Supplementary Data - The Royal Society of Chemistry · 1 Electronic Supplementary Information for Dalton Transactions Supplementary Data Synthesis, spectroscopic, electrochemical
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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.
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 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 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.
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)
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
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
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.
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-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
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.
Calculated transitionsExperimental absorption; nm
(ε; M-1cm-1)
Major contribution (%) Character E [eV] λ [nm] Oscillator
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
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
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.
Calculated transitionsExperimental absorption
Major contribution Character E [eV] λ [nm] Oscillator
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; 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
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.
Calculated transitionsExperimental absorption; nm
(ε; M-1cm-1)
Major contribution (%) Character E [eV] λ [nm] Oscillator
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
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.
Calculated transitionsExperimental absorption; nm
(ε; M-1cm-1)
Major contribution (%) Character E [eV] λ [nm] Oscillator
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.
Calculated transitionsExperimental absorption; nm
(ε; M-1cm-1)
Major contribution (%) Character E [eV] λ [nm] Oscillator
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)
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.
Calculated transitionsExperimental absorption; nm
(ε; M-1cm-1)
Major contribution (%) Character E [eV] λ [nm] Oscillator
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
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; nm (ε; M-1cm-1)
Major contribution (%) Character E [eV] λ [nm] Oscillator
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.
Calculated transitionsExperimental absorption; nm
(ε; M-1cm-1)
Major contribution (%) Character E [eV] λ [nm] Oscillator
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%)
MLLCT/ILCTMLLCT/ILCT
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