Rhenium(I)-Based Monocyclic- and Bicyclic Phosphine Oxide Coordinated. Supramolecular Complexes

Transcription

1 Supporting Information Rhenium(I)-Based Monocyclic- and Bicyclic Phosphine Oxide Coordinated Supramolecular Complexes Bhaskaran Shankar, Ramar Arumugam, Palani Elumalai, and Malaichamy Sathiyendiran*, School of Chemistry, University of Hyderabad, Prof. C. R. Rao Road, Gachibowli, Central University P.O., Hyderabad , India or Contents 1. Figure S1. The 31 P-{ 1 H} NMR spectra of free ligand and 1 in dmso d Figure S2. The 31 P-{ 1 H} NMR spectra of free ligand, 2 and 5 in dmso d Figure S3. The 31 P-{ 1 H} NMR spectra of free ligand, 3 and 6 in dmso d Figure S4. The 31 P-{ 1 H} NMR spectra of free ligand, 4 and 7 in dmso d Figure S5. The 31 P-{ 1 H} NMR spectra of free ligand and 8 in dmso d Figure S6. The 31 P-{ 1 H} NMR spectra of free ligand and 9 in dmso d Figure S7. The 31 P-{ 1 H} NMR spectra of free ligand and 10 in dmso d Figure S8. The 1 H NMR spectra of free ligand and 1 in dmso d 6 (*= solvents and solvent water peaks). 9. Figure S9. The 1 H NMR spectra of free ligand, 2 and 5 in dmso d 6 (*= solvent water peaks). 10. Figure S10. The 1 H NMR spectra of free ligand, 3 and 6 in dmso d 6 (*= solvent water peaks). 11. Figure S11. The 1 H NMR spectra of free ligand, 4 and 7 in dmso d Figure S12. The 1 H NMR spectra of free ligand and 8 in dmso d 6 (*= solvent peaks). 13. Figure S13. The 1 H NMR spectra of free ligand and 9 in dmso d 6 (*= solvent water peaks). 14. Figure S14. The 1 H NMR spectra of free ligand and 10 in dmso d 6 (*= solvent water peaks). 15. Figure S15. Molecular structure of 1. H atoms are omitted for clarity. Color code: gray = C, red = O, pink = P, and orange = Re. S1

2 16. Figure S16. Molecular structure of 3. H atoms are omitted for clarity. Color code: gray = C, red = O, pink = P, green=cl and orange = Re. 17. Figure S17. Molecular structure of 4 (A), and 7 (B). H atoms are omitted for clarity. Color code: gray = C, red = O, pink = P, green=cl and orange = Re. 18. Scheme S1. Synthesis of Bicyclic SCCs 9-10 and III. 19. Figure S18. Calculated UV-vis spectra of complexes in THF solvent model (except complexes I and II ). 20. Figure S19. Frontier molecular orbitals involved in TDDFT transition of Table S1. Crystal Data for the Structural Determination of Complexes 1-5 and Table S2. Crystal Data for the Structural Determination of Complexes Table S3. Selected Bond Distances (Å) and Angles (deg) of P=O Re CO(trans) and DHBQ/thq unit in the Complexes 24. Table S4. Selected singlet excited state transitions for 1 as obtained from TDDFT calculations in the THF. 25. Table S5. Selected singlet excited state transitions for 2 as obtained from TDDFT calculations in the THF. 26. Table S6. Selected singlet excited state transitions for 3 as obtained from TDDFT calculations in the THF. 27. Table S7. Selected singlet excited state transitions for 4 as obtained from TDDFT calculations in the THF. 28. Table S8. Selected singlet excited state transitions for 5 as obtained from TDDFT calculations in the THF. 29. Table S9. Selected singlet excited state transitions for 6 as obtained from TDDFT calculations in the THF. 30. Table S10. Selected singlet excited state transitions for 7 as obtained from TDDFT calculations in the THF. 31. Table S11. Selected singlet excited state transitions for 8 as obtained from TDDFT calculations in the THF. 32. Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of 6. S2

3 38. Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of 8. S3

4 Figure S1. The 31 P-{ 1 H} NMR spectra of free ligand and 1 in dmso d 6. S4

5 Figure S2. The 31 P-{ 1 H} NMR spectra of free ligand, 2 and 5 in dmso d 6. S5

6 Figure S3. The 31 P-{ 1 H} NMR spectra of free ligand, 3 and 6 in dmso d 6. S6

7 Figure S4. The 31 P-{ 1 H} NMR spectra of free ligand, 4 and 7 in dmso d 6. S7

8 Figure S5. The 31 P-{ 1 H} NMR spectra of free ligand and 8 in dmso d 6. S8

9 Figure S6. The 31 P-{ 1 H} NMR spectra of free ligand and 9 in dmso d 6. S9

10 Figure S7. The 31 P-{ 1 H} NMR spectra of free ligand and 10 in dmso d 6. S10

11 Figure S8. The 1 H NMR spectra of free ligand and 1 in dmso d 6 (*= solvents and solvent water peaks). S11

12 Figure S9. The 1 H NMR spectra of free ligand, 2 and 5 in dmso d 6 (*= solvent water peaks). S12

13 Figure S10. The 1 H NMR spectra of free ligand, 3 and 6 in dmso d 6 (*= solvent water peaks). S13

14 Figure S11. The 1 H NMR spectra of free ligand, 4 and 7 in dmso d 6. S14

15 Figure S12. The 1 H NMR spectra of free ligand and 8 in dmso d 6 (*= solvent peaks). S15

16 Figure S13. The 1 H NMR spectra of free ligand and 9 in dmso d 6 (*= solvent water peaks). S16

17 Figure S14. The 1 H NMR spectra of free ligand and 10 in dmso d 6 (*= solvent water peaks). S17

18 Figure S15. Molecular structure of 1. H atoms are omitted for clarity. Color code: gray = C, red = O, pink = P, and orange = Re. S18

19 Figure S16. Molecular structure of 3. H atoms are omitted for clarity. Color code: gray = C, red = O, pink = P, green=cl and orange = Re. S19

20 A B Figure S17. Molecular structure of 4 (A), and 7 (B). H atoms are omitted for clarity. Color code: gray = C, red = O, pink = P, green=cl and orange = Re. S20

21 Scheme S1. Synthesis of Bicyclic SCCs 9-10 and III. S21

22 ε (M 1 cm 1 ) 3x10 4 2x10 4 1x I ƒ ε (M 1 cm 1 ) 3x10 4 2x10 4 1x ƒ Wavelength (nm) Wavelength (nm) 0.3 3x10 4 5x ε (M 1 cm 1 ) 2x10 4 1x ƒ ε (M 1 cm 1 ) 4x10 4 3x10 4 2x10 4 1x ƒ Wavelength (nm) Wavelength (nm) ε (M 1 cm 1 ) 6x10 4 5x10 4 4x10 4 3x10 4 2x II ƒ 0.2 1x Wavelength (nm) Figure S18. Calculated UV-vis spectra of complexes in THF solvent model (except complexes I and II ). S22

23 Figure S19. Frontier molecular orbitals involved in TDDFT transition of 1-8. S23

24 Table S1. Crystal Data for the Structural Determination of Complexes 1-5 and (C 7 H 8 ) chemical formula C 40 H 30 O 12 P 2 Re C 39 H 26 Cl 2 O 12 P 2 Re 2 C 65 H 52 Cl 2 O 12 P 2 Re 2 C 28 H 28 Cl 2 O 16 P 2 C 39 H 28 O 12 P 2 Re 2 C 28 H 30 O P 2 Re 2 2 Re 2 formula weight crystal system monoclinic monoclinic triclinic monoclinic monoclinic monoclinic space group P2 1 /c P 2 1 /n Pī P2 1 /c P2 1 /n P2 1 /m a (Å) (5) (12) (9) (5) (10) (9) b (Å) (12) (2) (12) (8) (16) (3) c (Å) (13) (2) (14) (9) (2) (11) α (deg) (2) β (deg) (2) (4) (3) (5) (3) (4) γ (deg) (2) V (Å 3 ) (4) (9) (4) (3) (8) (4) Z T (K) 296(2) 296(2) 100(2) 293(2) 296(2) 293(2) λ (Å) D calc (g cm 3 ) µ (mm 1 ) R 1 [I > 2σ(I)] a wr 2 (all data) b GooF a R 1 = Σ F o F c /Σ F o ; b wr 2 = {Σ[w(F o 2 F c 2 ) 2 ]/Σ[w(F o 2 ) 2 ]} 1/2 S24

25 Table S2. Crystal Data for the Structural Determination of Complexes chemical formula C 42 H 38 O 32 P 4 Re 4 C 72 H 52 O 22 P 4 Re 4 C 82 H 56 O 22 P 4 Re 4 formula weight crystal system monoclinic monoclinic triclinic space group P2 1 /n P2 1 /n Pī a (Å) (3) (6) (9) b (Å) (3) (6) (11) c (Å) (4) (7) (12) α (deg) (3) β (deg) (9) (5) (3) γ (deg) (3) V (Å 3 ) 7235(4) 7235(4) (4) Z T (K) 296(2) 150(2) 100(2) λ (Å) D calc (g cm 3 ) µ (mm 1 ) R 1 [I > 2σ(I)] a wr 2 (all data) b GooF a R 1 = Σ F o F c /Σ F o ; b wr 2 = {Σ[w(F o 2 F c 2 ) 2 ]/Σ[w(F o 2 ) 2 ]} 1/2 S25

26 Table S3. Selected Bond Distances (Å) and Angles (deg) of P=O Re CO(trans) and DHBQ/thq unit in the Complexes Compounds Free ligand P=O 1.497;1.485 (L 1 ) 1.482(2); 1.488(2) (L 2 ) (L 3 ) 1.485(7) 1.496(7) Re O(P) 2.152(6) 2.151(7) Re C(O) 1.890(14) 1.877(14) C O 1.150(13) 1.170(14) P Ο Ο Re 151.2(4) 143.5(5) (P)Ο Ο Re C 172.9(5) 173.4(4) C C of CA 2- / DHBQ 2 /thq (13) 1.389(14) 1.383(14) 1.500(13) 1.372(13) 1.370(13) 1.513(9) 1.506(10) 2.149(9) 2.147(8) 1.91(3) 1.899(16) 1.15(3) 1.138(19) 140.7(6) 138.8(5) 171.9(7) 173.1(6) 1.39(3) 1.36(2) 1.53(2) 1.41(3) 1.32(3) 1.49(3) 1.512(8) 1.509(9) 2.168(8) 2.157(8) 1.876(15) 1.902(15) 1.180(17) 1.159(17) 135.5(5) 135.8(5) 172.1(5) 174.3(4) 1.370(17) 1.408(17) 1.386(17) 1.410(17) 1.508(15) 1.510(16) 1.482(13) 1.457(13) 2.158(12) 2.174(12) 1.91(2) 1.90(2) 1.13(2) 1.17(3) 137.3(7) 138.6(7) 174.3(7) 175.4(7) 1.40(2) 1.54(2) 1.34(2) 1.36(2) 1.541(19) 1.39(2) 1.497(5) 1.501(5) 2.163(4) 2.149(5) 1.893(9) 1.896(12) 1.136(11) 1.125(13) 141.5(3) 141.1(3) 171.9(3) 173.1(5) 1.523(9) 1.371(9) 1.365(10) 1.520(10) 1.390(9) 1.377(9) 1.460(13) 1.465(5) 1.452(7) 2.166(12) 2.169(5) 2.165(6) 1.87(3) 1.894(10) 1.890(13) 1.16(3) 1.152(11) 1.139(12) 143.1(8) 152.2(3) 158.7(4) 174.1(9) 175.8(4) 173.8(4) 1.384(7) 1.393(7) 1.381(7) 1.396(7) 1.501(7) 1.505(7) 1.375(11) 1.515(11) 1.381(11) 1.365(11) 1.520(11) 1.382(11) 1.476(8) 1.496(8) 1.493(8) 1.481(7) 2.150(8) 2.149(8) 2.156(7) 2.159(8) 1.883(14) 1.871(14) 1.903(14) 1.897(16) 1.173(15) 1.169(16) 1.153(15) 1.161(16) 147.3(6) 132.2(5) 149.9(5) 154.2(5) 169.9(5) 173.5(4) 171.9(4) 172.2(5) 1.357(15) 1.475(14) 1.400(14) 1.360(15) 1.421(15) 1.493(15) 1.502(4) 1.461(5) 1.507(4) 1.474(5) 2.167(4) 2.082(5) 2.098(5) 2.151(4) 1.882(6) 1.892(7) 1.895(6) 1.887(6) 1.152(8) 1.143(8) 1.148(8) 1.147(8) 146.7(2) 149.8(3) 141.5(2) 149.0(3) 173.7(2) 174.2(2) 168.7(2) 172.4(2) 1.421(15) 1.357(15) 1.475(14) 1.400(14) 1.360(15) 1.493(15) S26

27 C O of CA 2 / DHBQ 2 /thq (11) 1.250(11) 1.280(12) 1.281(11) 1.27(2) 1.256(15) 1.28(2) 1.27(2) 1.268(15) 1.271(13) 1.256(15) 1.259(14) 1.243(18) 1.261(18) 1.249(18) 1.266(18) 1.283(7) 1.268(8) 1.277(8) 1.260(8) 1.246(19) 1.27(2) 1.275(9) 1.270(9) 1.270(9) 1.273(10) 1.240(13) 1.398(12) 1.266(12) 1.273(13) 1.373(11) 1.285(12) 1.281(6) 1.366(6) 1.273(6) 1.287(6) 1.365(6) 1.268(6) S27

28 Table S4. Selected singlet excited state transitions for 1 as obtained from TDDFT calculations in the THF. Trans band Wavelength (nm) Oscillator strength (f) Major contribution [%] Character H 4 LUMO (29 %) H 1 LUMO (69%) Re (51%) CO (23%) DHBQ 2 (91 %) DHBQ 2 (19 %) H 4 LUMO (66%) H 1 LUMO (26%) H 17 LUMO (11%) H 13 LUMO (78%) Re (57%) CO (25 %) DHBQQ 2 (91 %) DHBQ 2 (12 %) O=P P=O (98 %) DHBQ 2 (91 %) Table S5. Selected singlet excited state transitions for 2 as obtained from TDDFT calculations in the THF. Trans band Wavelength (nm) Oscillator strength (f) Major contribution [%] Character H 4 LUMO (26 %) H 1 LUMO (73%) Re (49%) CO (25%) CA 2 (91 %) CA 2 (24 %) H 4 LUMO (74%) H 1 LUMO (25%) Re (57%) CO (31 %) CA 2 (91 %) CA 2 (11 %) H 13 LUMO (92%) Re (11%) CA 2 (50 %) CA 2 (91 %) O=P P=O (36 %) S28

29 Table S6. Selected singlet excited state transitions for 3 as obtained from TDDFT calculations in the THF. Trans band Wavelength (nm) Oscillator strength (f) Major contribution [%] Character H 4 LUMO (17 %) H 1 LUMO (65%) Re (50%) CO (26%) CA 2 (91 %) CA 2 (20 %) H 3 LUMO (71%) H 2 LUMO (10%) H 4 LUMO (79%) H 1 LUMO (16%) Re (62%) CO (30 %) CA 2 (91 %) CA 2 (3 %) Re (58%) CO (31 %) CA 2 (91 %) CA 2 (9 %) H 17 LUMO (83%) Re (8%) CA 2- (43%) CA 2 (91 %) O=P P=O (47%) Table S7. Selected singlet excited state transitions for 4 as obtained from TDDFT calculations in the THF. Trans band Wavelength (nm) Oscillator strength (f) Major contribution [%] Character H 5 LUMO (36 %) H 1 LUMO (56%) Re (45%) CO (23 %) CA 2 (91 %) CA 2 (23 %) H 5 LUMO (49%) H 1 LUMO (29%) Re (56%) CO (30 %) CA 2 (91 %) CA 2 (11 %) H 9 LUMO (83%) Re (16%) CO (5 %) CA 2 (91 %) CA 2 (73 %) S29

30 Table S8. Selected singlet excited state transitions for 5 as obtained from TDDFT calculations in the THF. Trans band Wavelength (nm) Oscillator strength (f) Major contribution [%] Character H 4 LUMO (29 %) H 1 LUMO (69%) Re (48%) CO (3%) DHBQ 2 (91 %) DHBQ 2 (24 %) H 4 LUMO (70%) H 1 LUMO (29%) H 15 LUMO (71%) H 1 LUMO+2 (10%) Re (55%) CO (27 %) DHBQ 2 (91 %) DHBQ 2 (13 %) Re (9%) DHBQ 2 (26 %) DHBQ 2 (91 %) O=P P=O (63 %) Table S9. Selected singlet excited state transitions for 6 as obtained from TDDFT calculations in the THF. Trans band Wavelength (nm) Oscillator strength (f) Major contribution [%] Character H 4 LUMO (13 %) H 3 LUMO (18%) H 1 LUMO (61%) Re (49%) CO (26 %) DHBQ 2 (91 %) DHBQ 2 (21 %) H 3 LUMO (72%) H 1 LUMO (21%) H 19 LUMO (22%) H 17 LUMO (59%) Re (60%) CO (30%) DHBQ 2 (91 %) DHBQ 2 (7 %) Re (11%) DHBQ 2 (52 %) DHBQ 2 (91 %) O=P P=O (33%) S30

31 Table S10. Selected singlet excited state transitions for 7 as obtained from TDDFT calculations in the THF. Trans band Wavelength (nm) Oscillator strength (f) Major contribution [%] Character H 5 LUMO (49 %) H 1 LUMO (41%) Re (52%) CO (28 %) DHBQ 2 (91 %) DHBQ 2 (12 %) H 11 LUMO (24%) H 10 LUMO (29%) H 9 LUMO (35%) Re (18%) DHBQ 2 (69 %) DHBQ 2 (91 %) O=P P=O (8%) H 11 LUMO (57%) H 9 LUMO (31%) Re (13%) DHBQ 2 (80 %) (91 %) O=P P=O (3%) DHBQ 2 Table S11. Selected singlet excited state transitions for 8 as obtained from TDDFT calculations in the THF. Trans band Wavelength (nm) Oscillator strength (f) Major contribution [%] Character H 5 LUMO+1 (23 %) H 4 LUMO (24%) H 3 LUMO (17%) H 2 LUMO+1 (16%) Re (56%) CO (31 %) DHBQ 2 (91 %) DHBQ 2 (13 %) H 7 LUMO (31%) H 6 LUMO+1 (28%) H 3 LUMO (17%) H 2 LUMO+11 (16%) Re (58%) CO (31%) DHBQ 2 (91 %) DHBQ 2 (9%) H 9 LUMO+1 (37%) H 8 LUMO (39%) H 3 LUMO (11%) Re (59%) CO (31%) DHBQ 2 (91 %) DQ 2 (8%) H 21 LUMO (21%) H 20 LUMO+1 (21%) H 17 LUMO (23%) Re (17%) DHBQ 2 (69 %) DHBQ 2 (91 %) O=P P=O (8%) S31

32 H 16 LUMO+1 (26%) Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of S32

33 S33

34 Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of 2. Atom X Y Z S34

35 S35

36 Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of 3. Atom X Y Z S36

37 S37

38 Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of 4. S38

39 Atom X Y Z S39

40 Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of 5. S40

41 Atom X Y Z S41

42 Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of 6. S42

43 Atom X Y Z S43

44 S44

45 Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of 7. Atom X Y Z S45

46 S46

47 Cartesian coordinates of the DFT/B3LYP/SDD optimized structure of S47

48 S48

49 S49

50 S50