SUPPORTING INFORMATION FOR. Site-Selective Benzannulation of N-Heterocycles in Bidentate Ligands Leads

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1 SUPPORTING INFORMATION FOR Site-Selective Benzannulation of N-Heterocycles in Bidentate Ligands Leads to Blue-Shifted Emission from [(P^N)Cu] 2 (µ-x) 2 Dimers Rajarshi Mondal, a Issiah Byen Lozada, a Rebecca L. Davis, a J. A. Gareth Williams* b and David E. Herbert* a a Department of Chemistry and the Manitoba Institute for Materials, University of Manitoba, 144 Dysart Road, Winnipeg, Manitoba, R3T 2N2, Canada *david.herbert@umanitoba.ca b Department of Chemistry, Durham University, Durham, DH1 3LE, U.K *j.a.g.williams@durham.ac.uk SI-1

2 TABLE OF CONTENTS: SOLID-STATE GRINDING REACTIONS 5 Figure S1. Photographs taken under UV-light (λ = 365 nm) of solid-state samples of L1, L2, L3 and 1-I, 2-I, 3-I prepared by grinding the ligands with the appropriate CuX precursor and five drops of CH 3 CN. 5 Figure S2. 1 H NMR (0 MHz, 22 C) spectrum of 1-I in CDCl 3 prepared by solid-state grinding. 5 Figure S3. 31 P{ 1 H} (121 MHz, 22 C) NMR spectrum of 1-I in CDCl 3 prepared by solid-state grinding. 6 Figure S4. 1 H NMR (0 MHz, 22 C) spectrum of 2-I in CDCl 3 prepared by solid-state grinding. 6 Figure S5. 31 P{ 1 H} (121 MHz, 22 C) NMR spectrum of 2-I in CDCl 3 prepared by solid-state grinding. 7 Figure S6. 1 H NMR (0 MHz, 22 C) spectrum of 3-I in CDCl 3 prepared by solid-state grinding. 7 Figure S7. 31 P{ 1 H} (121 MHz, 22 C) NMR spectrum of 3-I in CDCl 3 prepared by solid-state grinding. 8 Figure S8. ORTEPs 1 of the solid-state structure of 2-Br crystallized in butterfly conformation. Ellipsoids are shown at % probability levels with hydrogen atoms omitted for clarity. Selected bond distances (Å) and angles ( ): Cu(1)-P(1) 2.204(3), Cu(2)-P(2) 2.201(4), Cu(1)-N(1) 2.100(9), Cu(2)-N(2) 2.085(10), Cu(1)-Br(1) 2.464(2), Cu(1)-Br(2) (19), Cu(2)-Br(2) 2.6(2), Cu(2)-Br(1) 2.425(2), Cu(1)-Cu(2); P(1)-Cu(1)-N(1) 86.6(3), P(2)- Cu(2)-N(2) 86.5(3), Cu(1)-Br(1)-Cu(2) 71.84(6), Cu(1)-Br(2)-Cu(2) 70.65(6). 9 Figure S9. Absorption spectra of L1 L3 in CH 2 Cl 2 at 298 ± 3 K. 10 Figure S10. Normalized phosphorescence spectra of L1, L2 and L3 in EPA at 77 K. Since L3 does not give a wellresolved spectrum under these conditions, the spectrum of 8-bromoquinoline (as a model for an 8-substituted quinoline with no methyl groups) is also included to offer a direct comparison with L1. The vertical black lines indicate the respective positions of the (0,0) bands of L1 and 8-bromoquinoline, highlighting the lower energy of the quinoline phosphorescence. 11 Figure S11. Cyclic voltammograms showing reduction of 2-Br and 3-Br ([analyte] = 1.1 mm; M [nbu 4 N][PF 6 ], 100 mv/s scan rate). 12 Figure S12. Comparison of the relative energies of the first triplet excited states of 2-I and 3-I. The S 0 S 1 energies were obtained from TD-DFT calculations, while T 1 S 0 energies were estimated from the difference of the sum of electronic and thermal free energies (frequency calculation) of the T 1 and S 0 states. 12 Figure S13. Overlay of optimized ground state (S 0, green) and excited state (T 1, red) geometries of 2-I and 3-I. 13 Figure S14. Comparison of bond distances within the quinolinyl and phenanthridinyl moieties of 2-I and 3-I in the DFT-optimized ground state (S 0 ) and first excited triplet state (T 1 ) structures. The pyridine sub-units are highlighted in bold. 13 NMR SPECTRA 14 Figure S15. 1 H NMR (300 MHz, 22 C) spectrum of L2 in CDCl Figure S C{ 1 H} (75 MHz, 22 C) NMR spectrum of L2 in CDCl SI-2

3 Figure S P{ 1 H} NMR (121 MHz, 22 C) spectrum of L2 in CDCl Figure S18. 1 H NMR (300 MHz, 22 C) spectrum of L3 in CDCl Figure S C{ 1 H} (75 MHz, 22 C) NMR spectrum of L3 in CDCl Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of L3 in CDCl Figure S21. 1 H NMR (0 MHz, 22 C) spectrum of 1-Cl in CDCl Figure S C{ 1 H} NMR (126 MHz, 22 C) spectrum of 1-Cl in CDCl Figure S P{ 1 H} NMR (202 MHz, 22 C) spectrum of 1-Cl in CDCl Figure S24. 1 H NMR (0 MHz, 22 C) spectrum of 1-I in CDCl Figure S C{ 1 H} (126 MHz, 22 C) NMR spectrum of 1-I in CDCl Figure S P{ 1 H} (202 MHz, 22 C) NMR spectrum of 1-I in CDCl Figure S27. 1 H NMR (300 MHz, 22 C) spectrum of 2-Cl in CDCl Figure S C{ 1 H} NMR (126 MHz, 22 C) spectrum of 2-Cl in CDCl Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of 2-Cl in CDCl Figure S30. 1 H NMR(0 MHz, 22 C) spectrum of 2-Br in CDCl Figure S C{ 1 H} (126 MHz, 22 C) NMR spectrum of 2-Br in CDCl Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of 2-Br in CDCl Figure S33. 1 H NMR (300 MHz, 22 C) spectrum of 2-I in CDCl Figure S C{ 1 H} NMR (126 MHz, 22 C) spectrum of 2-I in CDCl Figure S P{ 1 H} (202 MHz, 22 C) NMR spectrum of 2-I in CDCl Figure S36. 1 H NMR (300 MHz, 22 C) spectrum of 3-Cl in CDCl Figure S C{ 1 H} NMR (75 MHz, 22 C) spectrum of 3-Cl in CDCl Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of 3-Cl in CDCl Figure S39. 1 H NMR (300 MHz, 22 C) spectrum of 3-Br in CDCl Figure S C{ 1 H} NMR (75 MHz, 22 C) spectrum of 3-Br in CDCl Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of 3-Br in CDCl Figure S42. 1 H NMR (0 MHz, 22 C) spectrum of 3-I in CDCl SI-3

4 Figure S C{ 1 H} NMR (126 MHz, 22 C) spectrum of 3-I in CDCl Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of 3-I in CDCl COMPUTATIONAL DETAILS 29 Figure S45. Optimized (S 0 ) structure of 2-I and atom assignments. 29 Figure S46. Optimized structure (S 0 ) of 3-I and atom assignments. 29 Table S1. Selected bond distances and angles of optimized structures of 3-I. 30 Table S2. Selected bond distances and angles of optimized structures of 2-I. 31 Figure S47. Calculated and experimental bend angles for 3-X. Bend angles is defined as the dihedral angle between the two X-Cu-X triangles in 3-X. 32 Table S3. Atomic contributions (Mulliken) to the HOMO of 2-I and 3-I (S 0 ). 32 Table S4. Atomic contributions (Mulliken) to the LUMO (TD-DFT) of 2-I (S 1 state) and 3-I (S 2 state) from the first allowed excited state. 33 Table S5. Atomic contributions (Mulliken) to the LUMO+1 (TD-DFT) of 2-I (S 1 state) and 3-I (S 2 state) from the first allowed excited state. 33 Figure S48. Diagram illustrating parameters calculated using protocol described in experimental section. 34 Table S6. Calculated photophysical parameters for 2-I and 3-I 34 Table S7. TD-DFT calculated electronic transitions for 2-I along with their corresponding excitation energies and oscillator strengths (FWHM: 3000 cm -1 ; σ: 0.2). 35 Table S8. TD-DFT calculated electronic transitions for 3-I along with their corresponding excitation energies and oscillator strengths (FWHM: 3000 cm -1 ; σ: 0.2). 35 Table S9. Structural comparison between the S 0 and T 1 gas phase structures of 2-I. 36 Table S10. Structural comparison between the S 0 and T 1 gas phase structures of 3-I. 37 Energies and Reaction Coordinates 38 References 51 SI-4

5 SOLID-STATE GRINDING REACTIONS Figure S1. Photographs taken under UV-light (λ = 365 nm) of solid-state samples of L1, L2, L3 and 1-I, 2-I, 3-I prepared by grinding the ligands with the appropriate CuX precursor and five drops of CH 3 CN. Figure S2. 1 H NMR (0 MHz, 22 C) spectrum of 1-I in CDCl 3 prepared by solid-state grinding. SI-5

6 Figure S3. 31 P{ 1 H} (121 MHz, 22 C) NMR spectrum of 1-I in CDCl 3 prepared by solid-state grinding. Figure S4. 1 H NMR (0 MHz, 22 C) spectrum of 2-I in CDCl 3 prepared by solid-state grinding. SI-6

7 Figure S5. 31 P{ 1 H} (121 MHz, 22 C) NMR spectrum of 2-I in CDCl 3 prepared by solid-state grinding. Figure S6. 1 H NMR (0 MHz, 22 C) spectrum of 3-I in CDCl 3 prepared by solid-state grinding. SI-7

8 Figure S7. 31 P{ 1 H} (121 MHz, 22 C) NMR spectrum of 3-I in CDCl 3 prepared by solid-state grinding. SI-8

9 Figure S8. ORTEPs 1 of the solid-state structure of 2-Br crystallized in butterfly conformation. Ellipsoids are shown at % probability levels with hydrogen atoms omitted for clarity. Selected bond distances (Å) and angles ( ): Cu(1)-P(1) 2.204(3), Cu(2)-P(2) 2.201(4), Cu(1)-N(1) 2.100(9), Cu(2)-N(2) 2.085(10), Cu(1)-Br(1) 2.464(2), Cu(1)-Br(2) (19), Cu(2)-Br(2) 2.6(2), Cu(2)-Br(1) 2.425(2), Cu(1)-Cu(2); P(1)-Cu(1)-N(1) 86.6(3), P(2)-Cu(2)-N(2) 86.5(3), Cu(1)-Br(1)-Cu(2) 71.84(6), Cu(1)-Br(2)-Cu(2) 70.65(6). SI-9

10 60000 L1 extinction coefficient / M 1 cm L3 L wavelength / nm Figure S9. Absorption spectra of L1 L3 in CH 2 Cl 2 at 298 ± 3 K. SI-10

11 normalized emission intensity cm cm 1 L1 L2 L3 8-Br-quin wavelength / nm Figure S10. Normalized phosphorescence spectra of L1, L2 and L3 in EPA at 77 K. Since L3 does not give a well-resolved spectrum under these conditions, the spectrum of 8- bromoquinoline (as a model for an 8-substituted quinoline with no methyl groups) is also included to offer a direct comparison with L1. The vertical black lines indicate the respective positions of the (0,0) bands of L1 and 8-bromoquinoline, highlighting the lower energy of the quinoline phosphorescence. SI-11

12 E red,onset (3-Br) E red,onset (2-Br) 0.5 μa/cm 2 2-Br 3-Br E (V) vs FcH 0/+ Figure S11. Cyclic voltammograms showing reduction of 2-Br and 3-Br ([analyte] = 1.1 mm; M [nbu 4 N][PF 6 ], 100 mv/s scan rate). Figure S12. Comparison of the relative energies of the first triplet excited states of 2-I and 3-I. The S 0 S 1 energies were obtained from TD-DFT calculations, while T 1 S 0 energies were estimated from the difference of the sum of electronic and thermal free energies (frequency calculation) of the T 1 and S 0 states. SI-12

2-I 3-I Figure S13. Overlay of optimized ground state (S0, green) and excited state (T1, red) geometries of 2-I and 3-I. 1.413, 1.413 1.404, 1.413 1.413, 1.413 1.398, 1.412 1.384, 1.384 1.392, 1.

426 1.425, 1.425 1.413, 1.413 1.429, 1.413 1.421, 1.422 1.438, 1.422 1.420, 1.420 1.413, 1.419 1.375,1.375 1.405, 1.375 1.379, 1.379 1.408, 1.380 1.428, 1.428 1.443, 1.429 1.423, 1.423 1.390, 1.422 1.432, 1.

13 2-I 3-I Figure S13. Overlay of optimized ground state (S0, green) and excited state (T1, red) geometries of 2-I and 3-I , , , , , , , , , , , , , , , , , , N 1.385, , , , , , , , , , , , , , , , , , , , N 1.381, , , , , , , , [Cu] [P] 2-I (S0) 2-I (T1) 1.418, , , , , , , , [Cu] [P] 3-I (S0) 3-I (T1) Figure S14. Comparison of bond distances within the quinolinyl and phenanthridinyl moieties of 2-I and 3-I in the DFT-optimized ground state (S0) and first excited triplet state (T1) structures. The pyridine sub-units are highlighted in bold. SI-13

14 NMR SPECTRA RAJ B3H.1.fid MePN PROTON128 CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert CDCl Figure S15. 1 H NMR (300 MHz, 22 C) spectrum of L2 in CDCl 3. RAJ B3C.1.fid MePN C13CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert CDCl Figure S C{ 1 H} (75 MHz, 22 C) NMR spectrum of L2 in CDCl 3. SI-14

15 RAJ F3P.1.fid MePN ligand P31CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert Figure S P{ 1 H} NMR (121 MHz, 22 C) spectrum of L2 in CDCl 3. RAJ B3H.1.fid quinolinephosphine after etoh wash PROTON CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert CDCl Figure S18. 1 H NMR (300 MHz, 22 C) spectrum of L3 in CDCl 3. SI-15

16 RAJ D3C.1.fid MeQuin C13CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert CDCl Figure S C{ 1 H} (75 MHz, 22 C) NMR spectrum of L3 in CDCl 3. RAJ A3P.1.fid PN ligand check P31CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of L3 in CDCl 3. SI-16

17 RAJ D5H.1.fid PNCuCl Parent PROTON CDCl3 C:\\ Herbert CDCl Figure S21. 1 H NMR (0 MHz, 22 C) spectrum of 1-Cl in CDCl 3. RAJ D5C.1.fid PNCuCl Parent C13CPD CDCl3 C:\\ Herbert CDCl Figure S C{ 1 H} NMR (126 MHz, 22 C) spectrum of 1-Cl in CDCl 3. SI-17

18 RAJ D5P.1.fid PNCuCl Parent P31CPD CDCl3 C:\\ Herbert Figure S P{ 1 H} NMR (202 MHz, 22 C) spectrum of 1-Cl in CDCl 3. Figure S24. 1 H NMR (0 MHz, 22 C) spectrum of 1-I in CDCl 3. SI-18

19 Figure S C{ 1 H} (126 MHz, 22 C) NMR spectrum of 1-I in CDCl Figure S P{ 1 H} (202 MHz, 22 C) NMR spectrum of 1-I in CDCl 3. SI-19

20 RAJ C3H.1.fid MePNCuCl PROTON128 CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert CDCl Figure S27. 1 H NMR (300 MHz, 22 C) spectrum of 2-Cl in CDCl 3. RAJ B5C.1.fid MePNCuCl C13CPD CDCl3 C:\\ Herbert CDCl Figure S C{ 1 H} NMR (126 MHz, 22 C) spectrum of 2-Cl in CDCl 3. SI-20

21 RAJ B3P.1.fid MePNCuCl P31CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of 2-Cl in CDCl 3. RAJ E5H.1.fid MePNCuBr PROTON CDCl3 C:\\ Herbert CDCl Figure S30. 1 H NMR(0 MHz, 22 C) spectrum of 2-Br in CDCl 3. SI-21

22 RAJ E5C.1.fid MePNCuBr C13CPD CDCl3 C:\\ Herbert CDCl Figure S C{ 1 H} (126 MHz, 22 C) NMR spectrum of 2-Br in CDCl 3. RAJ B3P.1.fid MePNCuBr P31CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of 2-Br in CDCl 3. SI-22

23 RAJ D3H.1.fid MePNCuI PROTON128 CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert CDCl Figure S33. 1 H NMR (300 MHz, 22 C) spectrum of 2-I in CDCl 3. RAJ C5C.1.fid MePNCuI C13CPD CDCl3 C:\\ Herbert Figure S C{ 1 H} NMR (126 MHz, 22 C) spectrum of 2-I in CDCl 3. SI-23

24 RAJ G5P.2.fid MePNCuI P31CPD CDCl3 C:\\ Herbert Figure S P{ 1 H} (202 MHz, 22 C) NMR spectrum of 2-I in CDCl 3. RAJ C3H.1.fid PNquinCuCl PROTON128 CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert CDCl Figure S36. 1 H NMR (300 MHz, 22 C) spectrum of 3-Cl in CDCl 3. SI-24

25 RAJ C3C.1.fid PNquinCuCl C13CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert CDCl Figure S C{ 1 H} NMR (75 MHz, 22 C) spectrum of 3-Cl in CDCl 3. RAJ C3P.1.fid PNquinCuCl P31CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of 3-Cl in CDCl 3. SI-25

26 RAJ C3H.1.fid QuinolineCubr PROTON128 CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert CDCl Figure S39. 1 H NMR (300 MHz, 22 C) spectrum of 3-Br in CDCl 3. RAJ C3C.1.fid QuinolineCubr C13CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert CDCl Figure S C{ 1 H} NMR (75 MHz, 22 C) spectrum of 3-Br in CDCl 3. SI-26

27 RAJ D3P.1.fid PNquinCuBr P31CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of 3-Br in CDCl 3. RAJ A5H.2.fid MequinCuI PROTON CDCl3 C:\\ Herbert CDCl Figure S42. 1 H NMR (0 MHz, 22 C) spectrum of 3-I in CDCl 3. SI-27

28 RAJ A5C.1.fid MequinCuI C13CPD CDCl3 C:\\ Herbert Figure S C{ 1 H} NMR (126 MHz, 22 C) spectrum of 3-I in CDCl 3. RAJ E3P.1.fid PNquinCuI P31CPD CDCl3 {C:\Bruker\TOPSPIN1.3} Herbert Figure S P{ 1 H} (121 MHz, 22 C) NMR spectrum of 3-I in CDCl 3. SI-28

29 COMPUTATIONAL DETAILS Figure S45. Optimized (S 0 ) structure of 2-I and atom assignments. Figure S46. Optimized structure (S 0 ) of 3-I and atom assignments. SI-29

30 Table S1. Selected bond distances and angles of optimized structures of 3-I. Bond (Å) Crystal Calculated (DFT) 43N-41Cu P-41Cu Cu-42I Cu-86I I-86I Cu-85Cu I-85Cu I-85Cu Cu-88P Cu-87N Angle ( ) Crystal Calculated (DFT) 43N-41Cu-44P I-41Cu-86I Cu-42I-85Cu Cu-86I-85Cu I-85Cu-86I N-85Cu-88P P-41Cu-42I P-41Cu-86I N-41Cu-42I N-41Cu-86I P-85Cu-42I P-85Cu-86I N-85Cu-42I N-85Cu-86I SI-30

31 Table S2. Selected bond distances and angles of optimized structures of 2-I. Bond (Å) Crystal Calculated (DFT) 97N-93Cu P-93Cu Cu-95I Cu-96I I-96I Cu-94Cu I-94Cu I-94Cu Cu-100P Cu-98N Angle ( ) Crystal Calculated (DFT) 97N-93Cu-99P I-93Cu-96I Cu-95I-94Cu Cu-96I-94Cu I-94Cu-96I N-94Cu-100P P-93Cu-95I P-93Cu-96I N-93Cu-95I N-93Cu-96I P-94Cu-95I P-94Cu-96I N-94Cu-95I N-94Cu-96I SI-31

32 Bend angle ( ) Crystal DFT 3-Cl 3-Br 3-I Figure S47. Calculated and experimental bend angles for 3-X. Bend angles is defined as the dihedral angle between the two X-Cu-X triangles in 3-X. Table S3. Atomic contributions (Mulliken) to the HOMO of 2-I and 3-I (S 0 ). Cu1 Cu2 I1 I2 P1 P2 Ph1 Ph2 N-hc1 a N-hc2 a 2-I I a N-hc = N-heterocyclic ligand backbone (i.e. Me-phen for 2-I or Me-quin for 3-I). SI-32

33 Table S4. Atomic contributions (Mulliken) to the LUMO (TD-DFT) of 2-I (S 1 state) and 3-I (S 2 state) from the first allowed excited state. Cu1 Cu2 I1 I2 P1 P2 Ph1 Ph2 N-hc1 a N-hc2 a 2-I (S 1 ) 3-I (S 2 ) a N-hc = N-heterocyclic ligand backbone (i.e. Me-phen for 2-I or Me-quin for 3-I). Table S5. Atomic contributions (Mulliken) to the LUMO+1 (TD-DFT) of 2-I (S 1 state) and 3-I (S 2 state) from the first allowed excited state. Cu1 Cu2 I1 I2 P1 P2 Ph1 Ph2 N-hc1 a N-hc2 a 2-I (S 1 ) I (S 2 ) a N-hc = N-heterocyclic ligand backbone (i.e. Me-Phenan for 2-I or Me-quin for 3-I). SI-33

34 Figure S48. Diagram illustrating parameters calculated using protocol described in experimental section. Table S6. Calculated photophysical parameters for 2-I and 3-I E (ev) 2-I 3-I E adia E vert-abs E vert-phos λ T SI-34

35 Table S7. TD-DFT calculated electronic transitions for 2-I along with their corresponding excitation energies and oscillator strengths (FWHM: 3000 cm -1 ; σ: 0.2). Transition λ (nm) Osc. Major contributions Strength S H-3->L+1 (17%), HOMO->L+1 (69%) S H-2->LUMO (22%), H-1->LUMO (43%), HOMO- >LUMO (12%) S H-3->LUMO (10%), HOMO->LUMO (69%) S H-3->L+1 (37%), H-1->L+1 (20%), HOMO->L+1 (17%) S H-2->LUMO (10%), H-2->L+1 (36%), H-1->L+1 (34%) T HOMO(A)->LUMO(A) (38%), HOMO(B)->LUMO(B) (38%) Table S8. TD-DFT calculated electronic transitions for 3-I along with their corresponding excitation energies and oscillator strengths (FWHM: 3000 cm -1 ; σ: 0.2). Transition λ (nm) Osc. Strength Major contributions S1 S2 S3 S H-3->L+1 (29%), HOMO->LUMO (51%) H-3->LUMO (31%), HOMO->L+1 (49%) H-3->L+1 (11%), H-2->LUMO (14%), H-1->LUMO (24%), HOMO->LUMO (38%) H-3->LUMO (11%), H-2->L+1 (13%), H-1->L+1 (23%), HOMO->L+1 (40%) S5 T H-2->LUMO (%), H-1->LUMO (38%) HOMO(A)->LUMO(A) (38%), HOMO(B)->LUMO(B) (38%) SI-35

36 Table S9. Structural comparison between the S 0 and T 1 gas phase structures of 2-I. 2-I Structural Parameters Gas phase Bond S 0 T 1 ΔS 0 -T 1 97N-93Cu P-93Cu Cu-95I Cu-96I I-96I Cu-94Cu I-94Cu I-94Cu Cu-100P Cu-98N Angle S 0 T 1 ΔS 0 -T 1 97N-93Cu-99P I-93Cu-96I Cu-95I-94Cu Cu-96I-94Cu I-94Cu-96I N-94Cu-100P P-93Cu-95I P-93Cu-96I N-93Cu-95I N-93Cu-96I P-94Cu-95I P-94Cu-96I N-94Cu-95I N-94Cu-96I SI-36

37 Table S10. Structural comparison between the S 0 and T 1 gas phase structures of 3-I. 3-I Structural Parameters Gas phase Bond S 0 T 1 ΔS 0 -T 1 43N-41Cu P-41Cu Cu-42I Cu-86I I-86I Cu-85Cu I-85Cu I-85Cu Cu-88P Cu-87N Angle S 0 T 1 ΔS 0 -T 1 43N-41Cu-44P I-41Cu-86I Cu-42I-85Cu Cu-86I-85Cu I-85Cu-86I N-85Cu-88P P-41Cu-42I P-41Cu-86I N-41Cu-42I N-41Cu-86I P-85Cu-42I P-85Cu-86I N-85Cu-42I N-85Cu-86I SI-37

38 Energies and Reaction Coordinates 2-I (S 0 ) HF = hartrees Zero-point correction = (Hartree/Particle) Thermal correction to Gibbs Free Energy = Sum of electronic and zero-point Energies = Sum of electronic and thermal Free Energies= Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z SI-38

39 SI-39

40 SI-40

41 I (T 1 ) HF= hartrees Zero-point correction= (Hartree/Particle) Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Free Energies= Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z SI-41

42 SI-42

43 SI-43

44 I (S 0 ) HF= hartrees Zero-point correction= (Hartree/Particle) Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Free Energies= Standard orientation: Center Atomic Atomic Coordinates (Angstroms) SI-44

45 Number Number Type X Y Z SI-45

46 SI-46

47 SI-47

48 I (T 1 ) HF= hartrees Zero-point correction= (Hartree/Particle) Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Free Energies= Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z SI-48

49 SI-49

50 SI-

51 References 1. Macrae, C. F.; Bruno, I. J.; Chisholm, J. A.; Edgington, P. R.; McCabe, P.; Pidcock, E.; Rodriguez-Monge, L.; Taylor, R.; van de Streek, J.; Wood, P. A. Mercury CSD New Features for the Visualization and Investigation of Crystal Structures. J. Appl. Cryst. 2008, 41, SI-51

Department of Chemistry, University of Basel, St. Johanns-Ring 19, Spitalstrasse 51, and Klingelbergstrasse 80, CH-4056 Basel, Switzerland

Department of Chemistry, University of Basel, St. Johanns-Ring 19, Spitalstrasse 51, and Klingelbergstrasse 80, CH-4056 Basel, Switzerland Charge Transfer Pathways in Three Isomers of Naphthalene-Bridged Organic Mixed Valence Compounds Hauke C. Schmidt, Mariana Spulber, Markus Neuburger, Cornelia G. Palivan, Markus Meuwly,* and Oliver S.