Department of Chemical Organic Technology and Petrochemistry, Silesian University of Technology, Krzywoustego 4, Gliwice, Poland

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1 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2016 Tuning the photophysical properties of 4 -subsituted terpyridines - experimental and theoretical study ELECTRONIC SUPLEMENTARY INFORMATION Anna Maroń a, Agata Szlapa b, Tomasz Klemens a, Slawomir Kula b, Barbara Machura a *, Stanisław Krompiec b, Jan Grzegorz Małecki a, Anna Świtlicka-Olszewska a, Karol Erfurt c, Anna Chrobok c a Department of Crystallography, Institute of Chemistry, University of Silesia, 9 th Szkolna St., Katowice, Poland b Department of Inorganic, Organometallic Chemistry and Catalysis, Institute of Chemistry, University of Silesia, 9 th Szkolna St., Katowice, Poland c Department of Chemical Organic Technology and Petrochemistry, Silesian University of Technology, Krzywoustego 4, Gliwice, Poland Abstract: Several 2,2 :6,2 -terpyridines substituted in 4 -position were synthetized and their photophysical properties were investigated by absorption and photoluminescence spectroscopy in dilute solutions and solid state. The studies confirmed that the absorption and emission wavelengths, fluorescence quantum yields and lifetimes of 1-R 1-16 are strongly structure-related, demonstrating a decisive role of the nature of the substituent in determining photophysical properties of 4 -functionalized terpyridines. Additionally, the density functional theory (DFT) calculations were performed for 1-R 1-16 to get an insight into their electronic structure and spectroscopic properties. Keywords: 2,2 :6,2 -terpyridine derivatives, absorption and fluorescence spectra, effect of solvent polarity, intramolecular charge transfer, DFT calculations. * Corresponding author, bmachura@poczta.onet.pl 1

2 Tables: Table S1. Experimental and calculated bond lengths [Å] and angles [ ] for 2.2 :6.2 -terpyridine derivatives Table S2. Short intra- and intermolecular contacts detected in structures 1-R 3, 1-R 7, 1-R 8 and 1-R 14. Table S3. Calculated Onsager cavity radius (a) Table S4. Electrochemical properties and optical band gaps of 1-R 1-16 derivatives Table S5. The energies and characters of the selected calculated transitions assigned to the lowest experimental absorption bands of the compounds 1-R 1-16 (in acetonitrile) Figures: Figure S1. View of the packing of 1-R 3, 1-R 7, 1-R 8 and 1-R 14 showing short intra- and intermolecular C H O and C H N contacts. Figure S2. Hirshfeld surfaces, 2D fingerprint plots and percentage contributions to the Hirshfeld surface area for the various close intermolecular contacts for molecules of 1-R 3, 1-R 7 and 1-R 14 compounds. Figure S3. Plot of difference between absorption and fluorescence wavenumber parameter f for 1-R 4. st vs. solvent polarity Figure S4. Plot of difference between absorption and fluorescence wavenumber st vs. solvent polarity parameter f for 1-R 7. Figure S5. Plot of difference between absorption and fluorescence wavenumber st vs. solvent polarity parameter f for 1-R 9. Figure S6. Plot of difference between absorption and fluorescence wavenumber st vs. solvent polarity parameter f for 1-R 10. Figure S7. Plot of difference between absorption and fluorescence wavenumber st vs. solvent polarity parameter f for 1-R 11. Figure S8. Plot of difference between absorption and fluorescence wavenumber st vs. solvent polarity parameter f for 1-R 14. Figure S9. Frontier molecular orbitals of 1-R 1-16 calculated at DFT/B3LYP level using the polarizable continuum model (MeCN). Figure S10. Partial density of states diagrams for 1-R Figure S11. Electronic absorption spectra of compounds 1-R 3-6, 1-R 8-9, 1-R 11, 1-R Figure S12. Excitation and emission spectra of compounds 1-R 1-16 Figure S13. Relative orientation of the experimental (blue) and optimised (red) molecules of 1-R 3, 1-R 7, 1- R 8 and 1-R 14. Figure S14. Experimental and calculated with CIS(D) and TD-DFT method absorption spectra 2

3 Table S1. Experimental and calculated bond lengths [Å] and angles [ ] for 2.2 :6.2 -terpyridine derivatives. Bonds [Å] Angles [ ] 1-R 3 exp calc exp calc N(1) C(1) 1.340(2) N(4) C(27) 1.339(2) C(1) N(1) C(5) (17) C(27) N(4) C(31) (15) N(1) C(5) 1.345(2) N(4) C(31) 1.347(2) C(10) N(2) C(6) (15) C(32) N(5) C(36) 116.8(2) N(2) C(6) 1.337(2) N(5) C(32) 1.339(3) C(15) N(3) C(11) 116.8(2) C(41) N(6) C(37) (18) N(2) C(10) 1.342(3) N(5) C(36) 1.345(3) N(1) C(1) C(2) (17) N(4) C(27) C(28) (16) N(3) C(11) 1.345(3) N(6) C(37) 1.344(2) N(1) C(1) C(6) (15) N(4) C(27) C(32) (15) N(3) C(15) 1.334(3) N(6) C(41) 1.331(3) N(1) C(5) C(4) (15) N(4) C(31) C(30) (15) C(1) C(2) 1.388(2) C(27) C(28) 1.388(3) N(1) C(5) C(11) (16) N(4) C(31) C(37) (15) C(1) C(6) 1.493(3) C(27) C(32) 1.496(3) N(2) C(6) C(1) (16) N(5) C(32) C(27) (17) C(2) C(3) 1.393(3) C(28) C(29) 1.390(3) N(2) C(6) C(7) (18) N(5) C(32) C(33) (18) C(3) C(4) 1.388(2) C(29) C(30) 1.392(2) N(2) C(10) C(9) 124.1(2) N(5) C(36) C(35) 124.1(2) C(3) C(16) 1.490(2) C(29) C(42) 1.489(2) N(3) C(11) C(5) (18) N(6) C(37) C(31) (16) C(4) C(5) 1.381(3) C(30) C(31) 1.381(2) N(3) C(11) C(12) (18) N(6) C(37) C(38) (16) C(5) C(11) 1.492(2) C(31) C(37) 1.493(2) N(3) C(15) C(14) 124.9(3) N(6) C(41) C(40) 124.7(2) C(6) C(7) 1.383(3) C(32) C(33) 1.379(3) C(7) C(8) 1.378(3) C(33) C(34) 1.390(3) C(8) C(9) 1.365(4) C(34) C(35) 1.364(4) C(9) C(10) 1.368(4) C(35) C(36) 1.364(4) C(11) C(12) 1.377(3) C(37) C(38) 1.378(3) C(12) C(13) 1.388(3) C(38) C(39) 1.382(3) C(13) C(14) 1.370(4) C(39) C(40) 1.373(3) C(14) C(15) 1.357(5) C(40) C(41) 1.374(4) C(16) C(25) 1.425(3) C(42) C(51) 1.432(2) C(16) C(17) 1.373(2) C(42) C(43) 1.363(3) C(17) C(18) 1.398(3) C(43) C(44) 1.398(3) C(18) C(19) 1.365(3) C(44) C(45) 1.371(2) C(19) C(20) 1.431(2) C(45) C(46) 1.425(3) C(19) O(1) 1.357(2) C(45) O(2) 1.358(2) C(26) O(1) 1.421(2) C(52) O(2) 1.415(2) C(20) C(21) 1.408(3) C(46) C(47) 1.419(2) C(20) C(25) 1.418(2) C(46) C(51) 1.421(2) C(21) C(22) 1.366(3) C(47) C(48) 1.360(3) C(22) C(23) 1.398(3) C(48) C(49) 1.394(3) C(23) C(24) 1.354(3) C(49) C(50) 1.365(3) C(24) C(25) 1.422(2) C(50) C(51) 1.410(2) R 7 N(1) C(1) (17) C(1) N(1) C(5) (11) N(1) C(5) (18) C(10) N(2) C(6) (13) N(2) C(6) (18) C(15) N(3) C(11) (15) N(2) C(10) (19) N(1) C(1) C(2) (12) N(3) C(11) (19) N(1) C(1) C(6) (11) N(3) C(15) 1.333(2) N(1) C(5) C(4) (12) N(4) C(19) (17) N(1) C(5) C(11) (11) N(4) C(22) (19) N(2) C(6) C(1) (11) N(4) C(23) (19) N(2) C(6) C(7) (13) C(1) C(2) (18) N(2) C(10) C(9) (16) C(1) C(6) (19) N(3) C(11) C(5) (12) C(2) C(3) (18) N(3) C(11) C(12) (13) C(3) C(4) (18) N(3) C(15) C(14) (18) C(3) C(16) (17) C(4) C(5) (18) C(5) C(11) (18) C(6) C(7) (18) C(7) C(8) 1.378(2) C(8) C(9) 1.361(3) C(9) C(10) 1.371(2) C(11) C(12) (19) C(12) C(13) 1.376(2) C(13) C(14) 1.359(3) C(14) C(15) 1.366(3) C(16) C(21) (18) C(16) C(17) (19) C(17) C(18) (19) C(18) C(19) (19) C(19) C(20) (19) C(20) C(21) (18) R 8 N(1) C(1) (16) C(1) N(1) C(5) (17) N(1) C(1)# (16) C(4) N(2) C(8) (14) N(2) C(4) (18) C(11) N(3) C(11) (19) N(2) C(8) (19) N(1) C(1) C(2) (13) N(3) C(11) (18) N(1) C(1) C(4) (13) N(3) C(11)# (18) N(2) C(4) C(1) (13) C(1) C(2) 1.388(2) N(2) C(4) C(5) (13) C(1) C(4) (19) N(2) C(8) C(7) (16) C(2) C(3) (17) N(3) C(11) C(10) (15)

4 C(3) C(2)# (17) C(3) C(9) 1.490(3) C(4) C(5) 1.387(2) C(5) C(6) 1.378(2) C(6) C(7) 1.367(2) C(7) C(8) 1.368(2) C(9) C(10)# (17) C(9) C(10) (17) C(10) C(11) 1.371(2) R 14 N(1) C(1) 1.350(3) C(1) N(1) C(5) 119.2(2) N(1) C(5) 1.351(3) C(10) N(2) C(6) 116.6(3) N(2) C(6) 1.356(3) C(15) N(3) C(11) 115.8(3) N(2) C(10) 1.337(4) N(1) C(1) C(2) 121.3(2) N(3) C(11) 1.333(3) N(1) C(1) C(6) 116.6(3) N(3) C(15) 1.304(4) N(1) C(5) C(4) 120.9(2) C(1) C(2) 1.350(4) N(1) C(5) C(11) 117.4(2) C(1) C(6) 1.481(4) N(2) C(6) C(1) 116.9(2) C(2) C(3) 1.377(4) N(2) C(6) C(7) 122.2(2) C(3) C(4) 1.392(4) N(2) C(10) C(9) 122.8(3) C(3) C(16) 1.449(4) N(3) C(11) C(5) 117.2(2) C(4) C(5) 1.364(4) N(3) C(11) C(12) 121.5(3) C(5) C(11) 1.481(4) N(3) C(15) C(14) 123.8(3) C(6) C(7) 1.372(4) C(7) C(8) 1.340(4) C(8) C(9) 1.337(4) C(9) C(10) 1.357(4) C(11) C(12) 1.351(4) C(12) C(13) 1.296(4) C(13) C(14) 1.290(5) C(14) C(15) 1.318(5) C(16) O(1) 1.359(5) C(16) C(17) 1.321(12) C(17) C(18) 1.485(19) C(18) C(19) 1.23(2) Table S2. Short intra and intermolecular contacts detected in the structures 1 R 3, 1 R 7 and 1 R 14. D H A D H H A D A [Å] D H A [ ] 1 R 3 C(2) H(2) N(2) (2) C(4) H(4) N(3) (3) C(7) H(7) N(1) (3) 99.6 C(21) H(21) O(1) (3) C(28) H(28) N(5) (3) 99.9 C(30) H(30) N(6) (2) C(38) H(38) N(4) (2) R 7 C(2) H(2) N(2) (18) R 14 C(2) H(2) N(2) (4) C(4) H(4) O(1) (6) 99.9 C(4) H(4) N(3) (4) 99.8 C(7) H(7) N(1) (4) 99.6 C(12) H(12) N(1) (4)

5 Table S3. Calculated Onsager cavity radius (a). a [Å] a [Å] 1 R R R R R R R R R R R R R R R R Table S4. Electrochemical properties and optical band gaps of the compounds 1 R Compound CV b E opt g [ev] a E red [V] E ox [V] E HOMO [ev] E LUMO [ev] Eg [ev] 1 R R R R R R R R R R R R R R R R a. E g opt = 1241/λ em b. Measured in CH 2 Cl 2 solution, GC as working electrode, HOMO= 5.1 E ox ; LUMO= 5.1 E red ; scan rate 100 [mv/s] 5

6 Table S5. The energies and characters of the selected calculated transitions assigned to the lowest experimental absorption bands of the compounds 1 R 1 16 (in acetonitrile) 1 R 1 1 R 2 1 R 3 abs Calculated transitions [nm] λ [nm] f The most important orbital excitations Character CIS(D) H L (19%), H L+2 (81%) R * terpy H L (70%), H L+2 (18%) R * R TD H L (87%) R * R H L+2 (87%) R * terpy CIS(D) H L (88%) R * terpy H 2 L (78%) terpy * terpy H L+2 (58%), H L+3 (33%) R * terpy H 6 L+1 (29%), H 2 L+1 (46%) terpy * terpy H 6 L+1 (70%), H 2 L+1 (17%) terpy * terpy TD H L (97%) R * terpy H 1 L (55%), H L+1 (41%) terpy * terpy, R * terpy H 1 L+1 (89%) terpy * terpy CIS(D) H L (63%), H L+1 (27%) R * terpy H 2 L (52%) terpy * terpy H L+2 (28%) H 4 L+1 (25%), H 4 L (19%) R * R, terpy * terpy H 4 L (29%), H 4 L+1 (16%), H L+2 (24%) terpy * terpy, R * R, TD H L (90%) R * terpy 1 R 4 1 R 5 1 R 6 1 R 7 CIS(D) TD CIS(D) TD CIS(D) TD CIS(D) TD H 2 L (35%), H 1 L (19%) terpy * terpy H 3 L+1 (39%), H 1 L (55%) terpy * terpy, R * terpy H 3 L+1 (52%), H 1 L (26%) terpy * terpy, R * terpy H 3 L (73%) terpy * terpy H L (83%) terpy * terpy H L+1 (79%) terpy * terpy H 1 L (83%) R * terpy H 1 >L+1 (80%) R * terpy H 3 L (80%) terpy * terpy H 3 L+1 (43%), H 1 L (37%) terpy * terpy, R * terpy H 1 L+1 (69%) R * terpy H L (81%) terpy * terpy H 1 L (52%), H L+1 (40%) R * terpy H 1 L+1 (80%) R * terpy H 3 L+1 (32%), H 1 L (62%) terpy * terpy H 3 L+1 (40%), H 3 L (14%), H 1 L (13%) terpy * terpy H 4 L (11%), H 3 L (44%), H 3 L+1 (14%) terpy * terpy H L (85%) terpy * terpy H 3 L (28%), H L+1 (54%) terpy * terpy H 3 L (40%), H L+1 (39%) terpy * terpy H 1 L (82%) terpy * terpy H 1 >L+1 (76%) terpy * terpy H L+1 (91%) H L+2 (94%) R * terpy R * terpy H 2 L+1 (74%) terpy * terpy H L+4 (70%) R * terpy H L (99%) R * terpy H L+1 (99%) R * terpy 1 R 8 CIS(D) H 3 L (67%), H 1 L (18%) terpy * terpy, R * terpy H 6 L (16%), H 5 L (29%), H 3 L+1 (31%), terpy * terpy, R * terpy H 1 L+1 (14%) 6

7 H 2 L+2 (52%) terpy * terpy 1 R 9 1 R 10 1 R 11 1 R 12 1 R 13 1 R 14 TD H L (92%) terpy * terpy CIS(D) H 1 L (65%) terpy * terpy H 6 L (33%), H 1 L+1 (42%) terpy * terpy H 4 L+1 (47%) terpy * terpy H 6 L+1 (24%), H 1 L+2 (34%) terpy * terpy TD H L (90%) terpy * terpy CIS(D) H L+1 (78%) R * terpy H L+2 (91%) R * terpy TD H L (59%), H L+1 (37%) R * terpy H L (39%), H L+1 (60%) R * terpy CIS(D) H 2 L+1 (33%), H 1 L (33%), H 1 L+1 (15%) terpy * terpy, R * terpy H 1 L (37%), H 2 L (20%), H 5 L (10%) R * terpy, terpy * terpy H 2 L+1 (43%), H 2 L (19%), H 1 L (11%) terpy * terpy, R * terpy, TD H 1 L+1 (21%), H L (75%) R * terpy, terpy * terpy CIS(D) H L (74%) R * R/terpy H 2 L (86%) terpy * R/terpy H L+3 (49%), H L+2 (39%), R * terpy H L+3 (42%), H L+2 (22%), R * terpy TD H L (99%) R * R/terpy H L+1 (87%) R * terpy CIS(D) H 2 L (44%), H 4 L (23%), H L (11%) R/terpy * terpy, terpy * terpy H 2 L+1 (30%), H 4 L (29%), R/terpy * terpy, terpy * terpy H L+2 (54%), H L+3 (30%) R * terpy H 6 L (50%), H 4 L+1 (18%), H L+3 (10%) terpy * terpy, R * terpy H 2 L+2 (39%), H 6 L+1 (23%) R/terpy * terpy TD H 1 L (39%), H L+1 (41%) terpy * terpy, R * terpy H 3 L (56%), H 2 L (27%) terpy * terpy, R/terpy * terpy CIS(D) H L (70%) R * terpy H 2 L (70%) terpy * terpy H L+2 (71%) terpy * terpy H 2 L+1 (66%) terpy * terpy TD H 1 L (41%), H L+1 (57%) terpy * terpy, R * R H L (97%) R * terpy H 1 L (56%), H L+1 (42%) terpy * terpy, R * R H 1 L+1 (93%) terpy * R 7

8 1 R 15 1 R 16 CIS(D) TD CIS(D) TD H 2 L+1 (73%) terpy * terpy H 2 L (58%) terpy * terpy H L (99%) R * terpy H L+1 (99%) R * terpy H L (68%), H L+2 (23%) R * terpy H L+2 (52%) R * terpy H 2 L (64%), H 4 L+1 (29%) terpy * terpy H 4 L (57%), H 4 L+1 (13%) terpy * terpy H L (96%) R * terpy H 1 L (89%) terpy * terpy H L+2 (94%) R * terpy H 1 L+1 (63%) terpy * terpy 8

9 1 R 3 1 R 7 1 R 8 1 R 14 Figure S1: View of the packing of 1 R 3, 1 R 7, 1 R 8 and 1 R 14 showing short intra and intermolecular C H O and C H N contacts. 9

10 1 R 3 1 R 7 1 R 8 1 R 14 Figure S2. Hirshfeld surfaces, 2D fingerprint plots and percentage contributions to the Hirshfeld surface area for the various close intermolecular contacts for molecules of 1 R 3, 1 R 7 and 1 R 14 compounds. 10

11 Figure S3. Plot of difference between absorption and fluorescence wavenumber parameter f for 1 R 4. st vs. solvent polarity Solvent Δf Methanol Acetonitryle Acetone N.N dimethylformamide Dimethyl sulfoxide Dichloromethane Ethyl acetate Diethyl ether Dipropyl ether Cyclohexane 0.0 Figure S4. Plot of difference between absorption and fluorescence wavenumber parameter f for 1 R 7. st vs. solvent polarity Solvent Δf Methanol Acetonitryle Acetone N.N dimethylformamide Dimethyl sulfoxide Dichloromethane Ethyl acetate Diethyl ether Dipropyl ether Cyclohexane

12 Figure S5. Plot of difference between absorption and fluorescence wavenumber parameter f for 1 R 9. st vs. solvent polarity Solvent Δf Methanol Acetonitryle Acetone N.N dimethylformamide Dimethyl sulfoxide Dichloromethane Ethyl acetate Diethyl ether Dipropyl ether Cyclohexane 0.0 Figure S6. Plot of difference between absorption and fluorescence wavenumber parameter f for 1 R 10. st vs. solvent polarity Solvent Δf Methanol Acetonitryle Acetone N.N dimethylformamide Dimethyl sulfoxide Dichloromethane Ethyl acetate Diethyl ether Dipropyl ether Cyclohexane

13 Figure S7. Plot of difference between absorption and fluorescence wavenumber parameter f for 1 R 11. st vs. solvent polarity Solvent Δf Methanol Acetonitryle Acetone N.N dimethylformamide Dimethyl sulfoxide Dichloromethane Ethyl acetate Diethyl ether Dipropyl ether Cyclohexane 0.0 Figure S8. Plot of difference between absorption and fluorescence wavenumber parameter f for 1 R 14. st vs. solvent polarity Solvent Δf Methanol Acetonitryle Acetone N.N dimethylformamide Dimethyl sulfoxide Dichloromethane Ethyl acetate Diethyl ether Dipropyl ether Cyclohexane

14 Figure S9. Frontier molecular orbitals of 1 R 1 16 calculated at DFT/B3LYP level using the polarizable continuum model (MeCN). Compound HOMO (energy in ev) LUMO 1 R 1 1 R 2 ( 5.34 ev) ( 1.80 ev) 1 R 3 ( 6.07 ev) ( 1.71 ev) ( 5.61 ev) ( 1.60 ev) 14

15 1 R 4 1 R 5 ( 6.43 ev) ( 1.74 ev) 1 R 6 ( 6.43 ev) ( 1.73 ev) ( 6.43 ev) ( 1.75 ev) 15

16 1 R 7 1 R 8 ( 5.11 ev) ( 1.52 ev) 1 R 9 ( 6.46 ev) ( 1.89 ev) ( 6.39 ev) ( 1.87 ev) 16

17 1 R 10 1 R 11 ( 5.65 ev) ( 1.57 ev) 1 R 12 ( 6.43 ev) ( 1.83 ev) ( 5.64 ev) ( 2.04 ev) 17

18 1 R 13 1 R 14 ( 6.07 ev) ( ev) 1 R 15 ( 6.15 ev) ( 1.77 ev) ( 5.67 ev) ( 1.57 ev) 18

19 1 R 16 ( 5.53 ev) ( 1.69 ev) 19

20 Figure S10. Partial density of states diagrams for 1 R

21 21

22 Figure S11. Electronic absorption spectra of compounds 1 R 3 6, 1 R 8 9, 1 R 11, 1 R Compound CH 3 CN CH 2 Cl 2 1 R 3 1 R 4 1 R 5 1 R 6 22

23 1 R 8 1 R 9 1 R 11 1 R 13 1 R 14 23

24 Figure S12. Excitation and emission spectra of compounds 1 R Medium Excitation and emission spectra PL lifetime curve 1 R 1 CH 2 Cl 2 MeCN Solid CH 2 Cl 2 1 R 2 MeCN Solid 1 R 3 24

25 CH 2 Cl 2 MeCN Solid CH 2 Cl 2 1 R 4 MeCN 25

26 Solid CH 2 Cl 2 1 R 5 MeCN Solid CH 2 Cl 2 1 R 6 26

27 MeCN Solid CH 2 Cl 2 1 R 7 MeCN Solid 1 R 8 27

28 CH 2 Cl 2 MeCN Solid CH 2 Cl 2 1 R 9 MeCN 28

29 Solid CH 2 Cl 2 1 R 10 MeCN Solid CH 2 Cl 2 1 R 11 29

30 MeCN Solid CH 2 Cl 2 1 R 12 MeCN Solid 1 R 13 30

31 CH 2 Cl 2 MeCN Solid CH 2 Cl 2 1 R 14 MeCN 31

32 Solid CH 2 Cl 2 1 R 15 MeCN Solid CH 2 Cl 2 1 R 16 32

33 MeCN Solid Figure S13. Relative orientation of the experimental (blue) and optimised (red) molecules of 1 R 3, 1 R 7, 1 R 8 and 1 R R 3 1 R 7 33

34 1 R 8 1 R 14 Figure S14. Experimental and calculated with CIS(D) and TD-DFT method absorption spectra 1 R 1 1 R 3 1 R 6 1 R 7 1 R 8 1 R 9 34

35 1 R 10 1 R 11 1 R 13 1 R 14 1 R 15 1 R 16 35