Syntheses of Bipyricorroles and their meso-meso coupled dimers

Transcription

1 SUPPORTING INFORMATION Syntheses of Bipyricorroles and their meso-meso coupled dimers B. Adinarayana, Ajesh P. Thomas, Pardhasaradhi Satha and A. Srinivasan* School of Chemical Sciences, National Institute of Science Education and Research (NISER), Homi Bhabha National Institute, Bhubaneswar , Odisha, India. Table of Contents: 1. General Information : 2 2. Synthesis and spectral characterization : NMR spectral analysis : Single crystal X-ray structure and analysis : Electronic absorption and emission spectral analysis :

2 1. General Information: The reagents and materials for the synthesis were used as obtained from Sigma - Aldrich chemical suppliers. All solvents were purified and dried by standard methods prior to use. The NMR solvents were used as received and the spectra were recorded with Bruker 400 MHz spectrometer with TMS as internal standard. The ESI mass spectra were recorded with Bruker, micro-tof-qii mass spectrometer. The Electronic absorption spectra and steady state fluorescence spectra were recorded with Perkin Elmer Lambda 750 UV-Visible spectrophotometer and Perkin Elmer LS55 Fluorescence spectrometer respectively. Timeresolved fluorescence measurements were recorded on an Edinburgh instrument. X-ray quality crystals for the complexes were grown by the slow diffusion of n-hexane over CH2Cl2 solution of the complexes. Single-crystal X-ray diffraction data of 2a, 3, 3a and 5 were collected on a Bruker KAPPA APEX-II, four angle rotation system and Mo-Kα radiation ( Å). Fluorescence quantum yields were determined by using meso-tetraphenylporphyrin (TPPH2) in toluene (Фf = 0.11) as a reference. 2

3 2. Synthesis and spectral characterization: 2a. Synthetic Scheme: 3

4 2b. Synthetic procedure and spectral characterization: Synthesis of 1: Freshly prepared POCl3 (0.05 ml, 0.53 mmol), DMF(3 ml) complex solution was added into the solution of bipyridyldipyrromethane (200 mg, 0.41 mmol) in 100 ml ClCH2CH2Cl under N2 atmosphere at 0 o C. The reaction mixture was kept at same temperature for 10 min and then allowed to attain RT. After 8 h the reaction was quenched with Na2CO3 and extracted with EtOAc, dried over Na2SO4 and concentrated by rotary evaporator. The crude compound was purified by column chromatography using silica gel (silica mesh) in 25% EtOAc/n-hexane to afford 1 in 65% (137.6 mg, 0.27mmol) yield. 1 H NMR (400 MHz, CDCl3, 298 K): δ = (d, J = 12.0 Hz, 1H), 9.45 (d, J = 3.3 Hz, 1H), 9.05 (brs, 1H), 8.30 (d, J = 8.0 Hz, 1H), 8.24 (d, J = 7.9 Hz, 1H), 7.86 (td, J = 7.8, 2.2 Hz, 1H), 7.77 (t, J = 7.8 Hz, 1H), (m, 12H), 6.90 (s, 1H), 6.75 (d, J = 1.5 Hz, 1H), 6.17 (dd, J = 4.6, 2.6 Hz, 2H), 6.02 (s, 1H), 5.65 (d, J = 1.4 Hz, 1H), 5.60 (s, 1H); 13 C NMR (100 MHz, CDCl3): δ = , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ; m.p: o C; HR-MS: m/z (ESI-MS) calculated for C33H26N4O = (M+nH); found = Synthesis of 2: A solution of Ni(OAc)2 (70 mg, 0.4 mmol) in 5 ml CH3OH was added into the solution of 1 (20 mg, 0.04 mmol) in CH2Cl2 (100 ml) under open air atmosphere and allowed to stir for 3 h. The completion of the reaction was monitored by TLC. The residue was purified by silica gel (silica mesh) in 2% CH3OH/CH2Cl2 and identified as 2. The complex 2 was further recrystallized from CH2Cl2/n-hexane to afford green crystalline solid in 80% (19 mg 0.032mmol) yield. 1 H NMR (400 MHz, CDCl3, 298 K): δ = (d, J = 7.0 Hz, 2H), 8.93 (t, J = 7.7 Hz, 2H), 8.52 (d, J = 8.0 Hz, 2H), 7.82 (d, J = 5.0 Hz, 3H), (m, 6H), (m, 6H), 1.25 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ = , , , , , , , , , , , , , , ; m.p: 4

5 300 o C (decomposition); HR-MS: m/z (ESI-MS) calculated for C33H21N4Ni (without axial ligand) = (M) found = ; UV-Vis (CH2Cl2): λmax (nm) (ε [M -1 cm -1 ]) = 364 (45,487), 384 (33,873), 580 (12,518) 627 (36,819). Synthesis of 2a: The complex 2 (10 mg, mmol) was dissolved in 5ml CHCl3 and added to the solution of AgPF6 (20 mg, 0.08 mmol) in 5 ml CH3OH. The mixture was allowed to stir at reflux condition under open air atmosphere for 3 h. The crude reaction mixture was purified by silica gel (silica mesh) in 2% CH3OH/CH2Cl2 and identified as 2a. The complex 2a was further recrystallized from CH2Cl2/n-hexane to afford green crystalline solid in 90% (10.2 mg, mmol) yield. 1 H NMR (400 MHz, CDCl3, CD3OD (few drops), 298 K): δ = 9.34 (d, J = 8.7 Hz, 2H), 8.64 (t, J = 8.0 Hz, 2H), 8.48 (d, J = 8.2 Hz, 2H), 7.76 (s, 1H), 7.73 (d, J = 5.2 Hz, 2H), (m, 12H); 19 F NMR (376 MHz, CDCl3 & CD3OD (few drops)): δ = (d, J = Hz); 31 P NMR (162 MHz, CDCl3 CD3OD (few drops)): δ = (hept, J = Hz). 1 H NMR (400 MHz, CDCl3, 298 K): δ = 9.71 (d, J = 7.1 Hz, 2H), 8.85 (t, J = 7.7 Hz, 2H), 8.56 (d, J = 8.0 Hz, 2H), 7.82 (3H), (m, 12H). 19 F NMR (376 MHz, CDCl3): δ = (d, J = Hz); 31 P NMR (162 MHz, CDCl3): δ = (able to observe only quintet, J = Hz). Synthesis of 2b: The complex 2 (10 mg, mmol) was dissolved in 5ml CHCl3 and added to the solution of AgOTf (20 mg, 0.08 mmol)in 5 ml CH3OH. The mixture was allowed to stir at reflux condition under open air atmosphere for 3 h. The crude reaction mixture was purified by silica gel (silica mesh) in 3% CH3OH/CH2Cl2 and identified as 2b. The complex 2b was further recrystallized from CH2Cl2/n-hexane to afford green crystalline solid in 90% (10.3 mg, mmol) yield. 1 H NMR (400 MHz, CDCl3, 298 K): δ = (d, J = 7.3 Hz, 2H), 8.87 (t, J = 7.8 Hz, 2H), 8.52 (d, J = 8.0 Hz, 2H), 7.81 (3H), (m, 12H); 19 F NMR (376 MHz, CDCl3): δ =

6 Synthesis of 3: A solution of Pd(OAc)2 (45 mg, 0.2 mmol) in 5 ml CH3OH was added in to the solution of 1 (20.5 mg, 0.04 mmol) in CH2Cl2 (100 ml) under open air atmosphere and allowed to stir for 3 h. The completion of the reaction was monitored by TLC. The residue was purified by silica gel (silica mesh) in 2% CH3OH/CH2Cl2 and identified as 3. The complex 3 was further recrystallized from CH2Cl2/n-hexane to afford green crystalline solid in 90% (23.2 mg mmol) yield. 1 H NMR (400 MHz, CDCl3, 298 K): δ = (d, J = 6.5 Hz, 2H), 9.05 (t, J = 7.8 Hz, 2H), 8.60 (d, J = 8.1 Hz, 2H), 7.86 (3H), (m, 10H), 7.53 (d, J = 5.1 Hz, 2H), 1.25 (s, 3H); 13 C NMR (100 MHz, CDCl3): δ = , , , , , , , , , , , , , , , , , , , , , ; m.p: 300 o C (decomposition); HR-MS: m/z (ESI-MS) calculated for C33H21N4Pd (without axial ligand) = (M) found = ; UV-Vis (CH2Cl2): λmax (nm) (ε [M -1 cm -1 ]) = 360 (37,242), 378 (49,128), 584 (15,848) 634 (45,959); Quantum yield (Фf) = Synthesis of 3a: The complex 3 (10 mg, mmol) was dissolved in 5 ml CHCl3 and added to the solution of AgPF6 (19 mg, mmol) in 5 ml CH3OH. The mixture was allowed to stir at reflux condition under open air atmosphere for 3 h. The crude reaction mixture was purified by silica gel (silica mesh) in 3% CH3OH/CH2Cl2 and identified as 3a. The complex 3a was further recrystallized from CH2Cl2/n-hexane to afford green crystalline solid in 90% (10.1 mg mmol) yield. 1 H NMR (400 MHz, CDCl3, CD3OD (few drops), 298 K): δ = 9.51 (d, J = 7.7 Hz, 2H), 8.77 (t, J = 8.0 Hz, 2H), 8.57 (d, J = 8.3 Hz, 2H), 7.82 (s, 1H), 7.78 (d, J = 5.1 Hz, 2H), 7.58 (m, 10H), 7.43 (d, J = 5.1 Hz, 2H); 1 H NMR (400 MHz, CDCl3, 298 K): δ = 9.82 (d, J = 7.5 Hz, 2H), 8.94 (t, J = 7.9 Hz, 2H), 8.64 (d, J = 8.2 Hz, 2H), 7.86 (d, J = 5.5 Hz, 3H), 7.71 (m, 10H), 7.56 (d, J = 5.1 Hz, 2H); 19 F NMR (376 MHz, CDCl3): δ = (d, J = Hz); 31 P NMR (162 MHz, CDCl3): δ = (hept, J = Hz). 6

7 Synthesis of 3b: The complex 3 (10 mg, mmol) was dissolved in 5ml CHCl3 and added to the solution of AgOTf (19 mg, mmol) in 5 ml CH3OH. The mixture was allowed to stir at reflux condition under open air atmosphere for 3 h. The crude reaction mixture was purified by silica gel (silica mesh) in 3% CH3OH/CH2Cl2 and identified as 3b. The complex 3b was further recrystallized from CH2Cl2/n-hexane to afford green crystalline solid in 90% (10.2 mg, mmol) yield. 1 H NMR (400 MHz, CDCl3, 298 K): δ = (d, J = 7.5 Hz, 2H), 8.99 (t, J = 7.9 Hz, 2H), 8.62 (d, J = 8.3 Hz, 2H), 7.86 (3H), 7.70 (m, 10H), 7.55 (d, J = 5.2 Hz, 2H); 19 F NMR (376 MHz, CDCl3): δ = Synthesis of 4: FeCl3 (135 mg, mmol) was added into the solution of 2 (20 mg, 0.03 mmol) in 100 ml CHCl3 and allowed to stir for 4 h at 55 o C under open air atmosphere. The completion of the reaction was monitored by TLC and extracted with CH2Cl2. The organic layer was washed with NaPF6 aqueous solution to exchange the counter ion of the complex. Residue was purified by silica gel (silica mesh) in 2% CH3OH/CH2Cl2 and identified as 4. The complex was further recrystallized from CH2Cl2/n-hexane to afford blue crystalline solid 4 in 80% (18.2 mg mmol) yield. 1 H NMR (400 MHz, CDCl3, 298 K): δ = 9.61 (d, J = 7.9 Hz, 4H), 8.83 (t, J = 8.0 Hz, 4H), 8.59 (d, J = 7.2 Hz, 4H), (m, 20H), 7.51 (d, J = 5.4 Hz, 4H), 7.23 (d, J = 5.4 Hz, 4H); 13 C NMR (100 MHz, CDCl3): δ = , , , , , , , , , , , , , , , , ; 19 F NMR (376 MHz, CDCl3): δ = (d, J = Hz); 31 P NMR (162 MHz, CDCl3): δ = (hept, J = Hz); m.p: 300 o C (decomposition); HR-MS: m/z (ESI-MS) calculated for C66H40N8Ni2PF6 (One PF6 less) = (M); found = ; UV-Vis (CH2Cl2): λmax (nm) (ε [M -1 cm -1 ]) = 365 (50,352), 402 (70.742), 600 (15,412), 639 (30,597). Synthesis of 5: FeCl3 (125 mg, mmol) was added into the solution of 3 (20 mg, 0.03 mmol) in 100 ml CHCl3 and allowed to stir for 3 h at 55 o C under open air atmosphere. The 7

8 completion of the reaction was monitored by TLC and extracted with CH2Cl2, and the organic layer was washed with NaPF6 aqueous solution to exchange the counter ion of the complex. Residue was purified by silica gel (silica mesh) in 3% CH3OH/CH2Cl2 and identified as 5. The complex was further recrystallized from CH2Cl2/n-hexane to afford blue crystalline solid 5 in 80% (18.1 mg mmol) yield. 1 H NMR (400 MHz, CDCl3, 298 K): δ = 9.78 (d, J = 7.7 Hz, 4H), 8.93 (t, J = 8.1 Hz, 4H), 8.67 (d, J = 8.1 Hz, 4H), (m, 20H), 7.41 (d, J = 5.4 Hz, 4H), 7.25 (d, J = 5.5 Hz, 4H); 1 H NMR (400 MHz, CDCl3 and CD3OD, 298 K): δ = 9.60 (d, J = 7.8 Hz, 4H), 8.81 (t, J = 8.1 Hz, 4H), 8.58 (d, J = 8.3 Hz, 4H), 7.54 (m, 20H), 7.27 (d, J = 5.8 Hz, 4H), 7.09 (d, J = 5.4 Hz, 4H). 13 C NMR (100 MHz, CDCl3 and MeOD): δ = , , , , , , , , , , , , , , F NMR (376 MHz, CDCl3): δ = (d, J = Hz); 31 P NMR (162 MHz, CDCl3): δ = (hept, J = Hz); m.p: 300 o C (decomposition); HR-MS: m/z (ESI-MS) calculated for C66H40N8Pd2PF6 (One PF6 less) = (M); found = ; UV-Vis (CH2Cl2): λmax (nm) (ε [M -1 cm -1 ]) = 360 (45,504), 401 (62,678), 604 (15,041), 643 (35,661). Quantum yield (Фf) =

9 3. NMR spectral analysis: Figure S1. 1 H-NMR spectrum of 1 in CDCl3. Figure S2. 13 C-NMR spectrum of 1 in CDCl3. 9

10 Figure S3. 1 H-NMR spectrum of 2 in CDCl3 (*Residual solvent and impurity grease). Figure S4. 13 C-NMR spectrum of 2 in CDCl3. 10

11 Figure S5. 1 H - 1 H COSY spectrum of 2 in CDCl3. 11

12 Figure S6. a) 1 H-NMR, b) 19 F-NMR and c) 31 P-NMR spectra of 2a in CDCl3 (*Residual solvents and impurity grease). 12

13 Figure S7. a) 1 H-NMR, b) 19 F-NMR and c) 31 P-NMR spectra of 2a in CDCl3 and CD3OD (*Residual solvents and impurity grease). 13

14 Figure S8. 1 H - 1 H COSY spectrum of 2a in CDCl3 and CD3OD. 14

15 Figure S9. 1 H-NMR spectrum of 2b in CDCl3 (*Residual solvents and impurity grease). Figure S F-NMR spectrum of 2b in CDCl3. 15

16 Figure S11. 1 H-NMR spectrum of 3 in CDCl3 (*Residual solvent and impurity grease). Figure S C-NMR spectrum of 3 in CDCl3. 16

17 Figure S13. 1 H - 1 H COSY spectrum of 3 in CDCl3. Figure S14. 1 H-NMR spectrum of 3a in CDCl3 (*Residual solvents and impurity grease). 17

18 Figure S15. a) 1 H-NMR, b) 19 F-NMR and c) 31 P-NMR spectra of 3a in CDCl3 and CD3OD (*Residual solvent and impurity grease). 18

19 Figure S16. 1 H - 1 H COSY spectrum of 3a in CDCl3 and CD3OD. 19

20 Figure S17. 1 H-NMR spectrum of 3b in CDCl3 (*Residual solvents and impurity grease). Figure S F-NMR spectrum of 3b in CDCl3. 20

21 Figure S19. a) 1 H-NMR, b) 19 F-NMR and c) 31 P-NMR spectra of 4 in CDCl3 (*Residual solvents and impurity grease). 21

22 Figure S20. 1 H - 1 H COSY spectrum of 4 in CDCl3. Figure S C-NMR spectrum of 4 in CDCl3. 22

23 Figure S22. a) 1 H-NMR, b) 19 F-NMR and c) 31 P-NMR spectra of 5 in CDCl3 (*Residual solvent and impurity grease). 23

24 Figure S23. 1 H - 1 H COSY spectrum of 5 in CDCl3. 24

25 Figure S24. a) 1 H-NMR and b) 13 C-NMR spectrum of 5 in CDCl3 and CD3OD (*Residual solvent and impurity grease). 25

26 4. Single crystal X-ray structure and analysis: Figure S25. Single crystal X-ray structure of 3. a) Top view and b) side view. The bond distance and angle in b) is: C35-H35c N1(π) is: 2.66 Å and 122. The meso-phenyl groups are omitted for clarity in the side view. 26

27 Figure S26. Single crystal X-ray structure of 3a. a) Top view, b) side view and c) 1-D array. The bond distance and angle in c) is: C30-H30 Ph(π) is : 2.84 Å and 169. The meso-phenyl groups are omitted for clarity in b). Figure S27. Bond lengths (Å) in 3 (a) and 3a (b). The anionic ligands in a) and b) are omitted for clarity. 27

28 Figure S28. Single crystal X-ray structure of 2a. a) Top view, b) side view and c) 1-D array. The bond distance and angle in c) is: C26-H26 Ph(π) is: 2.84 Å and 166. The meso-phenyl groups are omitted for clarity in b). 28

29 Figure S29. Bond lengths in 2a (Å). The PF6 unit is omitted for clarity. Table S1. Saddling dihedral angle ( ) and the Bond angle around the metal ion ( ) in 2a. Saddle dihedral angle ( ) Bond angle around metal ion ( ) C4-C5-C7-C N1-Ni-N C9-C10-C12-C N2-Ni-N C14-C15-C17-C N3-Ni-N C20-C21-C1-C N4-Ni-N Average

30 Figure S30. Single crystal X-ray structure of 5. a) Top view and b) side view. The meso-phenyl groups are omitted for clarity in the side view. 30

31 Table S2. Bond length (Å) and the Bond angle around the metal ion ( ) in a) 3, b) 3a and c) 5. The PF6 units are omitted for clarity in c). 3 (Å) 3a (Å) 5 (Å) N1-Pd N5-Pd N2-Pd N6-Pd N3-Pd N7-Pd N4-Pd N8-Pd ( ) 3a ( ) 5 ( ) N1-Pd-N N5-Pd-N N2-Pd-N N6-Pd-N N3-Pd-N N7-Pd-N N4-Pd-N N8-Pd-N Average

32 Figure S31. Bond lengths in 5 (Å). The PF6 units are omitted for clarity. Table S3. Selected bond angles in 5 ( ). N1 unit Bipyridyl (N1 & N4) unit Bond angle ( ) N4 unit Bond angle ( ) N5 unit Bipyridyl (N5 & N8) unit Bond angle ( ) N8 unit Bond angle ( ) C5-N1-C C21-N4-C C38-N5-C C54-N8-C N1-C1-C N4-C17-C N5-C34-C N8-C50-C C1-C2-C C17-C18-C C34-C35-C C50-C51-C C2-C3-C C18-C19-C C35-C36-C C51-C52-C C3-C4-C C19-C20-C C36-C37-C C52-C53-C C4-C5-N C20-C21-N C37-C38-N C53-C54-N Average Average Average Average

33 Table S4. Saddling dihedral angle ( )in a) 3, b) 3a and c) 5. The PF6 units are omitted for clarity in c). 3 ( ) 3a ( ) 5 ( ) C4-C5-C7-C C37-C38-C40-C C9-C10-C12-C C42-C43-C45-C C14-C15-C17-C C47-C48-C50-C C20-C21-C1-C C53-C54-C34-C

34 Table S5. Mean plane deviation (containing 25 atoms) of various units in a) 3, b) 3a and c) 5. The PF6 units are omitted for clarity in c). 3 ( ) 3a ( ) 5 ( ) Pyridine (N1) Pyridine (N5) 4.38 Pyrrole (N2) Pyrrole (N6) 3.73 Pyrrole (N3) Pyrrole (N7) 3.98 Pyridine (N4) Pyridine (N8) 1.29 Phenyl-1 (Ph-1) Phenyl-3 (Ph-3) Phenyl-2 (Ph-2) Phenyl-4 (Ph-4) Pd1 Plane Pd2 Plane

35 Table S6: Crystal data for 2a, 3, 3a and 5: Crystal 2a 3 3a 5 parameters Formula C 33H 21N 4F 6PNi C 35H 26N 4O 3Pd C 33H 21N 4F 6PPd C 66H 40F 12N 8P 2Pd 2 M/g mol T/K 100 K 100 K 100 K 100 K Crystal 0.12 x 0.07 x 0.15 x 0.11 x 0.14 x 0.08 x 0.1 x 0.08 x 0.06 dimensions/mm Crystal system Orthorhombic Monoclinic Orthorhombic Monoclinic Space group Pcca P2(1)/n Pcca P2(1)/c a/å (6) (10) (15) (5) b/å (3) (10) (6) (5) c/å (9) (3) (2) (5) α/ (5) β/ (10) (5) γ/ (5) V/Å (3) (5) (7) 6018(3) Z ρ calcd/mg m μ/mm F(000) Reflns. collected Indep.reflns [0.1298] 7234 [0.0525] 5431 [0.0677] [0.0986] [R(int)] Max/min transmission and and and and Data/restraints 5177 / 6 / / 27 / 5431 / 4 / / 0 / 811 /parameters 396 GOF on F Final R indices[i > 2σ(I)] R1 = , wr2 = R1 = , wr2 = R1 = , wr2 = 0.23 R1 = , wr2 = R indices (all data) R 1= , wr2 = R1 = , wr2 = R 1= , wr2 = R1 = , wr2 = Largest diff peak and hole [e Å 3 ] and and and and The crystals have been deposited in the Cambridge Crystallographic Data Centre for 2a, 3, 3a and 5 are , , and respectively. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via The highly disordered solvent molecules were removed by the SQUEEZE routine using the PLATON program to proceed to the final refinement of the main structure Spek, A. Acta Crystallogr. 2015, C71,

36 There is a minor disordered component in the single crystal X-ray structure of 2a and 3a. Structural disorder in 2a and 3a: The difference Fourier maps for the X-ray models of 2a and 3a indicate the presence of a minor component of crystallographic positional disorder with respect to the orientations of the molecules. However, attempts to model this positional disorder as superposing molecular frameworks with opposite orientations (180 degree rotation around C-metal-C vector) did not result in stable refinement. Hence the structural models of 2a and 3a have been finalized based on three separate refinement models (Table S7). Model 1. Using SQUEEZE command to remove the solvent contributions and including no crystallographic constraints. The huge and uneven thermal ellipsoids seen in the unconstrained model may be arising from the minor component of the apparent structural disorder [Figure 32 (Model 1)]. Model 2. Modelling the CH2Cl2 solvent molecules in the crystal lattice and applying constraints on the ADPs for C atoms which are part of conjugated rigid molecular framework using EADP constraint. Although these additional constraints result in an increase in the R factors of both 2a and 3a, it refines to chemically more reasonable ADPs -where the atoms of the rigid framework showing similar ADPs. Model 3. Using SQUEEZE command to remove all solvent contributions (including the disordered CH2Cl2 solvent molecules) from the ADP constrained model (Model 2). 36

37 Table S7: Crystal data for 2a, 3a: Model 1 Model 2 Crystal parameters 2a 3a 2a 3a Formula C33H21N4F6PNi C33H21N4F6PPd C33H21N4F6PNi C33H21N4F6PPd T/K 100 K 100 K 100 K 100 K GOF on F Final R indices[i > 2σ(I)] R indices (all data) Largest diff peak and hole [e Å -3 ] R1 = , wr2 = R1= , wr2 = and R1 = , wr2 = R1= , wr2 = and R1 = , wr2 = R1= , wr2 = and R1 = , wr2 = R1= , wr2 = and Model 3 Crystal parameters 2a 3a Formula C33H21N4F6PNi C33H21N4F6PPd T/K 100 K 100 K GOF on F Final R indices[i > 2σ(I)] R1 = , wr2 = R1 = , wr2 = 0.23 R indices (all R1= , R1= , data) Largest diff peak and hole [e Å -3 ] wr2 = and wr2 = and

38 Figure S32. ORTEPs of 2a and 3a (with 50% probability ellipsoids). i) Model 1 with squeezed solvent contribution and without crystallographic constraints; ii) Model 2 is applying crystallographic constraints (EADP) without squeeze, and iii) Model 3 is applying crystallographic (EADP) constraints followed by squeeze. 38

39 5. Electronic absorption and emission spectral analysis: Figure S33. Electronic Absorption spectra of 2 and 3 in CH2Cl2. Figure S34. Electronic Absorption spectra of 2 and 4 in CH2Cl2. 39

40 Figure S35. Electronic Absorption spectra of 3 and 5 in CH2Cl2. Figure S36. Electronic Absorption spectra of 4 and 5 in CH2Cl2. 40

41 Figure S37. Emission spectra of 3 and 5 in CH2Cl2. 41

42 (a) (b) Figure S38. Lifetime measurement of 3a (a) and 5 (b) in CH2Cl2. 42