Supplementary materials

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1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Supplementary materials Synthesis, Photophysical Properties and Application in Organic Light Emitting Devices of Rhenium(I) Carbonyls incorporating Functionalized 2,2 :6,2 -terpyridines Tomasz Klemens, Anna Świtlicka-Olszewska, Barbara Machura, Marzena Grucela, Henryk Janczek, Ewa Schab-Balcerzak, Agata Szlapa, Slawomir Kula, Stanisław Krompiec, Karolina Smolarek, Dorota Kowalska, Sebastian Mackowski, Karol Erfurt, Piotr Lodowski Tables: Table S1. Comparison of experimental and theoretical bond lengths [Å] and angles [ ] for 1, 3, 4 and 6. Table S2. Short intra- and intermolecular contacts detected in the structures of the tricarbonyl rhenium(i) complexes. Table S3. Frontier molecular orbital composition (%) in the ground state for complex 1 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Table S4. Frontier molecular orbital composition (%) in the ground state for complex 2 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Table S5. Frontier molecular orbital composition (%) in the ground state for complex 3 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Table S6. Frontier molecular orbital composition (%) in the ground state for complex 4 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Table S7. Frontier molecular orbital composition (%) in the ground state for complex 5 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Table S8. Frontier molecular orbital composition (%) in the ground state for complex 6 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Table S9. Frontier molecular orbital composition (%) in the ground state for complexes 2, 3, and 6 calculated at the DFT/B3LYP level using different basis sets. Table S10. Main contributions to frontier molecular orbitals (%) in the ground state for complexes 2, 3, and 6 calculated at the DFT/B3LYP/TZ2P level using ADF software with ZORA relativistic approximation and COSMO solvent model. Table S11. The energies and characters of the selected spin-allowed electronic transitions for 1 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands. Table S12. The energies and characters of the selected spin-allowed electronic transitions for 2 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands. Table S13. The energies and characters of the selected spin-allowed electronic transitions for 3 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands. Table S14. The energies and characters of the selected spin-allowed electronic transitions for 4 calculated with the TDDFT/B3LYP method, together with assignment to the experimental Page:

2 absorption bands. Table S15. The energies and characters of the selected spin-allowed electronic transitions for 5 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands. Table S16. The energies and characters of the selected spin-allowed electronic transitions for 6 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands. Table S17. The energies and characters of the of two lowest vertical electronic transitions for 6 complex obtained in TDDFT calculations with using different functionals Figures: Page: Figure S1. A view of the crystal packing showing intermolecular stacking interactions for 1 and 6. Figure S2. DSC thermograms of compound 2. T c : crystallization temperature; T m melting point temperature; T g glass transition temperature. Figure S3. Molecular orbital energy level graph of complexes 2, 3 and 6 at the DFT/B3LYP level using different basis sets. Figure S4. Excitation and emission spectra together with PL lifetime curves for 1-6 in CHCl 3, MeCN, low-temperature MeOH:EtOH glass matrix and in solid state. Figure S5. Isodensity surface plots of the HSOMO and LSOMO for the complexes 1 6 at their T 1 state geometry calculated in MeCN medium at the TD-DFT/DFT/B3LYP level associated with the PCM model. Blue and grey colours show regions of positive and negative spin density values, respectively Figure S6. AFM images (10 µm x 10 µm) of the blend PVK with compound

3 Table S1. Comparison of experimental and theoretical bond lengths [Å] and angles [ ] for 1, 3, 4 and 6. Bond lengths Exp. Opt. Bond angles Exp. Opt. S 0 T 1 S 0 T 1 1 Re(1) C(1) 1.905(5) C(2) Re(1) C(1) 87.02(17) Re(1) C(2) 1.899(5) C(3) Re(1) C(1) 90.82(19) Re(1) C(3) 1.919(5) C(3) Re(1) C(2) 90.18(18) Re(1) N(1) 2.160(3) C(1) Re(1) N(1) (15) Re(1) N(2) 2.216(3) C(2) Re(1) N(1) 95.86(15) Re(1) Cl(1) (11) C(3) Re(1) N(1) 94.00(15) C(1) O(1) 1.154(5) C(1) Re(1) N(2) (14) C(2) O(2) 1.151(6) C(2) Re(1) N(2) (14) C(3) O(3) 1.121(5) C(3) Re(1) N(2) 96.55(14) Re(2) C(31) 1.918(5) N(1) Re(1) N(2) 74.61(11) Re(2) C(32) 1.881(5) C(1) Re(1) Cl(1) 89.59(14) Re(2) C(33) 1.902(5) C(2) Re(1) Cl(1) 91.12(14) Re(2) N(4) 2.164(3) C(3) Re(1) Cl(1) (12) Re(2) N(5) 2.216(3) N(1) Re(1) Cl(1) 85.53(8) Re(2) Cl(2) (10) N(2) Re(1) Cl(1) 82.11(8) C(31) O(4) 1.150(5) C(32) Re(2) C(31) 86.97(17) C(32) O(5) 1.167(5) C(33) Re(2) C(31) 87.85(18) C(33) O(6) 1.144(5) C(33) Re(2) C(32) 89.47(19) C(31) Re(2) N(4) (15) C(32) Re(2) N(4) 95.79(15) C(33) Re(2) N(4) 95.54(15) C(31) Re(2) N(5) (14) C(32) Re(2) N(5) (14) C(33) Re(2) N(5) 96.70(15) N(4) Re(2) N(5) 74.54(11) C(31) Re(2) Cl(2) 92.92(13) C(32) Re(2) Cl(2) 92.51(15) C(33) Re(2) Cl(2) (13) N(4) Re(2) Cl(2) 83.60(8) N(5) Re(2) Cl(2) 81.23(8) 3 Re(1) C(1) 1.929(8) C(2) Re(1) C(1) 86.5(3) Re(1) C(2) 1.898(7) C(3) Re(1) C(1) 93.7(3) Re(1) C(3) 1.969(8) C(3) Re(1) C(2) 90.7(3) Re(1) N(1) 2.174(5) C(1) Re(1) N(1) 175.3(2) Re(1) N(2) 2.231(5) C(2) Re(1) N(1) 95.1(2) Re(1) Cl(1) (18) C(3) Re(1) N(1) 90.7(3) C(1) O(1) 1.156(8) C(1) Re(1) N(2) 103.2(2) C(2) O(2) 1.156(8) C(2) Re(1) N(2) 169.5(2) C(3) O(3) 1.065(8) C(3) Re(1) N(2) 92.7(2) N(1) Re(1) N(2) 74.97(19) C(1) Re(1) Cl(1) 91.0(2) C(2) Re(1) Cl(1) 90.5(2) C(3) Re(1) Cl(1) 175.2(2) N(1) Re(1) Cl(1) 84.62(14) N(2) Re(1) Cl(1) 85.39(13) Re(1) C(1) 1.919(9) C(2) Re(1) C(1) 86.5(3) Re(1) C(2) 1.894(8) C(3) Re(1) C(1) 93.4(4) Re(1) C(3) 1.950(9) C(3) Re(1) C(2) 91.0(3) Re(1) N(1) 2.164(6) C(1) Re(1) N(1) 175.1(3) Re(1) N(2) 2.227(6) C(2) Re(1) N(1) 95.3(3) Re(1) Cl(1) 2.459(2) C(3) Re(1) N(1) 91.1(3) C(1) O(1) 1.163(9) C(1) Re(1) N(2) 102.9(3) C(2) O(2) 1.162(9) C(2) Re(1) N(2) 169.7(3) C(3) O(3) 1.063(10) C(3) Re(1) N(2) 92.5(3) N(1) Re(1) N(2) 75.0(2) C(1) Re(1) Cl(1) 91.0(2) C(2) Re(1) Cl(1) 90.7(3)

4 C(3) Re(1) Cl(1) 175.4(3) N(1) Re(1) Cl(1) 84.45(16) N(2) Re(1) Cl(1) 85.13(15) Re(1) C(1) 1.925(8) C(2) Re(1) C(1) 87.9(3) Re(1) C(2) 1.922(7) C(3) Re(1) C(1) 88.5(3) Re(1) C(3) 1.884(8) C(3) Re(1) C(2) 88.6(3) Re(1) N(1) 2.173(6) C(1) Re(1) N(1) 175.2(3) Re(1) N(2) 2.200(5) C(2) Re(1) N(1) 96.1(3) Re(1) Cl(1) (17) C(3) Re(1) N(1) 94.1(3) C(1) O(1) 1.159(9) C(1) Re(1) N(2) 101.7(2) C(2) O(2) 1.130(8) C(2) Re(1) N(2) 168.4(2) C(3) O(3) 1.167(9) C(3) Re(1) N(2) 98.1(3) N(1) Re(1) N(2) 74.03(19) C(1) Re(1) Cl(1) 93.6(2) C(2) Re(1) Cl(1) 91.8(2) C(3) Re(1) Cl(1) 177.8(2) N(1) Re(1) Cl(1) 83.71(14) N(2) Re(1) Cl(1) 81.12(13) Table S2. Short intra- and intermolecular contacts detected in the structures of the rhenium(i) complexes. D H A D H H A D A [Å] D H A [ ] 1 C(7) H(7) Cl(2)# (3) C(37) H(37) Cl(1)# (3) C(50) H(50) Cl(1)# (4) C(57) H(57) O(1)# (6) C(60) H(60) Cl(2)# (5) C(7) H(7) Cl(1)# (8) C(17) H(17) Cl(1)# (8) C(7) H(7) Cl(1)# (8) C(17) H(17) Cl(1)# (9) C(20) H(20) Cl(1)# (10) Symmetry codes: #1: -1+x,y,z; #2: 1+x,y,z; #3: 2-x,1-y,1-z; #4: x,1/2-y,-1/2+z; #5: x,3/2-y,-1/2+z 4

5 Table S3. Frontier molecular orbital composition (%) in the ground state for complex 1 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Orbital Energy Contribution (%) Character [ev] Re 3CO Cl R terpy LUMO d(re) + π*(co) + *(terpy) + *(R) LUMO d(re) + π*(co) + *(terpy) LUMO *(terpy) + d(re) + π*(co) + *(R) LUMO *(terpy) + d(re) LUMO *(terpy) + *(R) LUMO *(terpy) + d(re) HOMO (R) + d(re) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) + p(cl) + (R) HOMO d(re) + π(co) HOMO (R) HOMO (terpy) Table S4. Frontier molecular orbital composition (%) in the ground state for complex 2 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Orbital Energy Contribution (%) Character [ev] Re 3CO Cl R terpy LUMO d(re) + π*(co) + *(terpy) LUMO *(terpy) + π*(co) + π*(r) LUMO *(terpy) + π*(r) LUMO *(terpy) LUMO *(terpy) + *(R) LUMO *(terpy) + d(re) HOMO (R) + (terpy) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) HOMO (R) HOMO (terpy) Table S5. Frontier molecular orbital composition (%) in the ground state for complex 3 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Orbital Energy Contribution (%) Character [ev] Re 3CO Cl R terpy LUMO d(re) + π*(co) + *(terpy) LUMO *(terpy) + d(re) + π*(co) LUMO *(terpy) + d(re) LUMO *(terpy) LUMO *(terpy) + π*(r) LUMO *(terpy) + d(re) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) HOMO π(r) + (terpy) HOMO (terpy) HOMO (R) 5

6 Table S6. Frontier molecular orbital composition (%) in the ground state for complex 4 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Orbital Energy Contribution (%) Character [ev] Re 3CO Cl R terpy LUMO d(re) + π*(co) + *(terpy) LUMO *(terpy) + d(re) + π*(co) LUMO *(terpy) + d(re) LUMO *(terpy) LUMO *(terpy) + *(R) LUMO *(terpy) + d(re) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) HOMO (R) + (terpy) HOMO (terpy) HOMO (R) Table S7. Frontier molecular orbital composition (%) in the ground state for complex 5 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Orbital Energy Contribution (%) Character [ev] Re 3CO Cl R terpy LUMO d(re) + π*(co) + *(terpy) + *(R) LUMO *(terpy) + d(re) + π*(co) LUMO *(terpy) + d(re) LUMO *(terpy) LUMO *(terpy) + *(R) LUMO *(terpy) + d(re) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) + p(cl) HOMO d(re)+ π(co) HOMO (R) + (terpy) HOMO (terpy) HOMO (R) + (terpy) Table S8. Frontier molecular orbital composition (%) in the ground state for complex 6 calculated at the DFT/B3LYP/DEF2-TZVPD/6-31+G* level. Orbital Energy Contribution (%) Character [ev] Re 3CO Cl R terpy LUMO *(terpy) + d(re) + π*(co) LUMO d(re) + π*(co) + *(terpy) LUMO *(terpy) + d(re) + *(CO) LUMO *(terpy) + d(re) LUMO *(terpy) + *(R) LUMO *(terpy) HOMO (R) + (terpy) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) HOMO (terpy) + (R) HOMO (R) + (terpy) 6

7 Table S9. Frontier molecular orbital composition (%) in the ground state for complexes 2, 3, and 6 calculated at the DFT/B3LYP level using different basis sets. Compound Basis Set Orbital Energy Contribution (%) Character [ev] Re 3CO Cl R terpy LUMO *(terpy) + d(re) def2-tzvpd/ HOMO (R) + (terpy) 6-31+g* HOMO d(re) + π(co) + p(cl) LUMO *(terpy) 2 TZVP HOMO (R) + (terpy) HOMO d(re) + π(co) + p(cl) + (terpy) LUMO *(terpy) def2tzvpd HOMO (R) + (terpy) HOMO d(re) + π(co) + p(cl) Re 3CO Cl R terpy LUMO *(terpy) + d(re) HOMO d(re) + π(co) + p(cl) 3 6 def2-tzvpd/ 6-31+g* TZVP def2tzvpd def2-tzvpd/ 6-31+g* TZVP def2tzvpd HOMO d(re) + π(co) + p(cl) LUMO *(terpy) HOMO d(re) + π(co) + p(cl) + (terpy) HOMO d(re) + π(co) + p(cl) + (terpy) LUMO *(terpy) HOMO d(re) + π(co) + p(cl) HOMO d(re) + π(co) + p(cl) Re 3CO Cl R terpy LUMO *(terpy) HOMO (R) + (terpy) HOMO d(re) + π(co) + p(cl) LUMO *(terpy) + *(R) HOMO (R) + (terpy) HOMO d(re) + π(co) + p(cl) + (terpy) LUMO *(terpy) + *(R) + π*(co) HOMO (R) + (terpy) HOMO d(re) + π(co) + p(cl) Table S10. Main contributions to frontier molecular orbitals (%) in the ground state for complexes 2, 3, and 6 calculated at the DFT/B3LYP/TZ2P level using ADF software with ZORA relativistic approximation and COSMO solvent model. Compound MO orbital Energy [ev] Main contribution LUMO * terpy (91.84%) 2 HOMO R (81.92%) HOMO d Re (49.76%) + π CO (20.60%) + p Cl (18.56%) LUMO * terpy (80.51%) 3 HOMO d Re (50.61%) + π CO (18.06%) + p Cl (18.34%) HOMO d Re (46.43%) + π CO (18.22%) + p Cl (19.47%) LUMO * terpy (86.41%) 6 HOMO R (83.94%) HOMO d Re (49.44%) + π CO (20.76%) + p Cl (16.77%) 7

8 Table S11. The energies and characters of the selected spin-allowed electronic transitions for 1 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (10 3 ε; M -1 cm -1 ) (8.7) (37.9) (28.4) Major contribution (%) Calculated transitions Character E [ev] λ [nm] Oscillator strength H-1 L (65%) MLCT/LLCT H L (41%) ILCT/IL H-2 L (64%) MLCT/LLCT/ILCT H-3 L (91%) MLCT H L+1 (52%) ILCT H-5 L (64%) ILCT H-2 L+1 (72%) MLCT/LLCT H-1 L+2 (30%) MLCT/LLCT H L+2 (23%) H-9 L (25%) H-10 L (23%) H-3 L+2 (12%) H-2 L+2 (26%) H-3 L+2 (24%) H L+2 (19%) ILCT IL/LLCT LLCT/IL MLCT MLCT/LLCT/ILCT MLCT ILCT H L+3 (36%) ILCT H-5 L+1 (13%) IL/ILCT H-11 L (29%) H-5 L+1 (21%) LLCT/ILCT/IL IL/ILCT H-11 L (33%) LLCT/ILCT/IL H-5 L+1 (12%) IL/ILCT (126.9) H-15 L+1 (14%) IL H-14 L+1 (14%) IL/ILCT H L+14 (15%) LMCT/ILCT H-2 L+15 (11%) d-d/llct/ilct H-6 L+7 (26%) IL/ILCT H-6 L+10 (19%) IL H-10 L+6 (17%) LLCT/IL H-5 L+9 (11%) LLCT/IL H-7 L+7 (45%) LLCT/ILCT/IL ε molar absorption coefficient; H highest occupied molecular orbital; L lowest unoccupied molecular orbital 8

9 Table S12. The energies and characters of the selected spin-allowed electronic transitions for 2 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (10 3 ε; M -1 cm -1 ) (42.3) (90.7) (184) (235.1) Calculated transitions Major contribution (%) Character E [ev] λ [nm] Oscillator strength H L (97%) ILCT/IL H-2 L (97%) MLCT/LLCT H L+1 (98%) ILCT H-5 L (57%) IL H-1 L+2 (57%) MLCT/LLCT H L+3 (57%) ILCT H-5 L+1 (36%) IL/ILCT H-7 L+1 (17%) IL/ILCT H-8 L+1 (34%) IL/LLCT/ILCT H-7 L+1 (12%) IL/ILCT H-12 L (47%) LLCT/ILCT/IL H-13 L (34%) LLCT/ILCT/IL H-4 L+3 (27%) ILCT/IL H-5 L+5 (18%) LMCT/IL H-7 L+2 (17%) IL H-10 L+3 (15%) LLCT/IL/ILCT H-4 L+7 (12%) IL/ILCT H-11 L+2 (18%) IL H-7 L+8 (12%) IL/ILCT H L+14 (14%) LMCT/ILCT H-14 L+1 (13%) IL/ILCT H-6 L+7 (13%) IL/ILCT H-12 L+2 (44%) H-11 L+2 (25%) LLCT/ILCT IL ε molar absorption coefficient; H highest occupied molecular orbital; L lowest unoccupied molecular orbital 9

10 Table S13. The energies and characters of the selected spin-allowed electronic transitions for 3 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (10 3 ε; M -1 cm -1 ) (3.3) (19.6) (18.2) (178.2) Major contribution (%) Calculated transitions Character E [ev] λ [nm] Oscillator strength H-1 L (98%) MLCT/LLCT H-3 L (80%) ILCT H L+2 (57%) MLCT/LLCT H-2 L+2 (54%) MLCT H-3 L+1 (63%) ILCT H-9 L (68%) LLCT/IL H-4 L+1 (58%) IL/ILCT H-2 L+4 (28%) MLCT H-2 L+3 (18%) MLCT H-3 L+6 (56%) ILCT H-17 L (23%) IL/ILCT H-15 L (16%) IL/ILCT/LLCT H-11 L+1 (13%) LLCT/ILCT H-12 L+1 (24%) IL/ILCT H-3 L+8 (23%) ILCT H-11 L+2 (59%) LLCT H-5 L+6 (32%) ILCT H-6 L+7 (23%) H-18 L (15%) H-16 L+1 (13%) H-9 L+6 (11%) ILCT/IL ILCT/IL IL LLCT/IL/ILCT ε molar absorption coefficient; H highest occupied molecular orbital; L lowest unoccupied molecular orbital Table S14. The energies and characters of the selected spin-allowed electronic transitions for 4 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands. Experimental absorption ; nm (10 3 ε; M -1 cm -1 ) (5.4) Major contribution (%) Calculated transitions Character E [ev] λ [nm] Oscillator strength H-1 L (98%) MLCT/LLCT H-3 L (70%) ILCT H-1 L+1 (75%) MLCT/LLCT (32.5) H-4 L (59%) IL H L+2 (59%) MLCT/LLCT H-3 L+1 (60%) ILCT (30.8) H-9 L (69%) LLCT/IL H-4 L+1 (68%) IL/ILCT H-2 L+4 (28%) MLCT H-2 L+3 (18%) MLCT (71.8) H-15 L (19%) IL/ILCT H-12 L+1 (13%) LLCT H-13 L+1 (53%) ILCT/LLCT/IL H-5 L+5 (70%) LMCT/ILCT H-6 L+7 (23%) ILCT H-1 L+16 (10%) d-d/llct/mlct H-9 L+6 (22%) LLCT/IL H-4 L+10 (15%) LMCT/IL H-10 L+3 (11%) IL ε molar absorption coefficient; H highest occupied molecular orbital; L lowest unoccupied molecular orbital 10

11 Table S15. The energies and characters of the selected spin-allowed electronic transitions for 5 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands. Experimental absorption Major contribution ; nm (%) (10 3 ε; M -1 cm -1 Calculated transitions Character E [ev] λ [nm] Oscillator strength (9.5) H-1 L (98%) MLCT/LLCT (46.5) H-4 L (63%) ILCT H-3 L (68%) ILCT/IL H L+2 (51%) MLCT/LLCT (60.9) (125.8) H-8 L (53%) LLCT H-3 L+1 (56%) ILCT H-3 L+1 (23%) H L+3 (14%) H-9 L (12%) ILCT MLCT/LLCT LLCT H-2 L+4 (31%) H-2 L+3 (17%) H-4 L+7 (36%) H-5 L+3 (15%) H-13 L+1 (36%) H-11 L+2 (14%) H-5 L+6 (26%) H-3 L+8 (21%) H-5 L+5 (16%) MLCT MLCT IL/ILCT ILCT/IL IL/ILCT LLCT IL ILCT/LMCT LMCT H-3 L+9 (23%) ILCT/LMCT ε molar absorption coefficient; H highest occupied molecular orbital; L lowest unoccupied molecular orbital 11

12 Table S16. The energies and characters of the selected spin-allowed electronic transitions for 6 calculated with the TDDFT/B3LYP method, together with assignment to the experimental absorption bands Experimental absorption Major contribution ; nm (%) (10 3 ε; M -1 cm (16.5) Calculated transitions Character E [ev] λ [nm] Oscillator strength H L (98%) ILCT H-1 L (98%) MLCT/LLCT H L+1 (96%) ILCT (9.3) H L+2 (98%) ILCT (14.2) H L+3 (89%) ILCT/LMCT H-4 L (59%) IL/ILCT H-2 L+1 (69%) MLCT/LLCT (17.7) (178.2) H-5 L (42%) ILCT/IL H-1 L+2 (27%) MLCT/LLCT H-4 L+1 (56%) IL H-11 L (31%) H-3 L+5 (13%) H-6 L+1 (11%) IL MLCT IL/LLCT/ILCT H-10 L+1 (13%) H-4 L+5 (12%) H-1 L+11 (10%) H-4 L+9 (23%) H-13 L+1 (17%) H-9 L+6 (38%) H-11 L+3 (16%) H-4 L+9 (31%) H-13 L+1 (14%) H-9 L+6 (13%) LLCT/ILCT IL/ILCT d-d/lmct LMCT/IL/ILCT IL/ILCT LLCT/IL IL/LMCT LMCT/IL/ILCT IL/ILCT LLCT/IL

13 ε molar absorption coefficient; H highest occupied molecular orbital; L lowest unoccupied molecular orbital 13

14 Table S17. The energies and characters of the of two lowest vertical electronic transitions for 6 complex obtained in TDDFT calculations with using different functionals. a Solvent State E [ev] [nm] f Character B3LYP ACN S 1 S H L H-1 L IL/ILCT MLCT CHCl 3 S H L IL/ILCT S H-1 L MLCT BP86 ACN S 1 S H L H L+1 IL/ILCT IL/ILCT CHCl 3 S H L IL/ILCT S H-1 L MLCT B97 S H L IL/ILCT ACN H-1 L S H-1 L+4 MLCT CHCl 3 S H L H-1 L IL/ILCT/MLCT S H-1 L H L MLCT/IL/ILCT B97x ACN S H L IL/ILCT S H-1 L MLCT CHCl 3 S H L H-1 L IL/ILCT/MLCT S H-1 L H L MLCT/IL/ILCT CAM-B3LYP ACN S 1 S H L H-1 L IL/ILCT MLCT CHCl 3 S H L IL/ILCT S H-1 L MLCT LC-BLYP S H L IL/ILCT ACN H-1 L S H-1 L+4 MLCT CHCl 3 S H L H-1 L IL/ILCT/MLCT S H-1 L H L MLCT/IL/ILCT 14

15 1 6 Figure S1. A view of the crystal packing showing intermolecular stacking interactions for 1 and 6. 15

16 Figure S2. DSC thermograms of compound 2. T c : crystallization temperature; T m melting point temperature; T g glass transition temperature. 16

17 Figure S3. Molecular orbital energy level graph of complexes 2, 3 and 6 at the DFT/B3LYP level using different basis sets. 17

18 Complex Excitation and emission Lifetime 1 MeCN λ=442 nm λ=671 nm CHCl 3 solid 77K 2 18

19 MeCN CHCl 3 solid 77K MeCN 3 19

20 CHCl 3 solid 77K MeCN 4 CHCl 3 20

21 Solid 77K MeCN 5 λ=516 nm λ=666 nm CHCl 3 21

22 solid 77K MeCN 6 CHCl 3 Solid 22

23 77K Figure S4 Excitation and emission spectra together with PL lifetime curves for 1-6 in CHCl 3, MeCN, lowtemperature MeOH:EtOH glass matrix and in solid state. 23

24 Compound HSOMO LSOMO

25 6 Figure S5. Isodensity surface plots of the HSOMO and LSOMO for the complexes 1 6 at their T 1 state geometry calculated in MeCN medium at the TD-DFT/DFT/B3LYP level associated with the PCM model. Blue and grey colours show regions of positive and negative spin density values, respectively. Figure S6. AFM images (10 µm x 10 µm) of the blend PVK with compound 3 25