1. 1 Systematic Synthesis, Isolation, and Photophysical Properties of Linear-Shaped Re(I) Oligomers and Polymers with 2-20 Units Youhei Yamamoto, Shuhei Sawa, Yusuke Funada, Tatsuki Morimoto, Magnus Falkenstro¨m, Hiroshi Miyasaka, Sayaka Shishido, Tomoji Ozeki, Kazuhide Koike, and Osamu Ishitani* J. Am. Chem. Soc. 2008, 130, 14659–14674 ，

2. 2 Linear-Shaped Metal Oligomers Shie-Ming Peng.Angen. Chem. Inr. Ed. Engl. 1997, 36, 56 [Co 5 (  5 -tpda) 4 (NCS) 2 ][Ni 5 (  5 -tpda) 4 CI 2 ]

3. 3 Motivation Excellent emitters Room-temperature luminescence, long lifetime High emission quantum yield Molecular-scale photonic wires

4. 4 Photochemical Ligand Substitution Reaction Ishitani, O, et. Al, J. Am. Chem. Soc. 2002, 124, 11448–11455. Schoonover, J. R. et. al, Inorg. Chem. 2001, 40, 5056–5057.

5. 5 Synthesis of a linear-shaped rhenium(I) diimine complexes Ishitani, O, et. Al, Chem. Commun., 2001, 1514–1515

6. 6 Photophysical Properties of linear-shaped rhenium(I) diimine complexes Ishitani, O, et. Al, Chem. Commun., 2001, 1514–1515 Fig. 1 (b) emission spectra (350 nm excitation) of 1 4+, 2b 3+, 3 2+ and 5 + in acetonitrile.

7. 7 Synthetic Strategy LL x “Target molecules” “Complex as ligand” “Complex as metal”

8. 8 Synthesis of Linear-Shaped Rhenium(I) Complexes (i) h (>330 nm) in CH 2 Cl 2 for 30 min; (ii) excess ac in CH 2 Cl 2 at room temperature for 1 day, then at 40 °C for 1 day; (iii) fac-Re(bpy)(CO) 3 (CF 3 SO 3 ) in CH 2 Cl 2 at room temperature for 1 day, then at 40 °C for 1 day; (iv) ac (0.5 equiv) in CH 2 Cl 2 at room temperature for 1 day, then at 40 °C for 1 day. 0.5 eq ac h (>330 nm) excess ac fac-Re(bpy)(CO) 3 (CF 3 SO 3 ) ac = -PPh 2 -C  C-PPh 2 -

9. 9 Synthesis of Oligomers with 5 and 7 Re(I) Units (i)h (>330 nm) in CH 2 Cl 2 for 1 h; (ii) [Re2ac(η 1 -ac) 1 ] 2+ in CH 2 Cl 2 at room temperature for 1 day, then at 40 °C for 1 day. Yield = 32%

10. 10 Synthesis [Re5ac] 5+ in higher yield Yield = 66%

11. 11 Synthesis of Linear-Shaped Re(I) Polymers (i) h (>330 nm) in MeCN for 1 h; (ii) excess ac in acetone/THF (1:1) at room temperature for 1 day, then at 40 °C for 1 day; (iii) in acetone/THF (1:1) at room temperature for 1 day, then at 40 °C for 2 days.

12. 12 Separation Using Size Exclusion Chromatography Figure S3. Chromatograms of analytical SEC. Reaction mixture (a), with isolation of [Re5ac] 5+, [Re10ac] 10+, [Re15ac] 15+, and [Re20ac] 20+. The eluent was a 1:1 (v/v) mixture of methanol and acetonitrile containing 0.3 M CH 3 CO 2 NH 4, and the flow rate was 5.0 ml min -1. The detection wavelength was 360 nm.

13. 13 ESI FTMS spectrum of [Re8ac] 8+ (PF 6 - ) 8. Figure 1. ESI FTMS spectrum of [Re8ac] 8+ (PF 6 - ) 8. The eluent was MeCN. ESI FTMS = electrospray ionization Fourier transform mass spectrometry Figure 2. ESI FTMS spectrum of the scale-extended segment for the seven charged [M + (PF 6 - )] 7+ (a) and calculated isotope distribution patterns(b).

14. 14 Aromatic regions in 1 H NMR spectra

15. 15 Aromatic regions in 1 H NMR spectra Hi6Hi6 Hi3Hi3 Hi4Hi4 H ii 5 H ii 5 +H iii 5

16. 16 Identify the Longest Isolated Polymer Made from [Re5ac] 5+ by 1 H NMR Figure 4. Relationship between the number of Re(I) units in the oligomers and polymers and ratios of the integrated areas of their 1 H NMR signals,A(H 5 i + H 5 ii )/A(H 6 iii ) (n = 3, 4, 6), measured in acetone-d3 at room temperature. See the structure as shown in Figure 3 for numbering of the protons. The red circle is the longest isolated polymer made from [Re5ac] 5+. the number of Re(I) units is 20.4  2.0

17. 17 (edge Re-CO) (interior Re-CO) IR spectra [Re2ac] 2+ Figure 5. IR spectra of [Re2ac] 2+ (dotted line), [Re4ac] 4+ (blue line), [Re6ac] 6+ (red line), and [Re8ac] 8+ (solid black line) measured in MeCN. They are standardized by the absorbance at 2048 cm -1. [Re6ac] 6+ [Re4ac] 4+ [Re8ac] 8+

18. 18 Identify the Longest Isolated Polymer Made from [Re5ac] 5+ by Ratio of (CO) Figure 6. Relationship between the ratios of the ν(CO) peak areas due to edge units (2048 cm -1 ) and interior units (1885 cm -1 ) of [Re2ac] 2+ to [Re16ac] 16+ (black dots), and the number of Re(I) units. The red circle is the polymer for the longest isolated polymer made from [Re5ac] 5+. the number of Re(I) units is 20.1  0.4

19. 19 Identify the Longest Isolated Polymer Made from [Re5ac] 5+ by Size Exclusion Chromatography. Figure 7. The logarithm of the molecular weight plotted against the distribution coefficient (K SEC ) of the Re(I) oligomers and polymers. The red circle shows the longest isolated polymer made from [Re5ac] 5+. the number of Re(I) units is 20.6  3.7

20. 20 ORTEP diagram of [Re2ac] 2+ (PF 6 - ) 2 Bond Angles Bond Lengths “Trans” - type π-π interaction Inversion center

21. 21 Packing diagram of [Re2ac] 2+ (PF 6 - ) 2 π-π interaction Figure S4. Packing diagram of [Re2ac] 2+ (PF 6 - ) 2, PF 6 - and hydrogen atoms omitted for clarity.

22. 22 ORTEP diagram of [Re3ac] 3+ (PF 6 - ) 3 U-shaped Bond Angles Bond Lengths Mirror plane

23. 23 Bond Angles Bond Lengths ORTEP diagram of [Re3et] 3+ (PF 6 - ) 3 U-shaped et = -PPh 2 -(CH 2 ) 2 -PPh 2 -

24. 24 ORTEP diagram of [Re4et] 4+ (PF 6 - ) 4 Circle-like structure

25. 25 UV-vis absorption spectra Figure 9. UV-vis absorption spectra of MeCN solutions containing [Re2ac] 2+ to [Re20ac] 20+ MLCT     

26. 26 Subtracted spectra UV-vis absorption spectrum Figure 10. Subtracted spectra UV-vis absorption spectrum of [Re2et] 2+ from those of [Re3et] 3+ - [Re7et] 7+, divided by the number of the biscarbonyl complex units; the red line is the UV-vis absorption spectrum of fac-[Re(bpy)(CO) 2 (PPh 2 Pr) 2 ] + in MeCN. Figure 9. Subtracted spectra UV-vis absorption spectrum of [Re2ac] 2+ from those of [Re3ac] 3+ to [Re20ac] 20+, divided by the number of biscarbonyl complex units.

27. 27 Emission spectra Figure 11. Emission spectra from degassed MeCN solutions containing [Re2ac] 2+ to [Re20ac] 20+ standardized by the absorbance at the excitation wavelength 350 nm. Red shift

28. 28 Emission decay curves of [Re8ac] 8+ Emission decay curves obtained at excitation wavelength of 365 nm. (a) Monitor : 500 nm (b) Monitor : 650 nm Main: 10 ns Minor: 100 ns, 734 ns Main: 113 ns, 750 ns Minor: 10 ns I em (t)= A 1 e t⁄τ1 + A 2 e t⁄τ2 +A 3 e t⁄τ3

29. 29 Time resolved emission spectra of [Re8ac] 8+ Figure 13. Time resolved emission spectra of [Re8ac] 8+. Black, red, and blue lines are emission spectra with lifetime of 10, 100, and 750 ns,respectively.  = 10 ns is emission from the 3 MLCT excited- state of the edge Re(I) units.

30. 30 Photophysical Properties Table 3. Photophysical Properties of [Re2ac] 2+ to [Re20ac] 20+ in a Deoxygenated Acetonitrile Solution at 25 °C, and Energy Transfer Rates from the Edge Unit to the Interior Unit in [Re3ac] 3+ to [Re20ac] 20+ a All complexes were PF 6 - salts. The excitation wavelength was 350 nm. b Emission maximum. c Quantum yield of emission. d Lifetime. Numbers in parentheses are percentages of pre-exponential factors, K et  K r

31. 31 MeCN/toluene mixed solution effect  em Figure 14. Dependence of Φem on toluene content in an MeCN/toluene mixed solution. cis,trans-[Re(bpy)(CO) 2 (PPh 3 ) 2]+  em  K r

32. 32 Conclusions We applied photochemical ligand substitution reactions of Re(I) diimine complexes with a phosphorus ligand, to find systematic synthetic routes for linear-shaped rhenium(I) oligomers and polymers bridged with bidentate phosphorus ligands. For oligomers and polymers with  3 Re(I) units, energy transfer from the edge unit to the interior unit occurs with a rate constant of (0.9 × 10 8 )-(2.5 × 10 8 ) s -1. Crystal structures were obtained of some trimers and a tetramer, showing interligand π-π interaction between the diimine ligand and the phenyl groups on the phosphorus ligand. Both emission and analytical SEC data indicate that the Re(I) polymers aggregate intramolecularly in an MeCN solution.

33. 33 Photochemical Ligand Substitution Reaction Ishitani, O.; Turner, J. J. J. Am. Chem. Soc. 2002, 124, 11448–11455.

34. 34 Efficient Photocatalytic System for CO 2 Reduction Ishitani O. J. Am. Chem. Soc., 2008, 130, 2023-2031

35. 35 S2S2 S1S1 S0S0 T1T1

36. 36 k et = the rate constant of energy transfer from the excited edge Re(I) unit to the interior Re(I) unit k = the observed rate constant of decay from the 3 MLCT excited-state of the edge Re(I) units in [Re8ac] 8+ k` = k r of [Re2ac] 2+ + k nr of [Re2ac] 2+ k et = k – k` If k r and k nr from the 3 MLCT excited-state of the edge Re(I) units in [Re8ac] 8+ are same as those from [Re2ac] 2+

37. 37 Synthesis [Re5ac] 5+ in higher yield this method cannot be applied to synthesize pentanuclear complexes with other bi-dentate phosphorus ligands, such as et, Because ac = -PPh 2 -C  C-PPh 2 - is a rigid ligand

38. 38 Isolated Yields with Various Bidentate Ligands Table 1. Isolated Yields of Linear-Shaped Di-, Tri-, and Tetranuclear Complexes with Various Bidentate Phosphorus Ligands a Isolated as PF6 - salts. b 4,4′-Dimethy-2,2′-bipyridine. c 4,4′-Dimethoxy-2,2′-bipyridine.

39. 39 Size Exclusion Chromatography

40. 40 electrospray ionization mass spectrometry

41. 41 Time resolved measurements Pulsed excitation and high speed detection, used for measuring intensity decays or anisotropy decays

42. 42