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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 Klemensa, Katarzyna Czerwińskaa, Agata Szlapa-Kulab, Slawomir Kulab, Anna Świtlickaa, Sonia Kotowiczc, Mariola Siwyd, Katarzyna Bednarczykc, Stanisław Krompiecb, Karolina Smolareke, Sebastian

Maćkowskie, Witold Danikiewiczf, Ewa Schab-Balcerzakc,d* and Barbara Machuraa*

aDepartment of Crystallography, Institute of Chemistry, University of Silesia, 9th Szkolna St., 40-006 Katowice, PolandbDepartment of Inorganic, Organometallic Chemistry and Catalysis, Institute of Chemistry, University of Silesia, 9th Szkolna

St., 40-006 Katowice, PolandcDepartment of Polymer Chemistry, Institute of Chemistry, University of Silesia in Katowice, 9th Szkolna St., 40-006 Katowice,

Poland

dCentre of Polymer and Carbon Materials, Polish Academy of Sciences, 34th M. Curie-Sklodowska St., 41-819 Zabrze, PolandeInstitute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University, 5th Grudziadzka St., 87-

100 Torun, PolandfInstitute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017

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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 rhenium(I) complexes.

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 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 1H NMR (a) and 13C 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.

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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 T1 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 T1 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(Rn-dtpy)] complexes as film registered under various excitation wavelength (ex).

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Table S1. Crystal data and structure refinement details of the rhenium(I) complexes.

3 4 5 7 8 9Empirical formula C19H10ClN4O3S2Re C18H9ClN3O3S3Re C22H11ClN3O3S4Re C20H11ClN3O4S2Re C19H12ClN4O3S2Re C28H20ClN4O4ReS2

Formula weight 628.08 633.11 715.23 643.09 630.10 762.25Temperature [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 0.71073Crystal system monoclinic orthorhombic monoclinic monoclinic monoclinic monoclinicSpace group P21/c Pbca I2/a P21/n P21/n P21/nUnit 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 4Density (calculated) [Mg/m3]

2.094 2.129 1.943 1.975 1.996 1.736

Absorption coefficient [mm-

1]6.472 6.629 5.450 5.966 6.152 4.441

F(000) 1200 2416 2752 1232 1208 1488Crystal 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 14010Independent reflections 3522 (Rint =

0.0339)3486 (Rint = 0.0395) 4323 (Rint = 0.0243) 3823 (Rint = 0.0560) 3686 (Rint = 0.0440) 5159 (Rint = 0.0606)

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 0.375Data / restraints / parameters

3522 / 0 / 271 3486/ 0 / 262 4323 / 0 / 339 3823/ 0 / 280 3686 / 0 / 272 5159 / 0 / 362

Goodness-of-fit on F2 1.194 1.027 1.044 1.030 0.999 1.041Final R indices [I>2(I)] R1 = 0.0268

wR2 = 0.0704R1 = 0.0282wR2 = 0.0577

R1 = 0.0220wR2 = 0.0482

R1 = 0.0408wR2 = 0.0982

R1 = 0.0358wR2 = 0.0763

R1 = 0.471wR2 = 0.1139

R indices (all data) R1 = 0.0340wR2 = 0.0726

R1 = 0.0449wR2 = 0.0621

R1 = 0.0278wR2 = 0.0506

R1 = 0.0538wR2 = 0.1050

R1 = 0.0465wR2 = 0.0814

R1 = 0. 0674wR2 = 0.1257

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Largest diff. peak and hole[eÅ-3]

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

CCDC numbers 1552300 1552301 1552302 1552303 1552304 1552305

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Table S2. The selected experimental and calculated bond lengths [Å] and angles [] for the rhenium(I) complexes.

3 4 5experimental calculated experimental calculated experimental calculated

Bond lengthsRe(1)–C(1) 1.916(8) 1.921 1.940(6) 1.921 1.922(4) 1.920Re(1)–C(2) 1.907(6) 1.902 1.885(6) 1.902 1.902(4) 1.902Re(1)–C(3) 1.908(7) 1.904 1.912(6) 1.904 1.891(4) 1.904Re(1)–N(1) 2.161(5) 2.169 2.164(4) 2.169 2.149(3) 2.169Re(1)–N(2) 2.239(4) 2.262 2.226(4) 2.261 2.241(2) 2.260Re(1)–Cl(1) 2.4817(15) 2.499 2.4851(13) 2.500 2.4836(8) 2.500C(1)–O(1) 1.162(8) 1.149 1.135(6) 1.150 1.146(4) 1.150C(2)–O(2) 1.145(7) 1.152 1.156(6) 1.152 1.145(4) 1.153C(3)–O(3) 1.134(7) 1.154 1.145(6) 1.154 1.158(4) 1.154

Bond anglesC(2)–Re(1)–C(1) 89.0(2) 86.81 86.9(2) 86.79 90.15(15) 86.79C(3)–Re(1)–C(1) 89.0(2) 89.59 88.4(2) 89.58 88.68(15) 89.57C(3)–Re(1)–C(2) 87.7(2) 88.70 89.6(2) 88.72 88.39(14) 88.71C(1)–Re(1)–N(1) 173.49(19) 174.08 174.84(18) 174.24 176.05(12) 174.28C(2)–Re(1)–N(1) 95.2(2) 96.44 96.20(19) 96.41 93.08(12) 96.44C(3)–Re(1)–N(1) 96.1(2) 95.41 95.77(18) 95.26 93.69(13) 95.21C(1)–Re(1)–N(2) 101.51(18) 102.15 102.50(18) 102.26 101.72(12) 102.22C(2)–Re(1)–N(2) 169.0(2) 170.08 169.22(18) 170.05 166.02(12) 170.09C(3)–Re(1)–N(2) 95.66(19) 95.54 96.0(2) 95.42 99.14(12) 95.41N(1)–Re(1)–N(2) 74.08(15) 74.27 74.09(14) 74.23 74.79(9) 74.24C(1)–Re(1)–Cl(1) 90.41(17) 90.99 91.71(16) 91.08 93.35(11) 91.12C(2)–Re(1)–Cl(1) 94.40(19) 93.54 92.46(16) 93.53 92.85(11) 93.51C(3)–Re(1)–Cl(1) 177.81(17) 177.71 177.98(18) 177.68 177.62(10) 177.71N(1)–Re(1)–Cl(1) 84.30(12) 83.89 84.02(11) 83.96 84.22(8) 83.98N(2)–Re(1)–Cl(1) 82.39(11) 82.17 82.03(10) 82.27 79.24(6) 82.31

7 8 9experimental calculated experimental calculated experimental calculated

Bond lengths

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Re(1)–C(1) 1.900(7) 1.920 1.916(6) 1.922 1.925(9) 1.922Re(1)–C(2) 1.927(9) 1.902 1.924(8) 1.904 1.903(9) 1.904Re(1)–C(3) 1.909(9) 1.903 1.902(7) 1.903 1.935(9) 1.903Re(1)–N(1) 2.166(5) 2.170 2.167(4) 2.169 2.150(6) 2.169Re(1)–N(2) 2.234(6) 2.259 2.230(5) 2.261 2.228(5) 2.262Re(1)–Cl(1) 2.485(2) 2.500 2.4762(16) 2.497 2.4794(19) 2.496C(1)–O(1) 1.152(8) 1.150 1.158(7) 1.150 1.140(9) 1.149C(2)–O(2) 1.105(10) 1.153 1.124(9) 1.152 1.141(10) 1.151C(3)–O(3) 1.127(9) 1.154 1.133(8) 1.155 1.111(9) 1.154

Bond anglesC(2)–Re(1)–C(1) 88.1(3) 86.78 87.8(3) 86.64 87.4(4) 86.66C(3)–Re(1)–C(1) 88.9(3) 89.53 89.9(3) 90.30 91.9(3) 90.44C(3)–Re(1)–C(2) 88.9(3) 88.69 90.2(3) 88.28 87.6(4) 88.30C(1)–Re(1)–N(1) 175.6(3) 174.34 173.0(2) 174.43 172.6(3) 174.26C(2)–Re(1)–N(1) 95.1(3) 96.42 97.6(2) 96.69 95.9(3) 96.73C(3)–Re(1)–N(1) 94.3(3) 95.19 94.3(2) 94.25 94.8(3) 94.28C(1)–Re(1)–N(2) 101.7(3) 102.21 99.4(2) 102.03 101.7(3) 101.96C(2)–Re(1)–N(2) 169.2(3) 170.09 168.9(2) 169.91 169.8(3) 169.94C(3)–Re(1)–N(2) 95.7(3) 95.46 98.2(2) 96.73 96.7(3) 96.73N(1)–Re(1)–N(2) 74.9(2) 74.28 74.59(18) 74.27 74.57(19) 74.27C(1)–Re(1)–Cl(1) 90.5(2) 91.18 92.70(19) 91.19 89.5(2) 90.99C(2)–Re(1)–Cl(1) 94.7(3) 93.44 91.9(2) 92.93 93.9(3) 92.78C(3)–Re(1)–Cl(1) 176.3(2) 177.78 176.73(19) 178.13 178.0(2) 178.26N(1)–Re(1)–Cl(1) 86.15(15) 83.99 82.89(13) 84.19 83.66(14) 84.23N(2)–Re(1)–Cl(1) 80.85(14) 82.34 79.39(11) 81.86 81.54(14) 82.00

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Table S3. Short intra- and intermolecular contacts detected in the structures of rhenium(I) complexes.

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;

D—H•••A D—H H•••A D•••A[Å]

D—H•••A[]

3C(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

4C(8)–H(8)•••Cl(1)#4 0.93 2.81 3.736(5) 172.7C(10)–H(10)•••S(3) 0.93 2.67 3.085(5) 108.1C(13)–H(13)•••S(3)#5 0.93 2.87 3.725(6) 153.6C(16)–H(16)•••Cl(1)#4 0.93 2.69 3.620(5) 175.6

5C(4)–H(4)•••N(3)#6 0.93 2.62 3.272(5) 127.7C(8)–H(8)•••S(1) 0.93 2.87 3.229(3) 104.3C(10)–H(10)•••S(3) 0.93 2.73 3.128(3) 106.5

7C(5)–H(5)•••Cl(1)#7 0.93 2.82 3.481(8) 129.3C(15)–H(15)•••O(4) 0.93 2.55 2.873(10) 100.4C(15)–H(15)•••Cl(1)#8 0.93 2.67 3.565(7) 162.8C(16)–H(16)•••O(1)#9 0.93 2.49 3.268(9) 141.0

8C(8)–H(8)•••S(1) 0.93 2.86 3.222(6) 104.0C(13)–H(13)•••S(1)#10 0.93 2.87 3.456(7) 122.0C(14)–H(14)•••N(3)#11 0.93 2.61 3.522(8) 168.0C(17)–H(17)•••O(3)#12 0.93 2.60 3.449(9) 153.0C(19)–H(19B)•••Cl(1)#13 0.96 2.72 3.555(7) 145.0C(19)–H(19C)•••Cl(1)#14 0.96 2.68 3.634(8) 171.0

9O(4)–H(4O)•••S(1) 0.84 2.50 3.323(17) 166.9O(4)–H(4P)•••N(3)#15 0.91 2.35 3.235(17) 164.6C(8)–H(8)•••S(1) 0.93 2.85 3.231(7) 105.8C(14)–H(14)•••Cl(1)#7 0.93 2.82 3.603(13) 142.2C(27)–H(27B)•••O(1)#16 0.97 2.56 3.281(11) 131.8

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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/ dm3·mol-1 ·cm-1)terpy MeCN 381.0 (4400), 321.2 (13200), 258.3 (12700), 193.7 (14900)dtpy MeCN 382.5 (5600), 330.7 (18720), 298.3 (13480), 263.1 (10880)terpy CHCl3 407.4 (23800), 333.1 (91300), 292.2 (97100), 260.0 (85700)

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dtpy CHCl3 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)dtpy MeCN 419.5 (30320), 329.9 (22000), 264.0 (20080)terpy CHCl3 427.9 (74900), 326.6 (57600), 260.2 (69700)

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dtpy CHCl3 431.3 (24480), 335.9 (19520), 296.0 (19480)terpy MeCN 383.7 (7800), 315.1 (45300), 279.3 (57600), 244.4 (60900)dtpy MeCN 395.8 (5000), 327.7 (16160), 247.0 (12000)terpy CHCl3 402.7 (24700), 334.3 (96000), 302.4 (88500), 260.9 (76200)

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dtpy CHCl3 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)

dtpy MeCN 399.3 (10960), 356.0 (14400), 316.2 (21120), 250.9 (14640)terpy CHCl3 408.2 (34600), 367.2 (42600), 314.1 (71500), 260.8 (77700)

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dtpy CHCl3 411.9 (11640), 363.1 (15640), 324.4 (21160), 257.9 (16920)

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Calculated transitionsExperimental absorption; nm

(ε; M-1cm-1)

Major contribution (%) Character E [eV] λ [nm] Oscillator

strength

H → L (98%) MLLCT* 2.60 476.16 0.0026H-1 → L (96%) MLLCT 2.84 436.02 0.0985H-2 → L (97%) MLCT/LC 3.10 399.71 0.0088408.4 (1560)H → L+1 (98%) MLLCT 3.31 374.54 0.0179

H-1 → L+1 (96%) MLLCT 3.46 358.21 0.0067H-3 → L (91%) LC/ILCT 3.66 338.52 0.2511335.8 (3780)

H-2 → L+1 (96%) MLCT/LC/ILCT 3.82 324.80 0.0036H-4 → L (88%) LC 4.09 303.01 0.0748H-8 → L (57%),

H-3 → L+1 (19%),H-7 → L (14%)

LLCT/LC/MLCTLC/ILCT

LLCT/LC/ILCT/MLCT

4.34 285.43 0.1270

291.4 (4800) H-3 → L+1 (44%),H-8 → L (22%),H-7 → L (13%),H-6 → L (12%)

LC/ILCTLLCT/LC/MLCT

LLCT/LC/ILCT/MLCTILCT

4.36 284.36 0.2332

H-4 → L+1 (79%) LC/ILCT 4.62 268.19 0.1589

266.2 (5540) H-2 → L+2 (48%),H-10 → L (19%),H-9 → L (14%)

MLCT/ILCT/LCLC/ILCT/LLCTLC/ILCT/LLCT

4.76 260.40 0.1484

*MLLCT – mixed MLCT/LLCT state



(ε; M-1cm-1)


strength

H → L (98%) MLLCT 2.65 468.27 0.0027H-1 → L (97%) MLLCT 2.88 430.53 0.1046H-2 → L (97%) MLCT/LC 3.14 394.35 0.0088387.1 (4800)H → L+1 (98%) MLLCT 3.35 369.94 0.0166

H-1 → L+1 (96%) MLLCT 3.50 354.14 0.0105H-3 → L (90%) LC 3.71 334.24 0.2676326.2 (24240)

H-2 → L+1 (96%) MLCT/LC/ILCT 3.86 321.44 0.0052H-5 → L (89%) LC/ILCT 4.13 299.95 0.2079

H-3 → L+1 (83%) LC/ILCT 4.35 285.08 0.2726302.5 (36560)H-4 → L+1 (79%) LC/ILCT/LLCT 4.61 268.89 0.2246H-3 → L+2 (82%) LC/ILCT 5.25 235.95 0.0628H-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/ILCTILCT/LLCT/LC

LC

5.74 215.82 0.0554


Calculated transitionsExperimental absorption

Major contribution Character E [eV] λ [nm] Oscillator

11

; nm (ε; M-1cm-1)

(%) strength

H → L (98%) MLLCT 2.63 472.26 0.0025H-1 → L (97%) MLLCT 2.86 433.87 0.1126H-2 → L (96%) MLCT/LC 3.12 397.54 0.0100394.3 (3000)H → L+1 (98%) MLLCT 3.34 370.83 0.0207

H-1 → L+1 (94%) MLLCT 3.48 355.80 0.0060H-3 → L (88%) LC 3.65 339.84 0.2545331.4 (8960)

H-2 → L+1 (96%) MLCT/LC 3.84 322.48 0.0055H-4 → L (50%),H-5 → L (40%)

ILCT/LC/LLCTLC

4.07 304.62 0.3048290.7 (15000)

H-3 → L+1 (71%) LC/ILCT 4.31 287.42 0.2168H-4 → L+1 (54%),H-5 → L+1 (12%),H-1 → L+4 (10%)

ILCT/LC/LLCTLC

MLCT/d-d/LLCT

4.58 270.72 0.1626

266.2 (12960)H-2 → L+2 (68%),H-1 → L+5 (10%)

MLCT/LC/ILCTd-d/MLCT/LLCT

4.79 258.65 0.604



(ε; M-1cm-1)


strength

H → L (98%) MLLCT 2.67 464.03 0.0033H-1 → L (97%) MLLCT 2.88 430.78 0.1545H-2 → L (96%) MLCT 3.16 391.81 0.0103382.5 (5600)H → L+1 (97%) MLLCT 3.36 368.78 0.0263

H-1 → L+1 (94%) MLLCT 3.48 356.36 0.0197H-3 → L (85%) ILCT/LC 3.60 344.60 0.3607330.7 (18720)H-4 → L (76%) LC 3.71 334.13 0.1906

H-3 → L+1 (84%) ILCT/LC 4.07 304.48 0.3200298.3 (13480) H-6 → L (86%) ILCT 4.25 291.70 0.0769263.1 (10880) H-5 → L+1 (83%) LC 4.68 265.10 0.1150



(ε; M-1cm-1)


strength

H-1 → L (63%),H → L (30%)

MLLCTILCT/LC

2.64 469.47 0.1176

H → L (58%),H-1 → L (34%)

ILCT/LCMLLCT

2.73 454.40 0.6561

H-2 → L (84%) MLLCT 2.99 414.38 0.1712H-3 → L (94%) MLCT/LC/ILCT 3.15 393.95 0.0100H → L+1 (89%) ILCT/LC 3.23 383.42 0.1887

419.5 (30320)

H-1 → L+1 (90%) MLLCT 3.35 370.46 0.0044H-2 → L+1 (94%) MLLCT 3.54 349.70 0.0341

H-4 → L (90%) LC/ILCT 3.67 337.48 0.2401329.9 (22000)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

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H-3 → L+2 (25%),H → L+3 (15%)

MLCT/ILCT/LCILCT/LC

H-4 → L+2 (51%),H-9 → L+1 (12%),H-3 → L+4 (10%)

LC/ILCTLLCT/LC/ILCT/MLCT

d-d/MLCT/LC

5.02 246.96 0.1227



(ε; M-1cm-1)


strength

H → L (98%) MLLCT 2.69 460.70 0.0036H-1 → L (96%) MLLCT 2.89 428.53 0.1630H-2 → L (89%) MLCT/LC 3.18 389.53 0.0114395.8 (5000)H → L+1 (97%) MLLCT 3.37 367.63 0.0230H-3 → L (77%) ILCT/LC/MLCT 3.54 349.94 0.3546H-4 → L (78%) LC 3.74 331.56 0.2208327.7 (16160)

H-3 → L+1 (86%) ILCT/LC/MLCT 4.00 310.25 0.3508H-5 → L+1 (84%) LC 4.69 264.05 0.0996H-2 → L+2 (49%),H-2 → L+4 (24%)

MLCT/LCd-d/LC

4.86 255.09 0.0746247.0 (12000)H-4 → L+2 (86%) LC 5.32 233.21 0.0732



(ε; M-1cm-1)


strength

H-1 → L (66%),H → L (29%)

MLLCTILCT/MLCT

2.61 475.91 0.0295

H → L (53%),H-1 → L (32%),H-2 → L (13%)

ILCT/MLCTMLLCT

MLLCT/ILCT

2.75 451.18 0.4880

H-2 → L (75%),H → L (15%)

MLLCT/ILCTILCT/MLCT

3.04 408.40 0.2568

398.8 (22320)

H-3 → L (90%) MLCT/LC 3.11 398.71 0.0312H → L+1 (69%),

H-1 → L+1 (23%)ILCT/MLCT

MLLCT3.40 364.72 0.2176

366.9 (27360) H-1 → L+1 (71%),H → L+1 (16%)

MLLCTILCT/MLCT

3.47 357.18 0.0498

H-4 → L (76%),H-2 → L+1 (15%)

LC/ILCTMLLCT/ILCT

3.63 341.26 0.2251

331.4 (23920) H-2 → L+1 (78%),H-4 → L (10%)

MLLCT/ILCTLC/ILCT

3.71 333.85 0.2594

H-3 → L+2 (77%) MLCT/LC/ILCT 4.69 264.60 0.0479260.3 (19200) H-5 → L+1 (75%) LC/ILCT 4.73 262.18 0.1296


Experimental absorption

Calculated transitions

13

; nm (ε; M-1cm-1)


strengthH → L (50%),

H-1 → L (46%)MLLCT/ILCT

MLLCT2.79 445.05 0.0176

H-1 → L (53%),H → L (38%)

MLLCTMLLCT/ILCT

2.93 423.70 0.2238

H-2 → L (80%) MLLCT/ILCT/LC 3.22 385.28 0.0521

399.3 (10960)

H-3 → L (90%) MLCT/LC 3.28 377.69 0.0104H → L+1 (77%),

H-1 → L+1 (18%)MLLCT/ILCT

MLLCT3.53 351.02 0.1765

356.0 (14400) H-1 → L+1 (80%),H → L+1 (15%)

MLLCTMLLCT/ILCT

3.59 345.01 0.0650

H-4 → L (70%),H-2 → L+1 (22%)

LCMLLCT/ILCT/LC

3.80 326.56 0.2199

316.2 (21120) H-2 → L+1 (74%),H-4 → L (20%)

MLLCT/ILCT/LCLC

3.86 321.02 0.2564

H-7 → L (54%),H-4 → L+1 (37%)

MLLCT/LCLC

4.51 274.80 0.1228

H-8 → L (59%),H-4 → L+1 (7%)

MLLCT/LCLC

4.62 268.37 0.0608

H → L+2 (41%),H → L+4 (21%)

MLLCT/ILCTd-d/ILCT/LC

4.64 267.33 0.0643

H-6 → L+1 (75%) LC/MLLCT 4.85 255.67 0.0665250.9 (14640)H-3 → L+3 (28%),H-1 → L+4 (12%),

H → L+3 (8%),H-2 → L+2 (7%),H-2 → L+4 (7%)

d-d/LCd-d/LLCT/LCd-d/ILCT/LC

MLLCT/ILCT/LCd-d/LLCT/ILCT/LC

4.87 254.57 0.0684



(ε; M-1cm-1)


strength

H-1 → L (54%),H → L (40%)

MLLCTILCT

2.78 445.29 0.1040

H → L (49%),H-1 → L (44%)

ILCTMLLCT

2.86 433.72 0.2617

H-2 → L (53%),H-3 → L (35%)

MLLCT/ILCTMLLCT/ILCT

3.06 404.64 0.0103

H-4 → L (95%) MLCT/LC/ILCT 3.28 377.43 0.0101H-3 → L (53%),H-2 → L (33%)


3.32 373.49 0.0067

410.8 (15720)

H → L+1 (83%) ILCT 3.41 363.45 0.3384H-5 → L (82%) LC/ILCT/MLCT 3.80 326.29 0.2804

318.4 (22480)H → L+2 (47%),

H-4 → L+1 (17%),H-3 → L+1 (16%),H-2 → L+1 (12%)

LC/ILCTMLCT/LC/ILCT


4.01 309.48 0.0739

H-6 → L (45%),H-7 → L (29%)

ILCT/LCLC/ILCT/MLLCT

4.26 290.97 0.1620

290.4 (21600) H-2 → L+2 (26%),H → L+3 (12%),H-5 → L+1 (9%)

MLLCT/LC/ILCTILCT/LC

LC/ILCT/MLCT

4.41 281.38 0.1099

14

H-5 → L+1 (66%) LC/ILCT/MLCT 4.43 280.00 0.3530

262.3 (22040)

H-2 → L+2 (21%),H → L+3 (11%),H-9 → L (7%),

H-3 → L+2 (7%),H-3 → L+5 (7%),H-1 → L+5 (7%)

MLLCT/LC/ILCTILCT/LC

LLCT/LC/ILCTMLLCT/LC/ILCTd-d/ILCT/MLCT

d-d/MLLCT

4.60 269.70 0.2884

245.1 (27720)H → L+5 (32%),H → L+4 (15%),H → L+6 (14%)

ILCT/LMCTILCT/LMCT

ILCT/LC

5.04 246.03 0.1313

236.1 (31400)H → L+7 (36%),

H-1 → L+7 (12%),H-1 → L+9 (6%)

ILCT/LCMLLCTMLLCT

5.34 232.28 0.0789

229.3 (31200)

H-1 → L+7 (22%),H → L+7 (14%),

H-1 → L+6 (11%),H → L+9 (9%)

MLLCTILCT/LCMLLCTILCT/LC

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

MeCNdtpy 744terpy 675

4CHCl3 dtpy 734

terpy 516MeCN

dtpy 682, 739terpy 484

5CHCl3 dtpy 691, 735

terpy 663MeCN

dtpy 720terpy 675

6CHCl3 dtpy 731

terpy 646MeCN

dtpy 716terpy 656

8CHCl3 dtpy 717

15

2

5Figure S1. Representative IR spectra of complexes 2 and 5.

16

(a)

(b)

Figure S2. Representative 1H NMR (a) and 13C NMR (b) spectra of complex 9.

17

3

4

18

5

7

19

9Figure S3. A view of the crystal packing showing intermolecular – stacking interactions for tricarbonyl rhenium(I) complexes.

20

Figure S4. Cyclic voltammograms of the rhenium(I) complexes.

(1)

(2)

(3)

21

(4)

(5)

(6)

22

(7)

(8)

(9)

23

Figure S5. Absorption spectra of the rhenium(I) complexes in chloroform and acetonitrile solutions.

Complex ACN CHCl3

1

2

3

4

24

5

6

7

8

26

Figure S6. Experimental and theoretical absorption spectra of 1-9 complexes in acetonitrile solution.

1 2 3

4 5 6

7 8 9

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