Temperature- and excitation wavelengthdependent emission in a manganese(ii) complex

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1 Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 218 Electronic Supplementary Information Temperature- and excitation wavelengthdependent emission in a manganese(ii) complex Alexei S. Berezin, a Katerina A. Vinogradova,* a,b Vladimir A. Nadolinny, a Taisiya S. Sukhikh, a,b Viktor P. Krivopalov, c Elena B. Nikolaenkova c and Mark B. Bushuev** a,b a Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Acad. Lavrentiev Ave., Novosibirsk, 639, Russia, addresses: kiossarin@mail.ru (K. A. Vinogradova), bushuev@niic.nsc.ru, mark.bushuev@gmail.com (M. B. Bushuev); Fax: ; Tel: b Novosibirsk State University, 2, Pirogova str., Novosibirsk, 639, Russia. c N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences, 9, Acad. Lavrentiev Ave., Novosibirsk, 639, Russia.

2 Table of contents Table S1. Crystallographic data for 1b and 1c..S3 Table S2. Selected bond lengths (Å) and angles ( ) for 1b and 1c S4 Fig. S1. IR spectrum of [MnL 2 ] H 2 O...S5 Fig. S2. X-ray powder diffraction patterns of two different simples of the complex [MnL 2 ] H 2 O...S5 Fig. S3. Crystal packing of 1b (left) and 1c (right) showing relative arrangement of disordered acetone, water and ethanol molecules in space-filling model.....s6 Fig. S4. Emission spectrum of polycrystalline [MnL 2 ] H 2 O at 3 K, λ Ex = 41 nm...s6 Fig. S5-S7. Kinetic curves of the photoluminescence for [MnL 2 ] H 2 O in the solid state at 295 K..S7 Fig. S8. The emission spectrum of polycrystalline [MnL 2 ] H 2 O (λ Ex = 3 nm) recorded at 77 K.S8 Fig. S9. Temperature dependence of the intensities ratio of the 345 nm and 365 nm lines.....s8 Fig. S1. The emission spectrum of polycrystalline L (λ Ex = 3 nm) recorded at 77 K...S9 Fig. S11. Temperature dependence of the intensities ratio of the 345 nm and 365 nm lines...s9 Fig. S12. The emission spectrum of polycrystalline [MnL 2 ] H 2 O (λ Ex = 38 nm) recorded at 77 K...S1 Fig. S13. Normalized UV-vis spectra (the Kubelka-Munk function) of [MnL 2 ] H 2 O and L in the solid state......s1 Fig. S14. Excitation and emission spectra of freshly prepared [MnL 2 ] Me 2 CO at 3 K....S11 Fig. S15. Absorption spectra of [MnL 2 ] H 2 O and L in acetonitrile and dichloromethane solutions..s11 Fig. S16. Absorption spectra of [MnL 2 ] H 2 O and L in dichloromethane solutions....s12 Fig. S17. Emission spectra of [MnL 2 ] H 2 O in acetonitrile solution...s12 Fig. S18. Emission spectrum of L in acetonitrile solution.....s13 Fig. S19. Emission spectra of [MnL 2 ] H 2 O in dichloromethane solution...s13 Fig. S2. Emission spectra of L in dichloromethane solution....s14 Fig. S21. Emission and excitation spectra of four different samples of [MnL 2 ] H 2 O...S14 Fig. S22. Emission and excitation spectra of [MnL 2 ] H 2 O of as prepared sample (left) and recrystallized sample (right)...s15 Fig. S23. DFT calculated (BP86/TZP) molecular structure of dimeric unit [MnL 2 ] 2...S15 Fig. S24. Experimental (a) and calculated (BP86/TZP) (b) molecular structures...s15 Fig. S25. IR-spectrum obtained by simulation in ADF with BP86 functional after numerical recalculation..s16 Fig. S26. HOMOs and LUMOs of n to π* transitions...s17-s18 Fig. S27. The contributions of d orbitals to MOs....S19 Fig. S28. The photographies of the emission of [MnL 2 ] H 2 O....S2 Fig. S29. CIE-1931 chromaticity diagram for polycrystalline [MnL 2 ] H 2 O...S2 S2

3 Table S1. Crystallographic data for 1b and 1c. Compound [MnL 2 ] H 2 O EtOH (1b) [MnL 2 ] Me 2 CO (1c) Empirical formula C 5 H 54 MnN 1 O 2 C 51 H 52 MnN 1 O Formula weight Temperature, K 15(2) 298 (RT) Crystal system Monoclinic Monoclinic Space group P2 1 /n С2/с Unit cell dimensions a, [Å] (3) (4) b, [Å] (5) (4) c, [Å] (7) 2.968(7) α, [ o ] 9 9, [ o ] 11.59(1) (17) γ, [ o ] 9 9 Volume [Å 3 ] (2) 4819(3) Z 4 4 Density (calcd.) [g cm -3 ] Abs. coefficient [mm -1 ] F() Crystal size [mm 3 ] max [ o ] Index range 14 h 14, 21 k 21, 28 l h 17, 15 k 16, 25 l 25 Reflections collected Independent reflections 917 [R(int) =.831] 4523 [R(int) =.587] Reflections, I 2 (I) Completness to [%] Parameters Final R indices [I > 2σ(I)] R 1 =.582, wr 2 =.1331 R 1 =.446, wr 2 =.1181 R indices (all data) R 1 =.162, wr 2 =.1563 R 1 =.654, wr 2 =.1296 GoF Residual electron density (min / max, e/å 3 ) -.58 / /.34 S3

4 Table S2. Selected bond lengths (Å) and angles ( ) for 1b and 1c. 1b 1c Mn1 Cl (9) Mn1 Cl (11) Mn1 Cl (1) Mn1 N11 2.5(2) Mn1 N (3) Mn1 N (3) Mn1 N (18) Mn1 N (3) Mn1 N (3) Cl1 Mn1 Cl (5) Cl1 Mn1 Cl (4) N11 Mn1 Cl (5) N11 Mn1 Cl (7) N21 Mn1 Cl (7) N11 Mn1 Cl (5) N11 Mn1 Cl (7) N21 Mn1 Cl (7) N11 Mn1 N (9) N11 Mn1 N21 8.8(9) N13 Mn1 Cl1 99.5(6) N13 Mn1 Cl (9) N23 Mn1 Cl1 92.9(8) N13 Mn1 Cl (5) N13 Mn1 Cl2 96.5(9) N23 Mn1 Cl (8) N13 Mn1 N (7) N13 Mn1 N (1) N13 Mn1 N (11) N13 Mn1 N (6) N23 Mn1 N (1) N23 Mn1 N (9) N13 Mn1 N (1) N13 Mn1 N (11) N11 N12 C14 N (3) N11 N12 C14 N (4) N21 N22 C24 N23 2.(4) S4

5 a b wavenumber, cm wavenumber, cm -1 Fig. S1. IR spectrum of [MnL 2 ] H 2 O recorded in fluorinated oil (a). IR spectra of two different simples of the complex [MnL 2 ] H 2 O recorded in KBr matrix (b) Fig. S2. X-ray powder diffraction patterns of two different simples of the complex [MnL 2 ] H 2 O. Black line is the aged sample, red line is the freshly prepared sample. S5

6 Fig. S3. Crystal packing of 1b (left) and 1c (right) showing relative arrangement of disordered acetone, water and ethanol molecules in space-filling model.,6,5 Photon energy, ev 2,8 2,7 2,6 2,5 2,4 2,3 2,2 2,1 2 1,9 1,8 a Exp b Sim max = 495(2)nm,4,3 Reduced 2 =3.7*1-7 Adj. R 2 =.99889,2,1, Fig. S4. Emission spectrum of polycrystalline [MnL 2 ] H 2 O at 3 K, λ Ex = 41 nm. This spectrum (λ Ex = 41 nm) is described by a single Gauss function with the maximum at 495(2) nm (red line). S6

7 1, ns t1 =.1 Intensity, 1-4 A1 = 869 (89%) t2 = 1.8 A2 = 26 (6%) t3 = 5.5 A3 = 4.3 (3%) t4 = 135 A4 =.84 (2%) = a b c, нс t1 = 1.2 Intensity, 1-4 A1 = 616 (4%) t2 = 7.2 A2 = 65 (26%) t3 = 92 A3 = 7 (34%) Excitation 3 nm Registration 38 nm 1 1 a b c = Excitation 3 nm Registration 5 nm Time, ns Time, ns Fig. S5. Kinetic curves of the photoluminescence for [MnL2Cl2] H2O in the solid state at 295 K: excitation at 3 nm and registration at 38 nm (left), excitation at 3 nm and registration at 5 nm for the 495 nm band (right); a) instrument response function, b) experimental points and c) approximation. Intensity A1 =.53 (99.88%) t2 = 14 A2 =.24 (.3%) t3 = 625 A3 =.12 (.9%) a b c = , ns t1 = 1 Excitation 3 nm Registration 38 nm 1 1, ns t1 = 4 Intensity A1 = 6.34 (31%) t2 = 43 A2 =.8 (4%) t3 = 88 A3 =.12 (14%) t4 = 775 A4 =.12 (51%) a b c = Excitation 3 nm Registration 495 nm Time, ns Time, ns 25 Fig. S6. Kinetic curves of the photoluminescence for [MnL2Cl2] H2O in the solid state at 295 K: excitation at 3 nm and registration at 38 nm (left), excitation at 3 nm and registration at 5 nm for the 495 nm band (right); a) instrument response function, b) experimental points and c) approximation., ns t1 = Intensity A1 = 4.8 (13%) t2 = A2 = (26%) t3 = 8627 A3 = 3.16 (61%) = a b c Excitation 39 nm Registration 5 nm 1 1 1, ns t1 =.1 Intensity, 1-3 A1 = 572 (68%) t2 = 2.6 A2 = 4.62 (13%) t3 = 9.5 A3 =.92 (1%) t4 = 144 A4 =.5 (9%) a b c = Excitation 39 nm Registration 5 nm Time, ns Time, ns Fig. S7. Kinetic curves of the photoluminescence for [MnL2Cl2] H2O in the solid state at 295 K: excitation at 39 nm and registration at 5 nm for the 495 nm band; a) instrument response function, b) experimental points and c) approximation. S7

8 Ratio of intensities 1,,9,8,7,6,5,4,3,2,1 Photon energy, ev 3,6 3,4 3,2 3 2,8 2,6 2,4 Reduced 2 =4.956*1-5 Adj. R 2 = k( 1-6 )= 14±4 cm Exp 1 =3.579 эв 2 =3.395 эв 3 =3.251 эв 4 =3.9 эв 5 =2.87 эв 6 =2.7 7 =2.5 Sum эв эв Fig. S8. The emission spectrum of polycrystalline [MnL 2 ] H 2 O (λ Ex = 3 nm) recorded at 77 K. The emission spectrum is resolved into seven Gauss functions. 1,2 1,1 345 nm/365 nm 382 nm/365 nm 45 nm/365 nm 1,,9,8,7,6,5 Model Equation Reduced Chi-Sqr Line y = A + B*x 1,8258E-4 Adj. R-Square,99747 Value Standard Error B A,49779,1348 B B -1,91195E-4 6,5176E-5 C A,83759,1348 C B,116 6,5176E-5 D A,56951,1348 D B,15 6,5176E-5, Temperature, K Fig. S9. Temperature dependence of the intensities ratio of the 345 nm and 365 nm lines (black); 382 nm and 365 nm lines (red); 45 nm and 365 nm lines (red) for [MnL 2 ] H 2 O. S8

9 Ratio of intensities 1,,9,8,7,6,5,4,3,2,1, Photon energy, ev 4 3,8 3,6 3,4 3,2 3 2,8 2,6 2,4 2,2 Reduced 2 =1,55421*1-4 Adj. R 2 = k( 1-5 )= 13±3cm -1 Exp 1 =3.599 ev 2 =3.43 ev 3 =3.243 ev 4 =3.119 ev 5 =2.961 ev 6 =2.61 ev Sum Fig. S1. The emission spectrum of polycrystalline L (λ Ex = 3 nm) recorded at 77 K. The emission spectrum is resolved into six Gauss functions. 1,1 1, Model Equation Reduced Chi-Sqr Line y = A + B*x 2,58273E-4 Adj. R-Square,9873 Value Standard Error B A 1,1316,1613 B B -,12 7,79336E-5 C A,53946,1613 C B 6,469E-4 7,79336E nm/365 nm 382 nm/365 nm,9,8,7, Temperature, K Fig. S11. Temperature dependence of the intensities ratio of the 345 nm and 365 nm lines (black); 382 nm and 365 nm lines (red) for L. S9

10 Normalized Photon energy, ev red. 2 =5.867*1-6 Adj. R 2 =.9988 k( 1-5 )= 14±3 cm -1 Experimental 1 =2.974 эв 2 =2.89 эв 3 =2.68 эв 4 =2.47 эв 5 =2.25 эв Sum Fig. S12. The emission spectrum of polycrystalline [MnL 2 ] H 2 O (λ Ex = 38 nm) recorded at 77 K. The emission spectrum is resolved into five Gauss functions, the 495(2) nm band is absent. The quintet corresponds to the vibrational structure with k = 14 ± 3 cm -1 (-1 is the main transition). However, the positions of the components of the quintet differ from the positions of the sextet observed upon excitation at 3 nm (Fig. S8). Photon energy, ev UV-vis spectrum of [MnL 2 ] H 2 O in the solid state UV-vis spectrum of L in the solid state Fig. S13. Normalized UV-vis spectra (the Kubelka-Munk function) of [MnL 2 ] H 2 O and L in the solid state. S1

11 Photon energy, ev a ( em =38 nm) b ( em =5 nm) c ( ex =25 nm) d ( ex =41 nm) Fig. S14. Excitation and emission spectra of freshly prepared [MnL 2 ] Me 2 CO at 3 K. Extinction, M -1 cm -1 Normalized Extinction, M -1 cm -1 Normalized Absorption spectra 1,,8 [MnL 2 ] H 2 O in MeCN L in MeCN Normalized absorption spectra [MnL 2 ] H 2 O in MeCN L in MeCN Absorption spectra [MnL 2 ] H 2 O in CH 2 L in CH 2 Normalized absorption spectra 1, 2,6 2,8 15,4,6 [MnL 2 ] H 2 O in CH 2 L in CH 2,2,4,2 5, , Fig. S15. Absorption spectra of [MnL 2 ] H 2 O and L in acetonitrile and dichloromethane solutions. S11

12 Optical Density Absorption Optical Density 1.6 Absorption of [MnL 2 ]. H 2 O in CH 2 (1.9*1-4 M) Absorption of L in CH 2 (1.*1-5 M) 1.2 1,5.8 1,,5 Absorption of [MnL 2 Cl 2 ]. H 2 O in CH 2 Cl 2 (5.2*1-3 M).4, wavelength, nm wavelength, nm Fig. S16. Absorption spectra of [MnL 2 ] H 2 O and L in dichloromethane solutions Emission spectra of [MnL 2 ] H 2 O in MeCN Excitation 25 nm Excitation 26 nm Excitation 27 nm Excitation 28 nm Excitation 29 nm Excitation 3 nm Excitation 31 nm Excitation 32 nm Excitation 33 nm Excitation 34 nm Excitation 35 nm Fig. S17. Emission spectra of [MnL 2 ] H 2 O in acetonitrile solution. S12

13 5 4 Emission spectrum of L in MeCN Excitation 32 nm Fig. S18. Emission spectrum of L in acetonitrile solution Emission spectra of [MnL 2 ] H 2 O in CH 2 Excitation 375 nm Excitation 4 nm Excitation 325 nm Excitation 3 nm Excitation 25 nm Excitation 275 nm Fig. S19. Emission spectra of [MnL 2 ] H 2 O in dichloromethane solution. S13

14 5 4 3 Emission spectra of L in CH 2 Excitation 35 nm Excitation 375 nm Excitation 4 nm Excitation 3 nm Excitation 325 nm Excitation 275 nm 2 Fig. S2. Emission spectra of L in dichloromethane solution [MnL 2 ] H 2 O, Sample 1 12 [MnL 2 ] H 2 O, Sample Excitation spectrum, em = 4 nm Excitation spectrum, em = 45 nm Excitation spectrum, em = 47 nm = 3 nm 8 = 26 nm = 3 nm = 34 nm = 38 nm = 42 nm 6 = 47 nm 6 = 4 nm = 44 nm 4 4 Excitation spectrum, em = 4 nm Excitation spectrum, em = 5 nm [MnL 2 ] H 2 O, Sample 3 12 [MnL 2 ] H 2 O, Sample 4 12 Excitation spectrum, em = 47 nm Emission spectrum, exc = 31 nm Excitation spectrum, em = 38 nm Emission spectrum, exc = 3 nm 8 6 Emission spectrum, exc = 38 nm Excitation spectrum, em = 31 nm 8 6 Excitation spectrum, em = 5 nm Emission spectrum, exc = 43 nm Fig. S21. Emission and excitation spectra of four different samples of [MnL 2 ] H 2 O. S14

15 12 [MnL 2 ] H 2 O, as prepared 7 [MnL 2 ] H 2 O, recrystallized 8 6 Excitation spectrum, em = 38 nm = 3 nm Excitation spectrum, em = 5 nm = 43 nm Excitation spectrum, em = 38 nm = 3 nm = 43 nm Excitation spectrum, em = 5 nm Fig. S22. Emission and excitation spectra of [MnL 2 ] H 2 O of as prepared sample (left) and recrystallized sample (right). Fig. S23. DFT calculated (BP86/TZP) molecular structure of dimeric unit [MnL 2 ] 2. Fig. S24. Experimental (a) and calculated (BP86/TZP) (b) molecular structures. S15

16 IR intensity, km*mol Wavenumber, cm -1 Fig. S25. IR-spectrum obtained by simulation in ADF with BP86 functional after numerical recalculation (1 Debye 2 - angstrom -2 -amu -1 = km*mol -1 ). S16

17 a) S17

18 b) Fig. S26. HOMOs and LUMOs of n to π* transitions. Each molecular orbital consists of a large number of atomic orbitals. The molecular orbitals participate in excitation. Therefore, a large number of atomic orbitals participate in each transition. Moreover, a large number of unoccupied MOs are involved in each transition. We have shown HOMOs (spin-up (a) and spin-down (b)) which consist of nitrogen lone-electron pair orbitals and lying in the UV-Vis excitation range. Also, we have shown π* LUMOs to which the transitions occur (from the HOMOs). S18

19 Fig. S27. The contributions of d orbitals to MOs. S19

20 Fig. S28. The photographies of the emission emission of [MnL 2 ] H 2 O: a) λ ex = 3 nm, b) λ ex = 3 nm with the light filter 5 nm, c) λ ex = 43 nm with the light filter 5 nm. Fig. S29. CIE-1931 chromaticity diagram for polycrystalline [MnL 2 ] H 2 O. S2