporting Information Triplet Energy Transfers in Well-Defined Host-Guest Porphyrin-

Carboxylates/Cluster Assemblies Peng Luo,a Paul-Ludovic Karsenti,a Benoit Marsanb* and Pierre D. Harveya*

aDépartement de chimie, Université de Sherbrooke, Sherbrooke, QC, J1K 2R1, Canada. b

Département de chimie, Université du Québec à Montréal, Montréal, QC, H2X 2J6, Canada.

Table of Content

Figure S1. UV-vis spectra of MCP and DCP with addition of [Pd32+ S3 ] in MeOH. Table S1. Selected distances in optimized geometries of [Pd32+] and [Pt32+ S3 ] (basis set 6-31g* for P, C, O and H, in MeOH solvent field). Figure S2. Displacements of the P-atom (in Å) away from the M32+ in the S0 and T1

S4 states (basis set 3-21g* for P, C, O and H, in MeOH solvent field). Table S2. Selected distances in optimized geometries of [Pd32+] and [Pt32+ S4 ] (basis set 3-21g* for P, C, O and H, in MeOH solvent field). Figure S3. Displacements of the P-atom (in Å) away from the M32+ in the S0 and T1

S5 states (basis set 6-31g* for P, C, O and H, in THF solvent field). Table S3. Selected distances in optimized geometries of [Pd32+] and [Pt32+ S5 ] (basis set 6-31g* for P, C, O and H, in THF solvent field). Figure S4. Displacements of the P-atom (in Å) away from the M32+ in the S0 and T1

S6 states (basis set 3-21g* for P, C, O and H, in THF solvent field). Table S4. Selected distances in optimized geometries of [Pd32+] and [Pt32+ S6 ] (basis set 3-21g* for P, C, O and H, in THF solvent field). Figure S5. Displacements of the P-atom (in Å) away from the M32+ in the S0 and T1

S7 states (basis set 6-31g* for P, C, O and H, without solvent field). Table S5 Selected distances in optimized geometries of [Pd32+] and [Pt32+ S7 ] (basis set 6-31g* for P, C, O and H, without solvent field). Figure S6. Displacements of the P-atom (in Å) away from the M32+ in the S0 and T1

S8 states (basis set 3-21g* for P, C, O and H, without solvent field). Table S6. Selected distances in optimized geometries of [Pd32+] and [Pt32+ S8 ] (basis set 3-21g* for P, C, O and H, without solvent field). Table S7. Computed S0-T1 energy gaps for [Pd32+] and [Pt32+ S9 ] using various basis sets and solvent fields. Table S8. Phosphorescence lifetimes for MCP and DCP in 1:1 MeOH/2MeTHF mixture with increasing amount of [Pd32+

S9 ] at 77 K. Figure S7. Optimized triplet geometry of MCP (Na+ S10 salt) in MeOH solvent field. Figure S8. Representations of the frontier semi-occupied MOs of MCP (Na+ S10 salt) i MeOH solvent field. Figure S9. Optimized triplet geometry of DCP (Na+ S10 salt) in MeOH solvent field. Figure S10. Representations of the frontier semi-occupied MOs of DCP (Na+ S10 salt) in MeOH solvent field.

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Figure S11. Comparison of the emission spectra of MCP and DCP in MeOH at 298 K and MeOH:2MeTHF 1:1 at 77 K.

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Figure S12. Representations of the frontier semi-occupied MOs of [Pd32+ S12 ] in MeOH solvent field. Figure S13. Representations of the frontier semi-occupied MOs of [Pd32+]••• DCP•••[Pd32+

S12 ] in MeOH solvent field. Figure S14. Optimized geometry of [Pd32+]•••DCP•••[Pd32+ S13 ] (basis set 6-31g* for P, C, O, N and H in MeOH solvent field). Figure S15. Representations of the semi-occupied MOs of MCP•••[Pd32+ S13 ] (energies in eV; basis set 6-31g* for P, C, O, N and H in MeOH solvent field). Figure S16. Optimized geometry of [Pd32+]•••DCP•••[Pd32+ S14 ] (basis set 6-31g* for P, C, O, N and H in MeOH solvent field). Figure S17. Representations of the semi-occupied MOs of [Pd32+]•••DCP••• [Pd32+ S14 ] (energies in eV; basis set 6-31g* for P, C, O, N and H in MeOH solvent field). Figure S18. Left: Various components deconvoluted from the emission spectra of [Pd32+ S15 ] in 1:1 MeOH/2MeTHF mixture at 298 K reported in Figure 7 of the text. Right: Emission decays monitored at 622 and 686 nm hoping to detect long components. Figure S19. Left: Comparison of the absorption (up) and transient absorption spectra (down) of [Pd32+ S15 ] in 1:1 MeOH:2MeTHF mixture at 77 K. Right: the three components deconvoluted from the transient absorption spectra of Figure 8. Figure S20. Representation of the relative orientations of the transition moments (red) within the dye and cluster in the [Pd32+]•••DCP•••[Pd32+ S16 ] assembly as an example. Figure S21. Structures and kET(T1 S16 ) data for various [Pt]-metalloporphyrin dyads and polymers. The arrows represent the direction of the TETs.

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Figure S1. Left: UV-vis spectra of MCP (0.46 × 10-5 M) with additions of [Pd32+] (1.21 × 10-4 M) in MeOH. Right: UV-vis spectra of DCP (0.38 × 10-5 M) with addition of [Pd32+] (1.18 × 10-4 M) in MeOH. Curves were obtained with successive addition of 0.1 mL [Pd32+

] solution while keeping the concentration of the dye constant.

DFT calculations for [Pd32+] and [Pt32+

] under various basis sets and solvent fields

Table S1. Selected distances in optimized geometries of [Pd32+] and [Pt32+] (basis set 6-31g* for P, C, O and H, in MeOH solvent field).

[Pd

a 3

2+ Singlet S] Triplet T0 1 Pd-Pd (Å) 2.712, 2.694, 2.687 (av.=2.698) 2.910, 2.875, 2.711 (av.=2.832)

Pd-P (Å) 2.419, 2.419, 2.405, 2.399, 2.392, 2.391 (av.=2.404) 2.474, 2.452, 2.434, 2.432, 2.416, 2.395 (av.=2.434)

Plane-P (Å) av.=0.283 av.=0.607 [Pt32+ Singlet S] Triplet T0 1

Pt-Pt (Å) 2.724, 2.702, 2.702 (av.=2.709) 2.944, 2.855, 2.801 (av.=2.867)

Pt-P (Å) 2.383, 2.366, 2.365, 2.363, 2.362, 2.361 (av.=2.367) 2.421, 2.419, 2.399, 2.377, 2.364, 2.350 (av.=2.388)

Plane-P (Å) av.=0.265 av.=0.897 a

Plane-P average values represent the average out-of-plane displacements in absolute values.

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Figure S2. Displacements of the P-atom (in Å) away from the M32+ in the S0 and T1

states (basis set 3-21g* for P, C, O and H, in MeOH solvent field).

Table S2. Selected distances in optimized geometries of [Pd32+] and [Pt32+] (basis set 3-21g* for P, C, O and H, in MeOH solvent field).

[Pd

a 3

2+ Singlet S] Triplet T0 1 Pd-Pd (Å) 2.685, 2.679, 2.649 (av.=2.671) 2.879, 2.855, 2.825 (av.=2.853)

Pd-P (Å) 2.398, 2.384, 2.374, 2.371, 2.367, 2.365 (av.=2.377) 2.432, 2.424, 2.422, 2.409, 2.405, 2.400 (av.=2.415)

Plane-P (Å) av.=0.275 av.=0.767 [Pt32+ Singlet S] Triplet T0 1

Pt-Pt (Å) 2.707, 2.706, 2.689 (av.=2.701) 2.888, 2.786, 2.780 (av.=2.818)

Pt-P (Å) 2.357, 2.344, 2.336, 2.335, 2.335, 2.333 (av.=2.340) 2.376, 2.371, 2.365, 2.365, 2.328, 2.313 (av.=2.353)

Plane-P (Å) av.=0.273 av.=0.741 aPlane-P average values represent the average out-of-plane displacements in absolute values.

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Figure S3. Displacements of the P-atom (in Å) away from the M32+ in the S0 and T1

states (basis set 6-31g* for P, C, O and H, in THF solvent field).

Table S3. Selected distances in optimized geometries of [Pd32+] and [Pt32+] (basis set 6-31g* for P, C, O and H, in THF solvent field).

[Pd

a 3

2+ Singlet S] Triplet T0 1 Pd-Pd (Å) 2.717, 2.696, 2.688 (av.=2.700) 2.941, 2.937, 2.815 (av.=2.898)

Pd-P (Å) 2.426, 2.411, 2.401, 2.398, 2.394, 2.387 (av.=2.403) 2.464, 2.453, 2.447, 2.430, 2.427, 2.409 (av.=2.438)

Plane-P (Å) av.=0.294 av.=0.556 [Pt32+ Singlet S] Triplet T0 1

Pt-Pt (Å) 2.728, 2.714, 2.701 (av.=2.714) 2.905, 2.837, 2.817 (av.=2.853)

Pt-P (Å) 2.381, 2.373, 2.369, 2.367, 2.361, 2.357 (av.=2.368) 2.407, 2.396, 2.390, 2.381, 2.355, 2.353 (av.=2.380)

Plane-P (Å) av.=0.284 av.=0.688 a

Plane-P average values represent the average out-of-plane displacements in absolute values.

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Figure S4. Displacements of the P-atom (in Å) away from the M32+ in the S0 and T1

states (basis set 3-21g* for P, C, O and H, in THF solvent field).

Table S4. Selected distances in optimized geometries of [Pd32+] and [Pt32+] (basis set 3-21g* for P, C, O and H, in THF solvent field).

[Pd

a 3

2+ Singlet S] Triplet T0 1 Pd-Pd (Å) 2.692, 2.668, 2.667 (av.=2.676) 2.992, 2.825, 2.785 (av.=2.867)

Pd-P (Å) 2.395, 2.391, 2.383, 2.372, 2.369, 2.366 (av.=2.379) 2.473, 2.417, 2.403, 2.402, 2.397, 2.394 (av.=2.414)

Plane-P (Å) av.=0.308 av.=0.613 [Pt32+ Singlet S] Triplet T0 1

Pt-Pt (Å) 2.710, 2.708, 2.690 (av.=2.703) 2.872, 2.808, 2.787 (av.=2.822)

Pt-P (Å) 2.353, 2.352, 2.337, 2.336, 2.336, 2.334 (av.=2.341) 2.378, 2.370, 2.367, 2.360, 2.329, 2.318 (av.=2.354)

Plane-P (Å) av.=0.287 av.=0.772 aPlane-P average values represent the average out-of-plane displacements in absolute values.

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Figure S5. Displacements of the P-atom (in Å) away from the M32+ in the S0 and T1

states (basis set 6-31g* for P, C, O and H, without solvent field).

Table S5. Selected distances in optimized geometries of [Pd32+] and [Pt32+

[Pd

] (basis set 6-31g* for P, C, O and H, without solvent field).

32+ Singlet S] Triplet T0 1

Pd-Pd (Å) 2.717, 2.699, 2.689 (av.=2.702) 2.977, 2.897, 2.818 (av.=2.897)

Pd-P (Å) 2.419, 2.402, 2.401, 2.398, 2.395, 2.395 (av.=2.402) 2.457, 2.438, 2.428, 2.427, 2.422, 2.398 (av.=2.428)

Plane-P (Å) av.=0.304 av.=0.736 [Pt32+ Singlet S] Triplet T0 1

Pt-Pt (Å) 2.727, 2.714, 2.709 (av.=2.717) 2.896, 2.849, 2.805 (av.=2.828)

Pt-P (Å) 2.376, 2.371, 2.362, 2.359, 2.359, 2.357, (av.=2.364) 2.401, 2.377, 2.372, 2.369, 2.353, 2.352 (av.=2.371)

Plane-P (Å) av.=0.279 av.=0.625 a

Plane-P average values represent the average out-of-plane displacements in absolute values.

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Figure S6. Displacements of the P-atom (in Å) away from the M32+ in the S0 and T1

states (basis set 3-21g* for P, C, O and H, without solvent field).

Table S6. Selected distances in optimized geometries of [Pd32+] and [Pt32+] (basis set 3-21g* for P, C, O and H, without solvent field).

[Pd

a 3

2+ Singlet S] Triplet T0 1 Pd-Pd (Å) 2.696, 2.677, 2.664 (av.=2.679) 2.963, 2.796, 2.776 (av.=2.845)

Pd-P (Å) 2.391, 2.390, 2.378, 2.374, 2.371, 2.365 (av.=2.378) 2.422, 2.413, 2.405, 2.405, 2.401, 2.372 (av.=2.403)

Plane-P (Å) av.=0.287 av.=0.935 [Pt32+ Singlet S] Triplet T0 1

Pt-Pt (Å) 2.710, 2.699, 2.696 (av.=2.702) 2.858, 2.830, 2.795 (av.=2.828)

Pt-P (Å) 2.350, 2.343, 2.338, 2.336, 2.332, 2.327 (av.=2.338) 2.368, 2.364, 2.346, 2.344, 2.337, 2.333 (av.=2.349)

Plane-P (Å) av.=0.301 av.=0.893 a

Plane-P average values represent the average out-of-plane displacements in absolute values.

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Table S7. Computed S0-T1 energy gaps for [Pd32+] and [Pt32+

1

] using various basis sets and solvent fields.

Singlet S0 Triplet T (a.u.)

1 ∆E(S (a.u.)

0-T1

∆E (S) (a.u.)

0-T1

Predicted position of phosphorescence (nm) ) (eV)

[Pd32+] -5441.12792 a -5441.09563 0.03229 0.87865 1413 [Pt32+] -5418.49189 a -5418.434646 0.05724 1.55764 797 [Pd32+] -5440.99210 b -5440.95962 0.03247 0.88360 1405 [Pt32+] -5418.35190 b -5418.29521 0.05670 1.54274 805 [Pd32+] -5414.63924 c -5414.60759 0.03165 0.86123 1441 [Pt32+] -5392.01505 c -5391.96077 0.05428 1.47704 840 [Pd32+] -5414.61683 d -5414.58696 0.02987 0.81267 1527 [Pt32+] -5391.99137 d -5391.93933 0.05204 1.41596 877 [Pd32+] -5414.47581 e -5414.44443 0.03138 0.85379 1453 [Pt32+] -5391.84601 e -5391.79700 0.04901 1.33354 931 aBasis set 6-31g* in THF field. bBasis set 6-31g* without solvent field. cBasis set 3-21g* in MeOH field. dBasis set 3-21g* in THF field. e

Basis set 3-21g* without solvent field.

Table S8. Phosphorescence lifetimes for MCP and DCP in 1:1 MeOH:2MeTHF mixture with increasing amount of [Pd32+

Porphyrins vs [Pd

] at 77 K.

32+ MCP (ms) ] DCP (ms)

1:0 24.11±0.40 25.21±0.44 1:1 24.07±0.41 25.18±0.45 1:2 24.05±0.47 25.14±0.48 1:4 24.01±0.38 25.09±0.50

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DFT triplet calculations for MCP and DCP

Figure S7. Optimized triplet geometry of MCP (Na+

salt) in MeOH solvent field.

Figure S8. Representations of the frontier semi-occupied MOs of MCP (Na+

salt) in MeOH solvent field (energies in eV).

Figure S9. Optimized triplet geometry of DCP (Na+

salt) in MeOH solvent field.

Figure S10. Representations of the frontier semi-occupied MOs of DCP (Na+ salt) in MeOH solvent field (energies in eV).

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Figure S11. Comparison of the emission spectra of MCP and DCP in MeOH at 298 K (left) and in MeOH:2MeTHF 1:1 mixture at 77 K (right). Note the phosphorescence peak at about 785 nm.

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Figure S12. Representations of the frontier semi-occupied MOs of [Pd32+

] in MeOH solvent field (energies in eV).

Figure S13. Representations of the frontier semi-occupied MOs of [Pd32+]•••DCP••• [Pd32+

] in MeOH solvent field (energies in eV).

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Figure S14. Optimized geometry of MCP•••[Pd32+

] (basis set 6-31g* for P, C, O, N and H in MeOH solvent field).

Figure S15. Representations of the semi-occupied MOs of MCP•••[Pd32+

] (energies in eV; basis set 6-31g* for P, C, O, N and H in MeOH solvent field).

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Figure S16. Optimized geometry of [Pd32+]•••DCP•••[Pd32+

] (basis set 6-31g* for P, C, O, N and H in MeOH solvent field).

Figure S17. Representations of the semi-occupied MOs of [Pd32+]•••DCP•••[Pd32+

] (energies in eV; basis set 6-31g* for P, C, O, N and H in MeOH solvent field).

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Figure S18. Left: Various components deconvoluted from the emission spectra of [Pd32+

] in 1:1 MeOH:2MeTHF mixture at 298 K similar to that reported in Figure 7 at 77 K. Note that the 6.5 ps values lies under the detection limit of the Streak camera at 298 K (i.e. < 8.7 ps), so it is inaccurate. The species labeled in green and red points are likely to be too weak to be observed with confidence. Right: Emission decays monitored at 622 and 686 nm hoping to detect ant long components for the spectra presented on the left.

Figure S19. Left: Comparison of the absorption (up) and transient absorption spectra (down) of [Pd32+] in 1:1 MeOH:2MeTHF mixture at 298 K; λexc = 600 nm. Right: the three components deconvoluted from the transient absorption spectra of Figure 8 (λexc

= 400 nm).

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Figure S20. Representation of the relative orientations of the transition moments (red) within the dye and cluster in the [Pd32+]•••DCP•••[Pd32+

] assembly as an example.

Figure S21. Structures and kET(T1

) data for various [Pt]-metalloporphyrin dyads and polymers. The arrows represent the direction of the TETs.