Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2017 Electronic Supplementary Information for Dalton Transactions Supplementary Data Synthesis, spectroscopic, electrochemical and computational studies of rhenium(i) tricarbonyl complexes based on bidentate-coordinated 2,6- di(thiazol-2-yl)pyridine derivatives Tomasz Klemens a, Katarzyna Czerwińska a, Agata Szlapa-Kula b, Slawomir Kula b, Anna Świtlicka a, Sonia Kotowicz c, Mariola Siwy d, Katarzyna Bednarczyk c, Stanisław Krompiec b, Karolina Smolarek e, Sebastian Maćkowski e, Witold Danikiewicz f, Ewa Schab-Balcerzak c,d* and Barbara Machura a * a Department of Crystallography, Institute of Chemistry, University of Silesia, 9 th Szkolna St., 40-006 Katowice, Poland b Department of Inorganic, Organometallic Chemistry and Catalysis, Institute of Chemistry, University of Silesia, 9 th Szkolna St., 40-006 Katowice, Poland c Department of Polymer Chemistry, Institute of Chemistry, University of Silesia in Katowice, 9 th Szkolna St., 40-006 Katowice, Poland d Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 th M. Curie-Sklodowska St., 41-819 Zabrze, Poland e Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University, 5 th Grudziadzka St., 87-100 Torun, Poland f Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland. 1
Tables: Table S1. Crystal data and structure refinement details of the rhenium(i) complexes. Table S2. The selected experimental and calculated bond lengths [Å] and angles [ ] for the rhenium(i) complexes. Table S3. Short intra- and intermolecular contacts detected in the structures of complexes. rhenium(i) Table S4. The absorption maxima and molar extinction coefficient values for complexes 4, 5, 6, 8 and their terpyridine analogues. Table S5. The energies and characters of the selected spin-allowed electronic transitions for 1 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Table S6. The energies and characters of the selected spin-allowed electronic transitions for 2 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Table S7. The energies and characters of the selected spin-allowed electronic transitions for 3 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Table S8. The energies and characters of the selected spin-allowed electronic transitions for 4 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Table S9. The energies and characters of the selected spin-allowed electronic transitions for 5 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Table S10. The energies and characters of the selected spin-allowed electronic transitions for 6 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Table S11. The energies and characters of the selected spin-allowed electronic transitions for 7 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Table S12. The energies and characters of the selected spin-allowed electronic transitions for 8 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Table S13. The energies and characters of the selected spin-allowed electronic transitions for 9 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Table S14. The emission maxima for complexes 4, 5, 6, 8 and their terpyridine analogues. Figures: Figure S1. Representative IR spectra of complexes 2 and 5. Figure S2. Representative 1 H NMR (a) and 13 C NMR (b) spectra of complex 9. Figure S3. A view of the crystal packing showing intermolecular stacking interactions for tricarbonyl rhenium(i) complexes. Figure S4. Cyclic voltammograms of the rhenium(i) complexes. Figure S5. Absorption spectra of the rhenium(i) complexes in chloroform and acetonitrile solutions. 2
Figure S6. Experimental and theoretical absorption spectra of 1-9 complexes in acetonitrile solution. Figure S7. HOMO-5 to HOMO molecular orbitals of 1-9 complexes. Figure S8. LUMO to LUMO+5 molecular orbitals of 1-9 complexes. Figure S9. Isodensity surface electron spin density for the complexes 1 9 at their T 1 state geometry. Blue and green colours show regions of positive and negative spin density values, respectively. Figure S10. Isodensity surface plots of the HSOMO and LSOMO for the complexes 1 9 at their T 1 TDDFT state geometry. Blue and grey colours show regions of positive and negative spin density values, respectively. Figure S11. Luminescent properties of 1-9 complexes in solid state, low temperature glass matrix (EtOH:MeOH, 4:1 v/v), acetonitrile and chloroform solutions. Figure S12. PL spectra of [ReCl(CO) 3 (R n -dtpy)] complexes as film registered under various excitation wavelength ( ex ). 3
Table S1. Crystal data and structure refinement details of the rhenium(i) complexes. 3 4 5 7 8 9 Empirical formula C 19 H 10 ClN 4 O 3 S 2 Re C 18 H 9 ClN 3 O 3 S 3 Re C 22 H 11 ClN 3 O 3 S 4 Re C 20 H 11 ClN 3 O 4 S 2 Re C 19 H 12 ClN 4 O 3 S 2 Re C 28 H 20 ClN 4 O 4 ReS 2 Formula weight 628.08 633.11 715.23 643.09 630.10 762.25 Temperature [K] 298.0(2) 298.0(2) 298.0(2) 298.0(2) 298.0(2) 298.0(2) Wavelength [Å] 0.71073 0.71073 0.71073 0.71073 0.71073 0.71073 Crystal system monoclinic orthorhombic monoclinic monoclinic monoclinic monoclinic Space group P2 1 /c Pbca I2/a P2 1 /n P2 1 /n P2 1 /n Unit cell dimensions [Å, ] a = 11.2580(4) a = 11.6598(3) a = 16.4100(5) a = 11.1652(11) a = 10.3501(3) a = 13.6914(6) b = 11.3920(4) b = 16.1704(6) b = 10.5443(4) b = 15.9975(12) b = 11.0261(5) b = 14.0788(8) c = 15.8305(5) c = 20.9566(6) c = 28.2940(9) c = 12.8167(12) c = 18.3976(7) c = 15.8901(6) = 101.048(3) = 92.541(3) = 109.094(11) = 93.019(3) = 107.775(4) Volume [Å 3 ] 1992.65(12) 3951.2(2) 4891.0(3) 2163.3(4) 2096.64(14) 2916.7(3) Z 4 8 8 4 4 4 Density (calculated) 2.094 2.129 1.943 1.975 1.996 1.736 [Mg/m 3 ] Absorption coefficient [mm - 6.472 6.629 5.450 5.966 6.152 4.441 1 ] F(000) 1200 2416 2752 1232 1208 1488 Crystal size [mm] 0.09 x 0.09 x 0.04 0.07 x 0.06 x 0.03 0.11 x 0.06 x 0.03 0.20 x 0.15 x 0.04 0.18 x 0.07 x 0.03 0.25 x 0.16 x 0.05 range for data collection 3.41 to 25.05 3.49 to 25.05 3.64 to 25.05 3.36 to 25.05 3.43 to 25.05 3.44 to 25.05 [ ] Index ranges -13 h 13-13 k 12-16 l 18-13 h 10-19 k 12-24 l 23-19 h 19-12 k 10-28 l 33-12 h 13-19 k 16-15 l 14-12 h 10-13 k 11-21 l 21-13 h 16-16 k 16-18 l 16 Reflections collected 11078 12761 11272 11778 9529 14010 Independent reflections 3522 (R int = 3486 (R int = 0.0395) 4323 (R int = 0.0243) 3823 (R int = 0.0560) 3686 (R int = 0.0440) 5159 (R int = 0.0606) 0.0339) Completeness to 2 =50º 99.8 99.8 99.7 99.7 99.8 99.7 [%] Max. and min. transmission 1.000 and 0.403 1.000 and 0.403 1.000 and 0.476 1.000 and 0.101 1.000 and 0.286 1.000 and 0.375 Data / restraints / 3522 / 0 / 271 3486/ 0 / 262 4323 / 0 / 339 3823/ 0 / 280 3686 / 0 / 272 5159 / 0 / 362 parameters Goodness-of-fit on F 2 1.194 1.027 1.044 1.030 0.999 1.041 Final R indices [I>2 (I)] R 1 = 0.0268 wr 2 = 0.0704 R 1 = 0.0282 wr 2 = 0.0577 R 1 = 0.0220 wr 2 = 0.0482 R 1 = 0.0408 wr 2 = 0.0982 R 1 = 0.0358 wr 2 = 0.0763 R 1 = 0.471 wr 2 = 0.1139 R indices (all data) R 1 = 0.0340 wr 2 = 0.0726 R 1 = 0.0449 wr 2 = 0.0621 R 1 = 0.0278 wr 2 = 0.0506 R 1 = 0.0538 wr 2 = 0.1050 R 1 = 0.0465 wr 2 = 0.0814 R 1 = 0. 0674 wr 2 = 0.1257 4
Largest diff. peak and 0.759 and -0.590 0.720 and -0.624 0.360 and -0.699 1.444 and -1.604 1.510 and -1.331 1.353 and -0.581 hole[eå -3 ] CCDC numbers 1552300 1552301 1552302 1552303 1552304 1552305 5
Table S2. The selected experimental and calculated bond lengths [Å] and angles [ ] for the rhenium(i) complexes. 3 4 5 experimental calculated experimental calculated experimental calculated Bond lengths Re(1) C(1) 1.916(8) 1.921 1.940(6) 1.921 1.922(4) 1.920 Re(1) C(2) 1.907(6) 1.902 1.885(6) 1.902 1.902(4) 1.902 Re(1) C(3) 1.908(7) 1.904 1.912(6) 1.904 1.891(4) 1.904 Re(1) N(1) 2.161(5) 2.169 2.164(4) 2.169 2.149(3) 2.169 Re(1) N(2) 2.239(4) 2.262 2.226(4) 2.261 2.241(2) 2.260 Re(1) Cl(1) 2.4817(15) 2.499 2.4851(13) 2.500 2.4836(8) 2.500 C(1) O(1) 1.162(8) 1.149 1.135(6) 1.150 1.146(4) 1.150 C(2) O(2) 1.145(7) 1.152 1.156(6) 1.152 1.145(4) 1.153 C(3) O(3) 1.134(7) 1.154 1.145(6) 1.154 1.158(4) 1.154 Bond angles C(2) Re(1) C(1) 89.0(2) 86.81 86.9(2) 86.79 90.15(15) 86.79 C(3) Re(1) C(1) 89.0(2) 89.59 88.4(2) 89.58 88.68(15) 89.57 C(3) Re(1) C(2) 87.7(2) 88.70 89.6(2) 88.72 88.39(14) 88.71 C(1) Re(1) N(1) 173.49(19) 174.08 174.84(18) 174.24 176.05(12) 174.28 C(2) Re(1) N(1) 95.2(2) 96.44 96.20(19) 96.41 93.08(12) 96.44 C(3) Re(1) N(1) 96.1(2) 95.41 95.77(18) 95.26 93.69(13) 95.21 C(1) Re(1) N(2) 101.51(18) 102.15 102.50(18) 102.26 101.72(12) 102.22 C(2) Re(1) N(2) 169.0(2) 170.08 169.22(18) 170.05 166.02(12) 170.09 C(3) Re(1) N(2) 95.66(19) 95.54 96.0(2) 95.42 99.14(12) 95.41 N(1) Re(1) N(2) 74.08(15) 74.27 74.09(14) 74.23 74.79(9) 74.24 C(1) Re(1) Cl(1) 90.41(17) 90.99 91.71(16) 91.08 93.35(11) 91.12 C(2) Re(1) Cl(1) 94.40(19) 93.54 92.46(16) 93.53 92.85(11) 93.51 C(3) Re(1) Cl(1) 177.81(17) 177.71 177.98(18) 177.68 177.62(10) 177.71 N(1) Re(1) Cl(1) 84.30(12) 83.89 84.02(11) 83.96 84.22(8) 83.98 N(2) Re(1) Cl(1) 82.39(11) 82.17 82.03(10) 82.27 79.24(6) 82.31 Bond lengths 7 8 9 experimental calculated experimental calculated experimental calculated 6
Re(1) C(1) 1.900(7) 1.920 1.916(6) 1.922 1.925(9) 1.922 Re(1) C(2) 1.927(9) 1.902 1.924(8) 1.904 1.903(9) 1.904 Re(1) C(3) 1.909(9) 1.903 1.902(7) 1.903 1.935(9) 1.903 Re(1) N(1) 2.166(5) 2.170 2.167(4) 2.169 2.150(6) 2.169 Re(1) N(2) 2.234(6) 2.259 2.230(5) 2.261 2.228(5) 2.262 Re(1) Cl(1) 2.485(2) 2.500 2.4762(16) 2.497 2.4794(19) 2.496 C(1) O(1) 1.152(8) 1.150 1.158(7) 1.150 1.140(9) 1.149 C(2) O(2) 1.105(10) 1.153 1.124(9) 1.152 1.141(10) 1.151 C(3) O(3) 1.127(9) 1.154 1.133(8) 1.155 1.111(9) 1.154 Bond angles C(2) Re(1) C(1) 88.1(3) 86.78 87.8(3) 86.64 87.4(4) 86.66 C(3) Re(1) C(1) 88.9(3) 89.53 89.9(3) 90.30 91.9(3) 90.44 C(3) Re(1) C(2) 88.9(3) 88.69 90.2(3) 88.28 87.6(4) 88.30 C(1) Re(1) N(1) 175.6(3) 174.34 173.0(2) 174.43 172.6(3) 174.26 C(2) Re(1) N(1) 95.1(3) 96.42 97.6(2) 96.69 95.9(3) 96.73 C(3) Re(1) N(1) 94.3(3) 95.19 94.3(2) 94.25 94.8(3) 94.28 C(1) Re(1) N(2) 101.7(3) 102.21 99.4(2) 102.03 101.7(3) 101.96 C(2) Re(1) N(2) 169.2(3) 170.09 168.9(2) 169.91 169.8(3) 169.94 C(3) Re(1) N(2) 95.7(3) 95.46 98.2(2) 96.73 96.7(3) 96.73 N(1) Re(1) N(2) 74.9(2) 74.28 74.59(18) 74.27 74.57(19) 74.27 C(1) Re(1) Cl(1) 90.5(2) 91.18 92.70(19) 91.19 89.5(2) 90.99 C(2) Re(1) Cl(1) 94.7(3) 93.44 91.9(2) 92.93 93.9(3) 92.78 C(3) Re(1) Cl(1) 176.3(2) 177.78 176.73(19) 178.13 178.0(2) 178.26 N(1) Re(1) Cl(1) 86.15(15) 83.99 82.89(13) 84.19 83.66(14) 84.23 N(2) Re(1) Cl(1) 80.85(14) 82.34 79.39(11) 81.86 81.54(14) 82.00 7
Table S3. Short intra- and intermolecular contacts detected in the structures of rhenium(i) complexes. D H A D H H A D A [Å] D H A [ ] 3 C(4) H(4) O(2)#1 0.93 2.55 3.301(8) 138.5 C(10) H(10) N(4) 0.93 2.43 2.765(7) 101.3 C(14) H(14) N(4)#2 0.93 2.59 3.508(8) 167.6 C(16) H(16) Cl(1)#3 0.93 2.69 3.620(6) 173.2 4 C(8) H(8) Cl(1)#4 0.93 2.81 3.736(5) 172.7 C(10) H(10) S(3) 0.93 2.67 3.085(5) 108.1 C(13) H(13) S(3)#5 0.93 2.87 3.725(6) 153.6 C(16) H(16) Cl(1)#4 0.93 2.69 3.620(5) 175.6 5 C(4) H(4) N(3)#6 0.93 2.62 3.272(5) 127.7 C(8) H(8) S(1) 0.93 2.87 3.229(3) 104.3 C(10) H(10) S(3) 0.93 2.73 3.128(3) 106.5 7 C(5) H(5) Cl(1)#7 0.93 2.82 3.481(8) 129.3 C(15) H(15) O(4) 0.93 2.55 2.873(10) 100.4 C(15) H(15) Cl(1)#8 0.93 2.67 3.565(7) 162.8 C(16) H(16) O(1)#9 0.93 2.49 3.268(9) 141.0 8 C(8) H(8) S(1) 0.93 2.86 3.222(6) 104.0 C(13) H(13) S(1)#10 0.93 2.87 3.456(7) 122.0 C(14) H(14) N(3)#11 0.93 2.61 3.522(8) 168.0 C(17) H(17) O(3)#12 0.93 2.60 3.449(9) 153.0 C(19) H(19B) Cl(1)#13 0.96 2.72 3.555(7) 145.0 C(19) H(19C) Cl(1)#14 0.96 2.68 3.634(8) 171.0 9 O(4) H(4O) S(1) 0.84 2.50 3.323(17) 166.9 O(4) H(4P) N(3)#15 0.91 2.35 3.235(17) 164.6 C(8) H(8) S(1) 0.93 2.85 3.231(7) 105.8 C(14) H(14) Cl(1)#7 0.93 2.82 3.603(13) 142.2 C(27) H(27B) O(1)#16 0.97 2.56 3.281(11) 131.8 Symmetry codes: #1: -x,1-y,-z, #2: 1-x,2-y,1-z, #3: 1-x,-1/2+y,1/2-z, #4: -1/2+x,1/2-y,2-z; #5: 1-x,1-y,2-z, #6: -1/2+x,1-y,z; #7: 1/2-x,-1/2+y,1/2- z; #8: 1-x,-y,1-z; #9: 1/2+x,1/2-y,1/2+z, #10: -1/2+x,1/2-y,-1/2+z, #11: 5/2-x,1/2+y,1/2-z; #12: 1/2+x,1/2-y,-1/2+z; #13: 1+x,y,z, #14: 3-x,-y,1-z; #15: 1-x,2-y,-z; #16: x,y,-1+z; 8
Table S4. The absorption maxima and molar extinction coefficient values for complexes 4, 5, 6, 8 and their terpyridine analogues. Complex Ligand (medium) /nm (ε/ dm 3 mol-1 cm -1 ) terpy MeCN 381.0 (4400), 321.2 (13200), 258.3 (12700), 193.7 (14900) 4 dtpy MeCN 382.5 (5600), 330.7 (18720), 298.3 (13480), 263.1 (10880) terpy CHCl 3 407.4 (23800), 333.1 (91300), 292.2 (97100), 260.0 (85700) dtpy CHCl 3 433.1 (5000), 350.2 (22300), 321.4 (16200), 281.4 (13000) terpy MeCN 406.3 (19800), 313.7 (14900), 257.4 (16300), 219.7 (23700) 5 dtpy MeCN 419.5 (30320), 329.9 (22000), 264.0 (20080) terpy CHCl 3 427.9 (74900), 326.6 (57600), 260.2 (69700) dtpy CHCl 3 431.3 (24480), 335.9 (19520), 296.0 (19480) terpy MeCN 383.7 (7800), 315.1 (45300), 279.3 (57600), 244.4 (60900) 6 dtpy MeCN 395.8 (5000), 327.7 (16160), 247.0 (12000) terpy CHCl 3 402.7 (24700), 334.3 (96000), 302.4 (88500), 260.9 (76200) dtpy CHCl 3 418.9 (6440), 336.3 (30520), 305.9 (25160), 261.6 (15920) terpy MeCN 383.8 (22200), 351.9 (21100), 301.3 (31400), 253.3 (28600), 221.9 (37800) 8 dtpy MeCN 399.3 (10960), 356.0 (14400), 316.2 (21120), 250.9 (14640) terpy CHCl 3 408.2 (34600), 367.2 (42600), 314.1 (71500), 260.8 (77700) dtpy CHCl 3 411.9 (11640), 363.1 (15640), 324.4 (21160), 257.9 (16920) 9
Table S5. The energies and characters of the selected spin-allowed electronic transitions for 1 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (ε; M -1 cm -1 ) 408.4 (1560) 335.8 (3780) 291.4 (4800) Major contribution (%) Calculated transitions Character E [ev] λ [nm] Oscillator strength H L (98%) * 2.60 476.16 0.0026 H-1 L (96%) 2.84 436.02 0.0985 H-2 L (97%) MLCT/LC 3.10 399.71 0.0088 H L+1 (98%) 3.31 374.54 0.0179 H-1 L+1 (96%) 3.46 358.21 0.0067 H-3 L (91%) LC/ILCT 3.66 338.52 0.2511 H-2 L+1 (96%) MLCT/LC/ILCT 3.82 324.80 0.0036 H-4 L (88%) LC 4.09 303.01 0.0748 H-8 L (57%), H-3 L+1 (19%), H-7 L (14%) H-3 L+1 (44%), H-8 L (22%), H-7 L (13%), H-6 L (12%) LLCT/LC/MLCT LC/ILCT LLCT/LC/ILCT/MLCT LC/ILCT LLCT/LC/MLCT LLCT/LC/ILCT/MLCT ILCT 4.34 285.43 0.1270 4.36 284.36 0.2332 H-4 L+1 (79%) LC/ILCT 4.62 268.19 0.1589 H-2 L+2 (48%), MLCT/ILCT/LC 4.76 260.40 0.1484 266.2 (5540) H-10 L (19%), LC/ILCT/LLCT H-9 L (14%) LC/ILCT/LLCT * mixed MLCT/LLCT state Table S6. The energies and characters of the selected spin-allowed electronic transitions for 2 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (ε; M -1 cm -1 ) Major contribution (%) Calculated transitions Character E [ev] λ [nm] Oscillator strength H L (98%) 2.65 468.27 0.0027 387.1 (4800) H-1 L (97%) 2.88 430.53 0.1046 H-2 L (97%) MLCT/LC 3.14 394.35 0.0088 H L+1 (98%) 3.35 369.94 0.0166 H-1 L+1 (96%) 3.50 354.14 0.0105 326.2 (24240) H-3 L (90%) LC 3.71 334.24 0.2676 H-2 L+1 (96%) MLCT/LC/ILCT 3.86 321.44 0.0052 H-5 L (89%) LC/ILCT 4.13 299.95 0.2079 302.5 (36560) H-3 L+1 (83%) LC/ILCT 4.35 285.08 0.2726 H-4 L+1 (79%) LC/ILCT/LLCT 4.61 268.89 0.2246 H-3 L+2 (82%) LC/ILCT 5.25 235.95 0.0628 H-10 L+1(66%) LC/ILCT 5.55 223.31 0.0587 220.4 (31120) H-5 L+2 (23%), H-11 L+1 (15%), H-13 L (13%) LC/ILCT ILCT/LLCT/LC LC 5.74 215.82 0.0554 Table S7. The energies and characters of the selected spin-allowed electronic transitions for 3 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Experimental absorption Calculated transitions 10
; nm (ε; M -1 cm -1 ) 394.3 (3000) 331.4 (8960) 290.7 (15000) 266.2 (12960) (%) strength H L (98%) 2.63 472.26 0.0025 H-1 L (97%) 2.86 433.87 0.1126 H-2 L (96%) MLCT/LC 3.12 397.54 0.0100 H L+1 (98%) 3.34 370.83 0.0207 H-1 L+1 (94%) 3.48 355.80 0.0060 H-3 L (88%) LC 3.65 339.84 0.2545 H-2 L+1 (96%) MLCT/LC 3.84 322.48 0.0055 H-4 L (50%), ILCT/LC/LLCT 4.07 304.62 0.3048 H-5 L (40%) LC H-3 L+1 (71%) LC/ILCT 4.31 287.42 0.2168 H-4 L+1 (54%), H-5 L+1 (12%), H-1 L+4 (10%) H-2 L+2 (68%), H-1 L+5 (10%) ILCT/LC/LLCT LC MLCT/d-d/LLCT MLCT/LC/ILCT d-d/mlct/llct 4.58 270.72 0.1626 4.79 258.65 0.604 Table S8. The energies and characters of the selected spin-allowed electronic transitions for 4 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (ε; M -1 cm -1 ) Major contribution (%) Calculated transitions Character E [ev] λ [nm] Oscillator strength H L (98%) 2.67 464.03 0.0033 382.5 (5600) H-1 L (97%) 2.88 430.78 0.1545 H-2 L (96%) MLCT 3.16 391.81 0.0103 H L+1 (97%) 3.36 368.78 0.0263 H-1 L+1 (94%) 3.48 356.36 0.0197 330.7 (18720) H-3 L (85%) ILCT/LC 3.60 344.60 0.3607 H-4 L (76%) LC 3.71 334.13 0.1906 298.3 (13480) H-3 L+1 (84%) ILCT/LC 4.07 304.48 0.3200 H-6 L (86%) ILCT 4.25 291.70 0.0769 263.1 (10880) H-5 L+1 (83%) LC 4.68 265.10 0.1150 Table S9. The energies and characters of the selected spin-allowed electronic transitions for 5 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (ε; M -1 cm -1 ) Major contribution (%) Calculated transitions Character E [ev] λ [nm] Oscillator strength H-1 L (63%), 2.64 469.47 0.1176 H L (30%) ILCT/LC H L (58%), ILCT/LC 2.73 454.40 0.6561 419.5 (30320) H-1 L (34%) H-2 L (84%) 2.99 414.38 0.1712 H-3 L (94%) MLCT/LC/ILCT 3.15 393.95 0.0100 H L+1 (89%) ILCT/LC 3.23 383.42 0.1887 H-1 L+1 (90%) 3.35 370.46 0.0044 H-2 L+1 (94%) 3.54 349.70 0.0341 329.9 (22000) H-4 L (90%) LC/ILCT 3.67 337.48 0.2401 H L+2 (91%) ILCT/LC 3.96 313.10 0.1043 264.0 (20080) H-6 L+1 (31%), LC/ILCT 4.62 268.09 0.1254 11
H-3 L+2 (25%), H L+3 (15%) H-4 L+2 (51%), H-9 L+1 (12%), H-3 L+4 (10%) MLCT/ILCT/LC ILCT/LC LC/ILCT LLCT/LC/ILCT/MLCT d-d/mlct/lc 5.02 246.96 0.1227 Table S10. The energies and characters of the selected spin-allowed electronic transitions for 6 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (ε; M -1 cm -1 ) 395.8 (5000) 327.7 (16160) 247.0 (12000) Major contribution (%) Calculated transitions Character E [ev] λ [nm] Oscillator strength H L (98%) 2.69 460.70 0.0036 H-1 L (96%) 2.89 428.53 0.1630 H-2 L (89%) MLCT/LC 3.18 389.53 0.0114 H L+1 (97%) 3.37 367.63 0.0230 H-3 L (77%) ILCT/LC/MLCT 3.54 349.94 0.3546 H-4 L (78%) LC 3.74 331.56 0.2208 H-3 L+1 (86%) ILCT/LC/MLCT 4.00 310.25 0.3508 H-5 L+1 (84%) LC 4.69 264.05 0.0996 H-2 L+2 (49%), MLCT/LC 4.86 255.09 0.0746 H-2 L+4 (24%) d-d/lc H-4 L+2 (86%) LC 5.32 233.21 0.0732 Table S11. The energies and characters of the selected spin-allowed electronic transitions for 7 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (ε; M -1 cm -1 ) 398.8 (22320) 366.9 (27360) 331.4 (23920) 260.3 (19200) Major contribution (%) Calculated transitions Character E [ev] λ [nm] Oscillator strength H-1 L (66%), 2.61 475.91 0.0295 H L (29%) ILCT/MLCT H L (53%), ILCT/MLCT 2.75 451.18 0.4880 H-1 L (32%), H-2 L (13%) /ILCT H-2 L (75%), H L (15%) /ILCT ILCT/MLCT 3.04 408.40 0.2568 H-3 L (90%) MLCT/LC 3.11 398.71 0.0312 H L+1 (69%), ILCT/MLCT 3.40 364.72 0.2176 H-1 L+1 (23%) H-1 L+1 (71%), 3.47 357.18 0.0498 H L+1 (16%) ILCT/MLCT H-4 L (76%), LC/ILCT 3.63 341.26 0.2251 H-2 L+1 (15%) /ILCT H-2 L+1 (78%), /ILCT 3.71 333.85 0.2594 H-4 L (10%) LC/ILCT H-3 L+2 (77%) MLCT/LC/ILCT 4.69 264.60 0.0479 H-5 L+1 (75%) LC/ILCT 4.73 262.18 0.1296 Table S12. The energies and characters of the selected spin-allowed electronic transitions for 8 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Experimental absorption Calculated transitions 12
; nm (ε; M -1 cm -1 ) 399.3 (10960) 356.0 (14400) 316.2 (21120) 250.9 (14640) Major contribution Oscillator Character E [ev] λ [nm] (%) strength H L (50%), /ILCT 2.79 445.05 0.0176 H-1 L (46%) H-1 L (53%), 2.93 423.70 0.2238 H L (38%) /ILCT H-2 L (80%) /ILCT/LC 3.22 385.28 0.0521 H-3 L (90%) MLCT/LC 3.28 377.69 0.0104 H L+1 (77%), /ILCT 3.53 351.02 0.1765 H-1 L+1 (18%) H-1 L+1 (80%), 3.59 345.01 0.0650 H L+1 (15%) /ILCT H-4 L (70%), LC 3.80 326.56 0.2199 H-2 L+1 (22%) /ILCT/LC H-2 L+1 (74%), /ILCT/LC 3.86 321.02 0.2564 H-4 L (20%) LC H-7 L (54%), /LC 4.51 274.80 0.1228 H-4 L+1 (37%) LC H-8 L (59%), /LC 4.62 268.37 0.0608 H-4 L+1 (7%) LC H L+2 (41%), /ILCT 4.64 267.33 0.0643 H L+4 (21%) d-d/ilct/lc H-6 L+1 (75%) LC/ 4.85 255.67 0.0665 H-3 L+3 (28%), d-d/lc 4.87 254.57 0.0684 H-1 L+4 (12%), d-d/llct/lc H L+3 (8%), d-d/ilct/lc H-2 L+2 (7%), /ILCT/LC H-2 L+4 (7%) d-d/llct/ilct/lc Table S13. The energies and characters of the selected spin-allowed electronic transitions for 9 calculated with the TDDFT/PBE1PBE method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (ε; M -1 cm -1 ) 410.8 (15720) 318.4 (22480) Major contribution (%) H-7 L (29%) 290.4 (21600) H-2 L+2 (26%), H L+3 (12%), H-5 L+1 (9%) Calculated transitions Character E [ev] λ [nm] Oscillator strength H-1 L (54%), 2.78 445.29 0.1040 H L (40%) ILCT H L (49%), ILCT 2.86 433.72 0.2617 H-1 L (44%) H-2 L (53%), /ILCT 3.06 404.64 0.0103 H-3 L (35%) /ILCT H-4 L (95%) MLCT/LC/ILCT 3.28 377.43 0.0101 H-3 L (53%), H-2 L (33%) /ILCT /ILCT 3.32 373.49 0.0067 H L+1 (83%) ILCT 3.41 363.45 0.3384 H-5 L (82%) LC/ILCT/MLCT 3.80 326.29 0.2804 H L+2 (47%), LC/ILCT 4.01 309.48 0.0739 H-4 L+1 (17%), MLCT/LC/ILCT H-3 L+1 (16%), /ILCT H-2 L+1 (12%) /ILCT H-6 L (45%), ILCT/LC 4.26 290.97 0.1620 LC/ILCT/ /LC/ILCT ILCT/LC LC/ILCT/MLCT 4.41 281.38 0.1099 13
262.3 (22040) 245.1 (27720) 236.1 (31400) 229.3 (31200) H-5 L+1 (66%) LC/ILCT/MLCT 4.43 280.00 0.3530 H-2 L+2 (21%), /LC/ILCT 4.60 269.70 0.2884 H L+3 (11%), ILCT/LC H-9 L (7%), LLCT/LC/ILCT H-3 L+2 (7%), /LC/ILCT H-3 L+5 (7%), d-d/ilct/mlct H-1 L+5 (7%) d-d/ H L+5 (32%), H L+4 (15%), H L+6 (14%) H L+7 (36%), H-1 L+7 (12%), H-1 L+9 (6%) H-1 L+7 (22%), H L+7 (14%), H-1 L+6 (11%), H L+9 (9%) ILCT/LMCT ILCT/LMCT ILCT/LC ILCT/LC ILCT/LC ILCT/LC 5.04 246.03 0.1313 5.34 232.28 0.0789 5.36 231.13 0.1058 Table S14. The emission maxima for complexes 4, 5, 6, 8 and their terpyridine analogues. Complex Medium Ligand [nm] terpy 664 MeCN dtpy 744 4 terpy 675 CHCl 3 dtpy 734 5 6 8 MeCN terpy 516 dtpy 682, 739 CHCl 3 terpy 484 dtpy 691, 735 MeCN terpy 663 dtpy 720 CHCl 3 terpy 675 dtpy 731 MeCN terpy 646 dtpy 716 CHCl 3 terpy 656 dtpy 717 14
2 5 Figure S1. Representative IR spectra of complexes 2 and 5. 15
(a) Figure S2. Representative 1 H NMR (a) and 13 C NMR (b) spectra of complex 9. (b) 16
3 4 17
5 7 18
9 Figure S3. A view of the crystal packing showing intermolecular stacking interactions for tricarbonyl rhenium(i) complexes. 19
Figure S4. Cyclic voltammograms of the rhenium(i) complexes. (1) (2) (3) 20
(4) (5) (6) 21
(7) (8) (9) 22
Figure S5. Absorption spectra of the rhenium(i) complexes in chloroform and acetonitrile solutions. Complex ACN CHCl 3 1 2 3 4 23
5 6 7 8 24
9 25
Figure S6. Experimental and theoretical absorption spectra of 1-9 complexes in acetonitrile solution. 1 2 3 4 5 6 7 8 9 26
27