Electronic Supplementary Information. Controlling Photophysics of Styrylnaphthalimides through TICT, Fluorescence and E,Z-Photoisomerization Interplay

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1 Electronic Supplementry Mteril (ESI) for Physicl Chemistry Chemicl Physics. This journl is the Owner Societies 216 Electronic Supplementry Informtion Controlling Photophysics of Styrylnphthlimides through TICT, Fluorescence nd E,Z-Photoisomeriztion Interply Pvel A. Pnchenko, * Antonin N. Arkhipov, Olg A. Fedorov, Yuri V. Fedorov, Mrin A. Zkhrko, Dmitry E. Arkhipov, Gedimins Jonususks CONTENTS 1. Synthesis of the compounds NI S2 2. Clcultion of the sorption spectr of Z-isomers nd the rtios of quntum yields / S5 3. Light intensity mesurement S6 4. Chnges in the sorption spectr of NI1 3 upon irrdition.... S8 5. X-ry dt...s11 6. Study of E,Z-photoisomeriztion y NMR spectroscopy.....s12 7. Stedy-stte sorption nd emission spectr of NI1 3...S22 8. Trnsient sorption spectroscopy dt of NI S38 9. Plots of fluorescence quntum yield versus excited stte lifetime......s56 S1

2 1. Synthesis of the compounds NI1 3 Mterils nd generl methods. 4-Bromo-1,8-nphthlic nhydride 1 1 nd 4-romo-Nutyl-1,8-nphthlimide 2 2 were prepred y literture procedures strting from cenphthene. All other regents were purchsed from commercil sources nd were of the highest grde. Solvents were purified nd dried ccording to stndrd procedures. Melting points were mesured on Melt-temp melting point electrotherml pprtus nd were uncorrected. The rection course nd purity of the finl products ws followed y TLC on silic gel (DC-Alufolien Kieselgel 6 F 254, Merck). Column chromtogrphy ws conducted over silic gel (Kieselgel 6, prticle size 63- mm, Merck). Elementl nlyses were crried out in the Micronlysis Lortory of the A.N. Nesmeynov Institute of Orgnoelement Compounds. NMR mesurements. 1 H nd 13 C NMR spectr were recorded on n, Avnce 4 nd Avnce 6 spectrometers (Bruker) operting t 43 nd 62 MHz (for 1 H) nd 1.61 nd MHz (for 13 C) respectively. The mesurements were performed in DMSO-d 6 solutions. The chemicl shifts (given s d) were determined with n ccurcy of 1 ppm reltive to the signls corresponding to the residul solvents nd reclculted to the internl stndrd (TMS); the spin-spin coupling constnts (J) were mesured with n ccurcy of Hz. The numering of cron toms in the compounds NI1 3 used y us for the description of 1 H nd 13 C NMR spectr elow is shown in Scheme S1. The ssignment of 1 H nd 13 C signls is sed on 1 H COSY, HMBC nd HSQC NMR spectr. Scheme S1. Numering of cron toms in the compounds NI1 3 1 S. D. Ross, M. Finkelstein, R. C. Petersen, J. Am. Chem. Soc., 1958, 8, ; M. Shhid, P. Srivstv, A. Misr, New J. Chem., 211, 35, P. Stnge, K. Fumino, R. Ludwig, Chem. Eur. J., 213, 19, S2

3 Mss spectrometry. LC-ESI-MS nlyses were performed on Finnign LCQ Advntge mss spectrometer equipped with octopole ion-trp mss-nlyzer, MS Surveyor pump, Surveyor uto smpler, Schmidlin-L nitrogen genertor (Germny) nd Finnign X- Cliur 1.3 softwre for dt collecting nd processing. Acetonitrile (Pnrec, HPLC-grdient grde) ws used s the moile phse. The isocrtic elution ws mintined t flow rte of 5 µl min 1 without column. The effluent from LC ws pssed directly into the electrospry ion source without split. Positive electrospry ioniztion ws chieved using ioniztion voltge t 3 kv with temperture t 2 C. Isotope ptterns were clculted with Moleculr Weight Clcultor, Version 6.37 (Mtthew Monroe). Generl procedure for the synthesis of compounds NI1 3. A solution of 4-romo-Nutyl-1,8-nphthlimide 2 (1 mmol), Pd(OAc) 2 (1 mmol), tris-(ortho-tolyl)phosphine (6 mmol), triethylmine (1 ml) nd corresponding styrene (1.2 mmol) in dry DMF (1 ml) ws stirred t 15 C during h under rgon tmosphere. The mixture ws cooled to mient temperture then diluted with wter nd exctrcted with CH 2 Cl 2. The orgnic lyer ws dried with MgSO 4 nd evported in vcuum. The residue ws sujected to chromtogrphy on silic gel y using grdient mixture hexne ethyl cette nd then recrystllized from ethnol. 2- utyl-6-(4-methoxystyryl)-1h-enzo[d,e]isoquinoline-1,3(2h)-dione (NI1). Yield 38%. M.p С. 1 H NMR (43 MHz, CDCl 3, 22 ºС, δ / ppm, J / Hz):.99 (t, 3Н, H(12), J = 8.4), (m, 2Н, H(11)), (m, 2Н, H(1)), 3.88 (s, 3Н, ОСН 3 ), 4.2 (t, 2Н, H(9), J = 8.4), 6.98 (d, 2Н, H(16), H(18), J = 8.6), 7.31 (d, 1Н, Н(13), J = 16.), 7.59 (d, 2Н, H(15), H(19), J = 8.6), (m, 2Н, Н(13), Н(6)), 7.98 (d, 1Н, Н(3), J = 7.7), (m, 2Н, Н(2), Н(5)), 8.63 (d, 1Н, Н(7), J = 8.3). 13 C NMR (15.93 MHz, CDCl 3, 22 С, δ / м. д., J / Hz): (С(12)), 2.89 (С(11)), 3.56 (С(1)), 45 (С(9)), (ОСН 3 ), (С(16), С(18)), (С(1)), (С(13а)), (С(8)), (С(3)), (С(8а)), (С(6)), (С(15), С(19)), (С(14)), 136 (С(4а)), 131 (С(5)), 133 (С(7)), (С(2)), (С(13)), (С(4)), (С(17)), (С(8)), (С(8с)). ESI-MS in MeCN, clculted for [M] +, m/z: ; found: Elementl nlysis: clculted (%) for C 25 H 23 NO 3 (MW ): С 77.89, Н 6.2, N 3.64; found С 77.94, Н 6.11, N utyl-6-(3,4-dimethoxystyryl)-1H-enzo[d,e]isoquinoline-1,3(2H)-dione (E-NI2). Yield 18%. M.p С. 1 H NMR (43 MHz, CDCl 3, 21 ºС, δ / ppm, J / Hz):.99 (t, 3Н, H(12), J = 8.4), (m, 2Н, H(11)), (m, 2Н, H(1)), 3.96 (s, 3Н, ОСН 3 ), 4.2 (s, 3Н, ОСН 3 ), 4.2 (t, 2Н, H(9), J = 8.4), 6.94 (d, 1Н, H(18), J = 8.2), (m, 2Н, H(15), H(19)), 7.3 (d, 1Н, Н(13), J = 16.), (m, 2Н, Н(13), Н(6)), 7.98 (d, 1Н, Н(3), J = 7.7), (м, 2Н, Н(2), Н(5)), 8.65 (d, 1Н, Н(7), J = 8.3). 13 C NMR (15.93 MHz, CDCl 3, 21 С, δ / ppm, J / Hz): (С(12)), 2.89 (С(11)), 3.56 (С(1)), 45 (С(9)), S3

4 55.26 (2 ОСН 3 ), (С(19)), (С(18)), (С(15)), (С(1)), (С(13а)), (С(8)), (С(3)), (С(6)), (С(8а)), (С(14)), (С(4а)), (С(5)), (С(7)), (С(2)), (С(13)), (С(4)), (С(16)), 157 (С(17)), (С(8)), (С(8с)). ESI-MS in MeCN, clculted for [M] +, m/z: ; found: Elementl nlysis: clculted (%) for C 26 H 25 NO 4 (MW ): С 75.17, Н 6.7, N 3.37; found С 75.21, Н 6.13, N utyl-6-(4-(dimethylmino)styryl)-1Henzo[d,e]isoquinoline-1,3(2H)-dione (E-NI3). Yield 28%. M.p С. 1 H NMR (43 MHz, CDCl 3, 23 ºС, δ / ppm, J / Гц):.98 (t, 3Н, H(12), J = 8.4), (m, 2Н, H(11)), (m, 2Н, H(1)), 3.7 (s, 6Н, N(СН 3 ) 2 ), 4.19 (t, 2Н, H(9), J = 8.4), (m, 2Н, Н(16), Н(18)), 7.33 (d, 1Н, Н(13), J = 16.), 7.58 (d, 2Н, Н(15), Н(19), J = 8.6), (m, 2Н, Н(6), Н(13а)), 7.99 (d, 1Н, Н(3), J = 7.7), (m, 3Н, Н(2), Н(5), Н(7)). 13 C NMR (15.93 МГц, CDCl 3, 22 С, δ / ppm, J / Гц): 13.2 (С (12)), 23 (С (11)), (С(1)), (С(9)), (2 N(СН 3 ) 2 ), (С(16), С(18)), (С(13а)), (С(1)), (С(3)), (С(8)), (С(8а)), (С(6)), (С(15)), С(19)), (С(14)), 139 (С(4а)), (С(5)), (С(7)), (С(2)), (С(13)), (С(4)), (С(17)), (С(8)), (С(8с)). ESI-MS in MeCN, clculted for [M] +, m/z: 398.2; found: Elementl nlysis: clculted (%) for C 26 H 26 N 2 O 2 (MW 398.5): С 78.35, Н 6.58, N 7.3; found С 78.43, Н 6.56, N 7.8. S4

5 2. Clcultion of the sorption spectr of Z-isomers nd the rtios of quntum yields / The Fisher method ws used to clculte the sorption spectr of Z-isomers. First, we recorded the sorption spectrum of solution of dye s E-isomer with known concentrtion C L nd the spectr of this solution in E,Z-photosttionry sttes otined y irrdition with light t two wvelengths λ = 365 nd 436 nm. 3 Using the ssumption tht the rtio of the quntum yields of the Z- nd E-isomers ( / ) does not depend on the irrdition wvelength, the frction of the Z-isomer in the photosttionry stte creted y light with λ = 436 nm ws clculted from these spectr using the formul: 436 D 365 / D365 - D = 1+ D / D - n / D 436 ( 1+ D / D ) where Δ 365 (Δ 436 ) is the difference etween the opticl density of the solution in the photosttionry stte creted y light with λ = 365 nm (436 nm) t wvelength of 365 nm (436 nm) nd the opticl density of the strting solution of the E-isomer t λ = 365 nm (436 nm); 365 E 436 E ( D - D ) ( D D ) n / =, where 365 D436 nd D 436 re the opticl densities of the solution in the photosttionry sttes creted y light with λ = 365 nd 436 nm, respectively, t the wvelength where the opticl density chnge is the highest (λ = 436 nm); E D 436 is the opticl density of the solution of the strting E-isomer t the wvelength where the sme wvelength (λ = 436 nm). Once α 436 ws determined, the opticl density of the pure Z-isomer ws clculted: D D ( l) = Z 436 ( l) - ( ) D where D E (λ) is the spectrum of the strting solution of the E-isomer; D 436 (λ) is the spectrum of E ( l) the solution in the photosttionry stte creted y light with λ = 436 nm. After tht, the rtio of the quntum yields of the direct nd reverse photoisomeriztion rections ws clculted: where 436 e E nd = (1 ) 436 e Z re the molr sorption coefficients for the E- nd Z-isomer, respectively, t λ = 436 nm; d is the opticl pth length tht equls 1 cm. In the clcultion of the theoreticl spectrum of the Z-isomer we ssume tht the C L vlues for the isomers re equl since the entire E-isomer is converted to the Z-isomer. 3 For the compound NI3 in cyclohexne, the wvelengths λ = 45 nd 436 nm were used. S5

6 3. Light intensity mesurement The solute light intensity ws mesured using chemicl ferrioxlte ctinometer. With chemicl ctinometer, the numer of light qunt is determined from the mount of the photochemicl rection product with quntum yield known in dvnce: N I = ª D F t (1-1 - ) where N is the numer of moles of the product formed; Ф is the quntum yield of product formtion; t is the irrdition time; (1-1 -D ) is the coefficient representing the frction of sored light (it usully equls 1, since the concentrtion of the ctinometer is most commonly chosen to ensure complete light sorption). N F t A ferrioxlte ctinometer is solution of the K 3 Fe(C 2 O 4 ) 3 ] 3H 2 O complex slt in N sulfuric cid. Under exposure to light, it undergoes the following rection: 2[Fe(С 2 О 4 ) 3 ] 3 2Fe C 2 O СО 2 The quntum yield of ferrioxlte decomposition depends on the wvelength. Ferrous iron tht is formed upon photolysis gives colored complex with 1,1-phennthroline. The complex of 1,1-phennthroline with Fe 2+ ions is formed reltively slowly t ph = 2.5 nd considerly more quickly t ph In this ph rnge, the resulting complex is stle to UV nd visile light, nd its sorption t 51 nm chnges linerly with vrition in the concentrtion of Fe 2+ ions. By mesuring the color intensity of this complex, one cn determine the mount of Fe 2+ ions formed nd hence the intensity of the light source. To mesure the light intensity y the ferrioxlte method, solution of potssium ferrioxlte is used with concentrtion tht, s rule, ensures complete light sorption t the irrdition wvelength. The following solutions re required to perform the mesurements: А) solution of potssium ferrioxlte in N sulfuric cid, where the required concentrtion of potssium ferrioxlte is selected depending on the irrdition wvelength; B) % queous solution of 1,1-phennthroline; C) uffer solution: 6 ml of 1 N sodium cette + 36 ml of 1 N sulfuric cid + wter (to dilute the solution to the volume of 1 ml). The light intensity is determined s follows. A preset volume (2 ml) of ctinometer solution A is irrdited with stirring for such time period t tht the opticl density chnges y.6 (e.g., t =, 6, 12, 24, 48 s). After tht, V 2 (e.g., 1.5 ml) of the irrdited solution is trnsferred into mesuring flsk of volume V 3 (e.g., 2 ml), then (8 V 2 ) ml of N sulfuric cid, 1.6 ml of solution B nd 4 ml of solution C re dded into the flsk. The solution volume in the flsk is rought to the mrk with wter, stirred nd kept in the drk for 3 min in S6

7 order to fully complete the complextion rection. Then, the opticl density of the solution of the resulting complex of ferrous iron with 1,1-phennthroline is mesured t 51 nm. The sme opertions re crried out with V 1 of the non-irrdited ctinometer solution used in the reference cell. the formul: The numer of moles of ferrous ions formed during photolysis, N 2+, is determined y = 1-3 N Fe V1 V3 D V l e where V 1 is the volume of the irrdited ctinometer olution, ml; V 2 is the volume of the irrdited ctinometer tken for the nlysis, ml; V 3 is the finl volume to which the V 2 solution ws diluted, ml; D is the solution opticl density t 51 nm; l is the opticl pth length, cm; nd ε is the extinction coefficient of the 1,1-phennthroline Fe 2+ complex t 51 nm tht equls M -1 cm -1. If N 2+, the F + Fe Fe 2 vlue t certin irrdition wvelength nd the irrdition time t re known, the intensity of incident light cn e clculted s: I = N 2+ Fe, [Einstein/s] F t Fe S7

8 4. Chnges in the sorption spectr of NI1 3 upon irrdition.5 Asornce E-NI1 E-NI1+Z-NI1@365nm E-NI1+Z-NI1@436nm Z-NI Figure S1. Asorption spectr of E- nd Z-isomers of NI1 nd photottionry sttes otined using light with λ = 365 nd 436 nm in cyclohexne. The spectrum of Z-isomer is clculted y Fisher method. The concentrtion of NI1 is М..5 E-NI2 E-NI2+Z-NI2@365nm E-NI2+Z-NI2@436nm Z-NI1 Asornce Figure S2. Asorption spectr of E- nd Z-isomers of NI2 nd photottionry sttes otined using light with λ = 365 nd 436 nm in cyclohexne. The spectrum of Z-isomer is clculted y Fisher method. The concentrtion of NI2 is М..5 E-NI3 E-NI3+Z-NI3@45nm E-NI3+Z-NI3@436nm Z-NI3 Asornce Figure S3. Asorption spectr of E- nd Z-isomers of NI2 nd photottionry sttes otined using light with λ = 45 nd 436 nm in cyclohexne. The spectrum of Z-isomer is clculted y Fisher method. The concentrtion of NI2 is М. S8

9 E-NI1 Z-NI1 Asornce Figure S4. Asorption spectr of E- nd Z-isomers of NI1 nd photottionry sttes otined using light with λ = 365 nd 436 nm in toluene. The spectrum of Z-isomer is clculted y Fisher method. The concentrtion of NI1 is М. E-NI2 E-NI2+Z-NI2@436nm E-NI2+Z-NI2@365nm Z-NI1 Asornce Figure S5. Asorption spectr of E- nd Z-isomers of NI2 nd photottionry sttes otined using light with λ = 365 nd 436 nm in toluene. The spectrum of Z-isomer is clculted y Fisher method. The concentrtion of NI2 is М. E-NI3 E-NI3+Z-NI3@436nm E-NI3+Z-NI3@365nm Z-NI3 Asornce nm Figure S6. Asorption spectr of E- nd Z-isomers of NI3 nd photottionry sttes otined using light with λ = 365 nd 436 nm in toluene. The spectrum of Z-isomer is clculted y Fisher method. The concentrtion of NI3 is М. S9

10 .5 Asornce E-NI Figure S7. Asorption spectr of E -isomers of NI1 nd photottionry sttes otined using light with λ = 365 nd 436 nm in cetonitrile. The concentrtion of NI1 is М..5 E-NI2 E-NI2+Z-NI2@365nm E-NI2+Z-NI2@436nm Asornce nm Figure S8. Asorption spectr of E -isomers of NI2 nd photottionry sttes otined using light with λ = 365 nd 436 nm in cetonitrile. The concentrtion of NI2 is М..5 Asornce E-NI3 E-NI2+Z-NI2@45nm E-NI2+Z-NI2@436nm Figure S9. Asorption spectr of E -isomers of NI3 nd photottionry sttes otined using light with λ = 45 nd 436 nm in cetonitrile. The concentrtion of NI3 is М. S1

11 5. X-ry dt Tle S1. Crystllogrphic dt nd refinement prmeters for the structures NI1 3 NI1 NI2 NI3 Formul C 25 H 23 NO 3 C 26 H 25 NO 4 C 26 H 26 N 2 O 2 Moleculr weight T, K Crystl system Monoclinic Monoclinic Triclinic Spce group P2 1 /c P2 1 /n P-1 Z 4 4 4, Å (1) (7) 7.466(13), Å (5) 9.474(5) (2) c, Å 15.33(9) (1) 282(3) α, (4) β, (1) (1) (4) γ, (4) V, Å (2) (2) 243.6(6) Density, g cm μ, cm F() θ mx, Reflections collected Independent reflections (R int ) 5579 (443) 6178 (442) 7886 (22) Numer of reflections with I > 2σ(I) Prmeters R 1 [I > 2 σ(i)] wr 2 (ll independent reflections) GOF ρ min /ρ mx, e Å -3 66/-24 79/-56 31/-72 S11

12 6. Study of E,Z-photoisomeriztion y NMR spectroscopy ) MeO O toluene toluene N n-bu E-NI1 O OMe Z-NI1 O N n-bu O ) Chemiclshift /ppm MeO toluene toluene MeO O E-NI2 N n-bu O OMe OMe Z-NI2 O N n-bu O Chemicl shift/ppm c) toluene Me 2N O toluene E-NI3 N O n-bu NMe 2 Z-NI3 O N n-bu O Chemicl shift /ppm Figure S1. 1 H NMR spectrum of NI1 () NI2 () nd NI3 (c) efore (top) nd fter (ottom) irrdition t 436 nm in toluene-d 8. The signls of Z-isomers re mrked with red rs. The concentrtion of NI1 3 is M. S12

13 Figure S11. 1 H COSY spectrum of compound NI1 in toluene-d 8. Figure S12. Aromtic prt of 1 H COSY spectrum of compound NI1 in toluene-d 8. S13

14 Figure S13. HSQC spectrum of compound NI1 in toluene-d 8. Figure S14. Aromtic prt of HSQC spectrum of compound NI1 in toluene-d 8. S14

15 Figure S15. HMBC spectrum of compound NI1 in toluene-d 8. Figure S16. Aromtic prt of HMBC spectrum of compound NI1 in toluene-d 8. S15

16 Figure S17. 1 H COSY spectrum of compound NI2 in toluene-d 8. Figure S18. Aromtic prt of 1 H COSY spectrum of compound NI2 in toluene-d 8. S16

17 Figure S19. HSQC spectrum of compound NI2 in toluene-d 8. Figure S2. Aromtic prt of HSQC spectrum of compound NI2 in toluene-d 8. S17

18 Figure S21. HMBC spectrum of compound NI2 in toluene-d 8. Figure S22. Aromtic prt of HMBC spectrum of compound NI2 in toluene-d 8. S18

19 Figure S23. 1 H COSY spectrum of compound NI3 in toluene-d 8. Figure S24. Aromtic prt of 1 H COSY spectrum of compound NI3 in toluene-d 8. S19

20 Figure S25. HSQC spectrum of compound NI3 in toluene-d 8. Figure S26. Aromtic prt of HSQC spectrum of compound NI3 in toluene-d 8. S2

21 Figure S27. HMBC spectrum of compound NI3 in toluene-d 8. Figure S28. Aromtic prt of HMBC spectrum of compound NI3 in toluene-d 8. S21

22 7. Stedy-stte sorption nd emission spectr of NI Asorption 5 5 Intensity /.u Figure S29. Asorption () nd emission () spectrum of compound NI1 in propylene cronte. The concentrtion of NI1 is M. Excittion wvelength 37 nm Asorption 5 5 Intensity /.u Figure S3. Asorption () nd emission () spectrum of compound NI1 in DMSO. The concentrtion of NI1 is M. Excittion wvelength 42 nm Asorption 5 Intensity /.u Figure S31. Asorption () nd emission () spectrum of compound NI1 in cetonitrile. The concentrtion of NI1 is M. Excittion wvelength 365 nm. S22

23 Asorption Intensity /.u Figure S32. Asorption () nd emission () spectrum of compound NI1 in cetone. The concentrtion of NI1 is M. Excittion wvelength 4 nm Asorption Intensity /.u Figure S33. Asorption () nd emission () spectrum of compound NI1 in 3-methylutnone-2. The concentrtion of NI1 is M. Excittion wvelength 4 nm Asorption Intensity /.u Figure S34. Asorption () nd emission () spectrum of compound NI1 in 4-methylpentnone-2. The concentrtion of NI1 is M. Excittion wvelength 435 nm. S23

24 Asorption Intensity /.u Figure S35. Asorption () nd emission () spectrum of compound NI1 in 1,2-dimethoxyethne. The concentrtion of NI1 is M. Excittion wvelength 35 nm Asorption Intensity /.u Figure S36. Asorption () nd emission () spectrum of compound NI1 in ethylcette. The concentrtion of NI1 is M. Excittion wvelength 365 nm Asorption Intensity /.u Figure S37. Asorption () nd emission () spectrum of compound NI1 in diethyl ether. The concentrtion of NI1 is M. Excittion wvelength 365 nm. S24

25 Asorption Intensity /.u Figure S38. Asorption () nd emission () spectrum of compound NI1 in toluene. The concentrtion of NI1 is M. Excittion wvelength 415 nm Asorption Intensity /.u Figure S39. Asorption () nd emission () spectrum of compound NI1 in cyclohexne. The concentrtion of NI1 is M. Excittion wvelength 365 nm Asorption Intensity /.u Figure S4. Asorption () nd emission () spectrum of compound NI1 in methnol. The concentrtion of NI1 is M. Excittion wvelength 35 nm. S25

26 Asorption Intensity /.u Figure S41. Asorption () nd emission () spectrum of compound NI1 in ethnol. The concentrtion of NI1 is M. Excittion wvelength 35 nm Asorption Intensity /.u Figure S42. Asorption () nd emission () spectrum of compound NI1 in n-utnol. The concentrtion of NI1 is M. Excittion wvelength 35 nm Asorption Intensity /.u Figure S43. Asorption () nd emission () spectrum of compound NI1 in n-hexnol. The concentrtion of NI1 is M. Excittion wvelength 35 nm. S26

27 Asorption Intensity /.u Figure S44. Asorption () nd emission () spectrum of compound NI1 in n-decnol. The concentrtion of NI1 is M. Excittion wvelength 35 nm Asorption Intensity /.u Figure S45. Asorption () nd emission () spectrum of compound NI2 in propylene cronte. The concentrtion of NI2 is M. Excittion wvelength 4 nm Asorption Intensity /.u Figure S46. Asorption () nd emission () spectrum of compound NI2 in DMSO. The concentrtion of NI2 is M. Excittion wvelength 4 nm. S27

28 Asorption Intensity /.u Figure S47. Asorption () nd emission () spectrum of compound NI2 in cetonitrile. The concentrtion of NI2 is M. Excittion wvelength 38 nm Asorption Intensity /.u Figure S48. Asorption () nd emission () spectrum of compound NI2 in cetone. The concentrtion of NI2 is M. Excittion wvelength 35 nm Asorption Intensity /.u Figure S49. Asorption () nd emission () spectrum of compound NI2 in 3-methylutnone-2. The concentrtion of NI2 is M. Excittion wvelength 37 nm. S28

29 Asorption Intensity /.u Figure S5. Asorption () nd emission () spectrum of compound NI2 in 4-methylpentnone-2. The concentrtion of NI2 is M. Excittion wvelength 37 nm..5 8 Asorption Intensity /.u Figure S51. Asorption () nd emission () spectrum of compound NI2 in 1,2-dimethoxyethne. The concentrtion of NI2 is M. Excittion wvelength 36 nm Asorption Intensity /.u Figure S52. Asorption () nd emission () spectrum of compound NI2 in ethylcette. The concentrtion of NI2 is M. Excittion wvelength 4 nm. S29

30 .5 8 Asorption Intensity /.u Figure S53. Asorption () nd emission () spectrum of compound NI2 in diethyl ether. The concentrtion of NI2 is M. Excittion wvelength 36 nm..5 4 Asorption Intensity /.u Figure S54. Asorption () nd emission () spectrum of compound NI2 in toluene. The concentrtion of NI2 is M. Excittion wvelength 415 nm Asorption Intensity /.u Figure S55. Asorption () nd emission () spectrum of compound NI2 in cyclohexne. The concentrtion of NI2 is M. Excittion wvelength 4 nm. S3

31 Asorption Intensity /.u Figure S56. Asorption () nd emission () spectrum of compound NI2 in methnol. The concentrtion of NI2 is M. Excittion wvelength 39 nm Asorption Asorption Figure S57. Asorption () nd emission () spectrum of compound NI2 in ethnol. The concentrtion of NI2 is M. Excittion wvelength 4 nm Asorption Intensity /.u Figure S58. Asorption () nd emission () spectrum of compound NI2 in n-utnol. The concentrtion of NI2 is M. Excittion wvelength 4 nm. S31

32 Asorption Intensity /.u Figure S59. Asorption () nd emission () spectrum of compound NI2 in n-hexnol. The concentrtion of NI2 is M. Excittion wvelength 39 nm Asorption Intensity /.u Figure S6. Asorption () nd emission () spectrum of compound NI2 in n-decnol. The concentrtion of NI2 is M. Excittion wvelength 4 nm Asorption Intensity /.u Figure S61. Asorption () nd emission () spectrum of compound NI3 in propylene cronte. The concentrtion of NI3 is M. Excittion wvelength 469 nm. S32

33 Asorption Intensity /.u Figure S62. Asorption () nd emission () spectrum of compound NI3 in DMSO. The concentrtion of NI3 is M. Excittion wvelength 48 nm..5 6 Asorption Intensity /.u Figure S63. Asorption () nd emission () spectrum of compound NI3 in cetonitrile. The concentrtion of NI3 is M. Excittion wvelength 4 nm Asorption Intensity /.u Figure S64. Asorption () nd emission () spectrum of compound NI3 in cetone. The concentrtion of NI3 is M. Excittion wvelength 4 nm. S33

34 .5 3 Asorption Intensity /.u Figure S65. Asorption () nd emission () spectrum of compound NI3 in 3-methylutnone-2. The concentrtion of NI3 is M. Excittion wvelength 4 nm..5 4 Asorption Intensity /.u Figure S66. Asorption () nd emission () spectrum of compound NI3 in 4-methylpentnone-2. The concentrtion of NI3 is M. Excittion wvelength 4 nm Asorption Intensity /.u Figure S67. Asorption () nd emission () spectrum of compound NI3 in 1,2-dimethoxyethne. The concentrtion of NI3 is M. Excittion wvelength 4 nm. S34

35 Asorption Intensity /.u Figure S68. Asorption () nd emission () spectrum of compound NI3 in ethylcette. The concentrtion of NI3 is M. Excittion wvelength 425 nm..5 8 Asorption Intensity /.u Figure S69. Asorption () nd emission () spectrum of compound NI3 in diethyl ether. The concentrtion of NI3 is M. Excittion wvelength 51 nm Asorption Intensity /.u Figure S7. Asorption () nd emission () spectrum of compound NI3 in toluene. The concentrtion of NI3 is M. Excittion wvelength 46 nm. S35

36 Asorption Intensity /.u Figure S71. Asorption () nd emission () spectrum of compound NI3 in cyclohexne. The concentrtion of NI3 is M. Excittion wvelength 45 nm Asorption Intensity /.u Figure S72. Asorption () nd emission () spectrum of compound NI3 in methnol. The concentrtion of NI3 is M. Excittion wvelength 43 nm Asorption Intensity /.u Figure S73. Asorption () nd emission () spectrum of compound NI3 in ethnol. The concentrtion of NI3 is M. Excittion wvelength 47 nm. S36

37 Asorption Intensity /.u Figure S74. Asorption () nd emission () spectrum of compound NI3 in n-utnol. The concentrtion of NI3 is M. Excittion wvelength 47 nm..5 8 Asorption Intensity /.u Figure S75. Asorption () nd emission () spectrum of compound NI3 in n-hexnol. The concentrtion of NI3 is M. Excittion wvelength 47 nm Asorption Intensity /.u Figure S76. Asorption () nd emission () spectrum of compound NI3 in n-decnol. The concentrtion of NI3 is M. Excittion wvelength 47 nm. S37

38 8. Trnsient sorption spectroscopy dt of NI1 3 Time dely / ps Asornce chnge incresing DA ps Wvelength/nm c 1 8 Intensity /.u Figure S77. Time-resolved TRABS mp (), TRABS spectrum t 2.5 ps time dely () nd stedy-stte fluorescence spectrum (c) of compound NI1 in cyclohexne. S38

39 Time dely + /ps Asornce chnge incresing DA Wvelength/nm ps 3 ps 7 ps 4 ps c DA nm 575 nm 69 nm ps ps 1 1 Time dely +.5 / ps Figure S78. Time-resolved TRABS mp (), TRABS spectrum t different time delys () nd TRABS kinetic curves t different wvelengths (c) for the compound NI1 in diethyl ether. S39

40 Time dely +.8 / ps E Asornce chnge incresing DA 8 6 ps.7 ps 1.2 ps 4.5 ps c 2 DA 8 TS134 DME 48 nm 565 nm 675 nm ps ps 1 1 Time dely + 1 / ps Figure S79. Time-resolved TRABS mp (), TRABS spectrum t different time delys () nd TRABS kinetic curves t different wvelengths (c) for the compound NI1 in 1,2-dimethoxyethne. S4

41 Time dely / ps E E Asornce chnge incresing ps.5 ps.7 ps 1 ps 2 DA wvelength / nm c DA ps 48 nm 575 nm 65 nm Time dely / ps Figure S8. Time-resolved TRABS mp (), TRABS spectrum t different time delys () nd TRABS kinetic curves t different wvelengths (c) for the compound NI1 in cetonitrile. S41

42 Time dely / ps E Asornce chnge incresing ps.5 ps 1.5 ps 5 ps 3 ps DA 5 c nm 575 nm ps DA ps Time dely / ps Figure S81. Time-resolved TRABS mp (), TRABS spectrum t different time delys () nd TRABS kinetic curves t different wvelengths (c) for the compound NI1 in methnol. S42

43 1 Time dely / ps Asornce chnge incresing ps.8 ps 3 ps 3 ps 5 ps c 8 6 DA ps 8 ps 49 nm 58 nm ps Time dely / ps Figure S82. Time-resolved TRABS mp (), TRABS spectrum t different time delys () nd TRABS kinetic curves t different wvelengths (c) for the compound NI1 in n-propnol. S43

44 Time dely +1.3 / ps E E Asornce chnge incresing DA c 6 5 Fluorescence intensity /.u Figure S83. Time-resolved TRABS mp (), TRABS spectrum () nd stedy-stte fluorescence spectrum (c) of compound NI2 in cyclohexne. S44

45 Time dely +1.5 / ps Asornce chnge incresing DA ps 1 ps 3 ps 2 ps c nm 6 nm 4 DA ps ps Time dely / ps Figure S84. Time-resolved TRABS mp (), TRABS spectrum t different time delys () nd TRABS kinetic curves t different wvelengths (c) for the compound NI2 in diethyl ether. S45

46 Time dely / ps E Asornce chnge incresing DA 5 5 ps.5 ps.8 ps 1.4 ps 3 ps 1 ps c nm 595 nm 6 4 DA 2.83 ps ps Time dely / ps Figure S85. Time-resolved TRABS mp (), TRABS spectrum t different time delys () nd TRABS kinetic curves t different wvelengths (c) for the compound NI2 in 1,2-dimethoxyethne. S46

47 Time dely / ps E Asornce chnge incresing DA 5 ps 5 ps.5 ps 1 ps 5 ps c 5 TS138 ACN 49 nm 595 nm 725 nm 4 ps DA ps -5 7 ps.63 ps Time dely / ps Figure S86. Time-resolved TRABS mp (), TRABS spectrum t different time delys () nd TRABS kinetic curves t different wvelengths (c) for the compound NI2 in cetonitrile. S47

48 Time dely / ps E Asornce chnge incresing ps.6 ps 5 ps 3 ps DA c ps 51 nm 59 nm 725 nm 6 4 DA ps 13 ps Time dely / ps Figure S87. Time-resolved TRABS mp (), TRABS spectrum t different time delys () nd TRABS kinetic curves t different wvelengths (c) for the compound NI2 in methnol. S48

49 Time dely / ps E Asornce chnge incresing ps 2.5 ps 1 ps 5 ps 5 DA -5 c nm 61 nm 725 nm DA ps 21 ps Time dely / ps Figure S88. Time-resolved TRABS mp (), TRABS spectrum t different time delys () nd TRABS kinetic curves t different wvelengths (c) for the compound NI2 in n-propnol. S49

50 Time dely / ps E Asornce chnge incresing DA c 5 Fluorescence intendsity /.u Figure S89. Time-resolved TRABS mp (), TRABS spectrum () nd stedy-stte fluorescence spectrum (c) of compound NI3 in cyclohexne. S5

51 Time dely / ps Asornce chnge incresing DA -5 - ps 1 ps 2 ps 2 ps Figure S9. Time-resolved TRABS mp () nd TRABS spectrum t different time delys () for the compound NI3 in diethyl ether. S51

52 1 Time dely / ps Asornce chnge incresing ps 3 ps 1 ps 5 ps DA Figure S91. Time-resolved TRABS mp () nd TRABS spectrum t different time delys () for the compound NI3 in 1,2-dimethoxyethne. S52

53 Time dely / ps Asornce chnge incresing ps ps.6 ps 5 ps DA Figure S92. Time-resolved TRABS mp () nd TRABS spectrum t different time delys () for the compound NI3 in cetonitrile. S53

54 Time dely / ps Asornce chnge incresing ps.5 ps.9 ps 1 ps 2 ps A Figure S93. Time-resolved TRABS mp () nd TRABS spectrum t different time delys () for the compound NI3 in methnol. S54

55 1 Time dely / ps E E Asornce chnge incresing ps 3.5 ps 15 ps 1 ps 4 2 DA Figure S94. Time-resolved TRABS mp () nd TRABS spectrum t different time delys () for the compound NI3 in n-propnol. S55

56 9. Plots of fluorescence quntum yield versus excited stte lifetime 2 j fl t / ns Eqution y = + *x Weight No Weightin Residul Sum of 4835 Squres Person's r Adj. R-Squre Vlue Stndrd Erro B Intercept -- B Slope j fl t / ns Eqution y = + *x Weight No Weighting Residul Sum of 6125 Squres Person's r Adj. R-Squre Vlue Stndrd Erro B Intercept -- B Slope 4 75 c j fl Eqution y = + *x Weight No Weightin Residul Sum of 252 Squres Person's r Adj. R-Squre Vlue Stndrd Erro B Intercept B Slope t / ns Figure S95. Plot of fluorescence quntum yield ( ) versus excited stte lifetime ( ) for the compound NI1 () NI2 () nd NI3 (c). The solvents re numered ccording to the sequence presented in Tle 1 (see the mnuscript text). The stright lines with zero intercepts represent the est lest-squre fit to the dt. The inserts show the fitting prmeters. S56