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Supporting Information Bright green-to-yellow emitting Cu(I) complexes based on bis(2-pyridyl)phosphine oxides: synthesis, structure and effective thermally activated-delayed fluorescence Alexander V. Artem’ev,*a Maxim R. Ryzhikov,a,b Ilya V. Taidakov,c,d Mariana I. Rakhmanova,a Evgenia A. Varaksina,c Irina Yu. Bagryanskaya,b,e Svetlana F. Malysheva,f Nataliya A. Belogorlovaf
a Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Akad. Lavrentiev Ave., Novosibirsk 630090, Russian Federation b Novosibirsk State University, (National Research University), Department of Natural Sciences, 2, Pirogova Str., Novosibirsk 630090, Russian Federation c P. N. Lebedev Institute of Physics, Russian Academy of Sciences, 119991 Moscow, Russian Federation d Dmitry Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, 125047 Moscow, Russian Federation e N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences, 9, Akad. Lavrentiev Ave., Novosibirsk 630090, Russian Federation f A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation *Author for correspondence: [email protected] (Alexander V. Artem’ev)
Table of Contents Pages
S2-3 X-Ray crystallography
S4-8 FT-IR spectra of 1-8
S8-9 ESI-MS spectra of 1, 3 and 5
S9 V.T. 31P NMR spectra of 5
S10-17 Photophysical data
S18-20 Computation details
S20-21 TGA/DTA curves for 1 and 6
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2018
S2
X-Ray crystallography
Table S1. Data collection and refinement parameters for 2–7.
Compound 2 3·2/3MeCN 4 5 6 7
CCDC number 1550541 1550542 1550543 1577810 1550544 1550545
Empirical formula C24H26Cu2I2N4O2P2 C39.33H56Cu2I2N4.67O2P2 C34H30Cu2I2N4O2P2 C42H34Cu2I2N4O2P2 C24H22Cu2N6O2P2S2 C30H34Cu2N6O2P2S2
Formula mass [g/mol] 845.31 1069.04 969.44 1069.55 679.62 763.77
Space group C2/c P-1 C2/c P-1 P-1 P-1
a [Å] 8.6569(3) 9.9811(4) 22.6984(7) 12.8420(9) 8.4316(4) 8.8655(10)
b [Å] 15.0992(5) 18.1601(8) 13.3472(4) 19.1700(12) 8.5325(4) 14.2395(16)
c [Å] 21.8930(8) 19.7982(9) 23.1883(6) 20.1670(13) 11.4693(6) 14.5066(16)
α [°] 90.00 71.782(2) 90.00 111.493(3) 74.268(2) 109.975(5)
β [°] 92.3170(10) 80.077(2) 90.8620(10) 94.250(3) 71.999(2) 90.384(5)
γ [°] 90.00 84.603(2) 90.00 108.188(3) 62.187(2) 103.193(5)
V [Å3] 2859.34(17) 3354.6(3) 7024.3(4) 4287.8(5) 686.14(6) 1668.5(3)
Z 4 3 8 4 1 2
Dcalcd. [g·cm-3] 1.964 1.588 1.833 1.657 1.645 1.520
μ [mm-1] 3.788 2.440 3.097 2.546 1.853 1.533
Temperature [K] 296(2) 200(2) 200(2) 296(2) 296(2) 296(2)
Reflections collected 17174 29117 66274 62633 12135 18525
Independent reflections
3293 [Rint = 0.0448]
11792 [Rint = 0.0317]
9742 [Rint = 0.0432]
14604 [Rint = 0.0553]
3615 [Rint = 0.0295]
5640 [Rint = 0.0475]
R1, wR2 [I > 2σ(I)] 0.0256, 0.0652 0.0750, 0.1820 0.0259, 0.0595 0.0873, 0.1821 0.0269, 0.0755 0.0834, 0.1904
R1, wR2 (all data) 0.0291, 0.0767 0.1018, 0.1986 0.0358, 0.0645 0.1673, 0.2381 0.0309, 0.0787 0.1384, 0.2095
Goodness of fit 1.145 1.089 1.032 1.046 1.077 1.066
Largest diff peak and hole [e/Å3]
1.10 and -0.79 2.56 and -2.13 1.22 and -1.03 2.91 and -2.12 0.40 and -0.38 1.88 and -0.60
S3
Table S2. The structures of the three independent molecules in 3·2/3MeCN and their selected bond lengths [Å] and angles [deg].
Cu–Cu 2.7187(19) Cu–I 2.6816(13) Cu–I’ 2.5797(13) Cu–N1 2.077(7) Cu–N2 2.088(7) I–Cu–I 117.81(4) Cu–I–Cu 62.19(4) N1–Cu–N2 100.4(3) I–Cu–I–Cu 0.0
Cu–Cu 2.623(2) Cu–I 2.6639(16) Cu–I’ 2.5582(15) Cu–N1 2.098(10) Cu–N2 2.5583(15) I–Cu–I 119.74(5) Cu–I–Cu 60.27(5) N1–Cu–N2 100.3(4) I–Cu–I–Cu 0.0
Cu–Cu 2.6913(19) Cu–I 2.5651(13) Cu–I’ 2.6697(14) Cu–N1 2.079(7) Cu–N2 2.070(8) I–Cu–I 118.16(4) Cu–I–Cu 61.84(4) N1–Cu–N2 101.8(3) I–Cu–I–Cu 0.0
Figure S1. The structure of asymmetric unit of 5.
Figure S2. Molecular structure of 5 (the H atoms are omitted for clarity). Selected bond lengths [Å]: Cu(1A)–Cu(1B) 2.7444(19), Cu(1A)–I(1A) 2.5828(17), Cu(1A)–I(1B) 2.6573(18), Cu(1B)–I(1A) 2.6784(18), Cu(1B)–I(1B) 2.5660(17), Cu(1A)–N(1A) 2.090(10), Cu(1A)–N(2A) 2.097(11), Cu(1B)–N(2B) 2.079(10), Cu(1B)–N(1B) 2.088(11), P(1A)–O(1A) 1.490(8), P(1B)–O(1B) 1.481(9).
S4
FT-IR spectra of 1-8
Figure S3. FT-IR spectrum of {Cu2I2[Py2(Me)P=O]2} (1) (top) and comparison (bottom) of experimental (black line) FT-IR spectrum of {Cu2I2[Py2(Me)P=O]2} (1) and theoretical IR spectra for 1-Ci (red line) and 1-C2 (blue dashed line). Calculated spectra are scaled by 0.97 factor.
B-15 1.spc
3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400Wavenumber (cm-1)
30823051 2972
2899
1580
1450 1425
12981271
12401209
11551148
11361086
1047
1003905
880
756704
633
505
417382
S5
Figure S4. FT-IR spectrum of {Cu2I2[Py2(Et)P=O]2} (2).
B-18 1.spc
3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400Wavenumber (cm-1)
30903059
297029262897
2874
15801562
14501425
13931371
12831234
12021153
11461134
1090 1001989
907880
772752
733691
635617
548505
453428413
Figure S5. FT-IR spectrum of {Cu2I2[Py2(n-C9H19)P=O]2} (3).
3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600Wavenumber (cm-1)
3055 2947 2924
2851 1578
14541423
12731200
114611341088
10451003
910
756733
633606
S6
Figure S6. FT-IR spectrum of {Cu2I2[Py2(PhCH2)P=O]2} (4). analises2016-06.bsp(5) ATR Artemyev B2 Solid 16.06.spc
3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600Wavenumber (cm-1)
3055
3032
29282901
2855
1740 1578
1493 14541423
139612771234 1207
11531123108410651049
10301007
910 826768
737 698664633
590563
Figure S7. FT-IR spectrum of {Cu2I2[Py2(1-NpCH2)P=O]2} (5).
3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600Wavenumber (cm-1)
3094 30553005 2924
29012855
1578
150814541423
1396
12651204
11501130
10881049
1007907868 833
799772
748718
694637
590555
S7
Figure S8. FT-IR spectrum of {Cu2(SCN)2[Py2(Me)P=O]2} (6).
3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400Wavenumber (cm-1)
30863055
2974 28952862
2097
15801562
14501427
1404
12961279
12421207
11551136
1082 1005968
905889
872
758731
702631
505449
413388
Figure S9. FT-IR spectrum of {Cu2(SCN)2[Py2(Bu)P=O]2} (7).
3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400Wavenumber (cm-1)
3055 29612932
2911 2860
2095
1582 14541427
13951346 1281
12211206
11501134
108810491003
970935
907870 799
777766
748731
635
548513
459446
413388
S8
Figure S10. FT-IR spectrum of {Cu2(SCN)2[Py2(PhCH2)P=O]2} (8)
3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400Wavenumber (cm-1)
30963055
29452899
2868
21062056
16011580
15621495
14541429
1393
12811227
120611571144
11341092
10471003
970 912
826770
748698
635590
528501
457415
ESI-MS spectra of 1, 3 and 5
Figure S11. ESI-Mass spectra of 1 in positive- (a) and negative-ion (b) modes (MeCN).
B15_esi_2_Centroid
24002200200018001600140012001000800600400m/z
10
20
30
40
50
60
70
80
90
100
Rel
ativ
e In
tens
ity (%
)
[CuL*MeCN]+
[CuL2]+
2412209619001643153111621047881
499
322
B15_esi_1_Centroid
24002200200018001600140012001000800600400m/z
8
16
24
32
40
48
56
64
72
80
88
96
Rel
ativ
e In
tens
ity (%
)
509
24152221
1841
1650
1460
1270
1080
888
698
317
(a) (b)
S9
Figure S12. ESI-Mass spectra of 3 in positive- (a) and negative-ion (b) modes (MeCN).
B1_esi_2_Centroid
850800750700650600550500450400m/z
8
16
24
32
40
48
56
64
72
80
88
96
Rel
ativ
e In
tens
ity (%
)
864836737
723
661611533466
434
369
B1_esi_1_Centroid
24002200200018001600140012001000800600400m/z
8
16
24
32
40
48
56
64
72
80
88
96
Rel
ativ
e In
tens
ity (%
)
2453
22631885
1650
1460
1274
1078
888507
317
Figure S13. ESI-Mass spectra of 5 in positive- (a) and negative-ion (b) modes (MeCN).
B12_esi_2_Centroid
850800750700650600550500450400m/z
8
16
24
32
40
48
56
64
72
80
88
96
Rel
ativ
e In
tens
ity (%
)
891842
751
711
657586558485
448
383
B12_esi_1_Centroid
24002200200018001600140012001000800600400m/z
8
16
24
32
40
48
56
64
72
80
88
96
Rel
ativ
e In
tens
ity (%
)
698
2033
24152220
1839
1653
14601270
1080
888
508
317
V.T. 31P NMR spectra of 5
Figure S14. 31Р{1H} NMR spectra of 5 measured at 23 and –60 oC in CDCl3 solution.
(a) (b)
(a) (b)
23 oC –60 oC
S10
Photophysical data
Figure S15. Photographs of the powder 1 under ambient light (left) and UV-light (right).
Figure S16. Excitation (at 300 K) and emission spectra ( = 400 nm) of 1 in the solid state at 77 and 300 K.
Figure S17. Excitation (at 300 K) and emission spectra ( = 470 nm) of 2 in the solid state at 77 and 300 K.
S11
Figure S18. Excitation (at 300 K) and emission spectra ( = 450 nm) of 3 in the solid state at 77 and 300 K.
Figure S19. Excitation (at 300 K) and emission spectra ( = 450 nm) of 4 in the solid state at 77 and 300 K.
Figure S20. Excitation (at 300 K) and emission spectra ( = 450 nm) of 5 in the solid state at 77 and 300 K.
S12
Figure S21. Excitation (at 300 K) and emission spectra ( = 400 nm) of 6 in the solid state at 77 and 300 K.
Figure S22. Excitation (at 300 K) and emission spectra ( = 480 nm) of 7 in the solid state at 77 and 300 K.
Figure S23. Excitation (at 300 K) and emission spectra ( = 450 nm) of 8 in the solid state at 77 and 300 K.
S13
0 50 100 150 200 250 300 350 400 450 500 550 600 6500,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
Inte
nsity
, cou
nts
Time, mks
Model ExpDec1
Equationy = A1*exp(-x/t1) + y0
Reduced Chi-Sqr
4,80541E-5
Adj. R-Square 0,99796Value Standard Error
Normalized1
y0 0,00811 5,38875E-5A1 0,96311 2,7111E-4t1 69,82805 0,03079y0 0,007 4,11323E-5A1 1,25345 0,00103t1 10,83523 0,00978
T=77K
T=300K
Figure S24. Emission decays for complex 1 in the solid state at 77 K and 300 К ( = 560 nm, = 355 nm).
0 5000 10000 15000 20000 25000 300000
100
200
300
400
500
600
Inte
nsity
, cou
nts
t, ns
Model ExpDec2
Equationy = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr
95,78056
Adj. R-Square 0,98876Value Standard Error
C y0 9,92396 0,55492C A1 308,91461 2,21915C t1 7043,00832 76,58587
C A2 253,28119 3,4944
C t2 906,80327 23,75789
Figure S25. Emission decays for complex 2 in the solid state at 300 К ( = 575 nm, = 470 nm).
0 5000 10000 15000 20000 25000 300000
100
200
300
400
500
600
Inte
nsity
, cou
nts
t, ns
Model ExpDec2
Equationy = A1*exp(-x/t1) + A2*exp(-x/t2) + y0
Reduced Chi-Sqr
66,33608
Adj. R-Square 0,97098Value Standard Error
C y0 25,43426 0,56777C A1 945,20809 12,76565C t1 356,27586 3,6986C A2 103,18087 0,66285C t2 9090,89579 182,56495
Figure S26. Emission decays for complex 3 in the solid state at 300 К ( = 537 nm, = 450 nm).
S14
0 5000 10000 15000 20000 25000 300000
250
500
750
1000
Inte
nsity
, cou
nts
t, ns
Model ExpDec1
Equationy = A1*exp(-x/t1) + y0
Reduced Chi-Sqr
308,80482
Adj. R-Square 0,99181Value Standard Error
C y0 79,80738 0,607C A1 814,99986 1,31004C t1 5891,40351 20,94498
Figure S27. Emission decays for complex 4 in the solid state at 300 К ( = 536 nm, = 450 nm).
0 5000 10000 15000 20000 25000 300000
200
400
600
800
1000
1200
1400
Inte
nsity
, cou
nts
t, ns
Model ExpDecay3
Equation
y = y0 + A1*exp(-(x-x0)/t1) + A2*exp(-(x-x0)/t2) + A3*exp(-(x-x0)/t3)
Reduced Chi-Sqr
66,61207
Adj. R-Square 0,99686Value Standard Error
C
y0 12,39661 0,33092x0 255,84514 2,55932E7A1 87,33237 477550,545t1 4680,38015 293,98727A2 755,83457 1,67787E7t2 1152,90414 32,50618A3 499,95629 3,6188E7t3 353,58408 13,86996
Figure S28. Emission decays for complex 5 in the solid state at 300 К ( = 536 nm, = 450 nm).
0 100 200
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1,1
T=77K
T=300K
Inte
nsity
, cou
nts
Time, mks
Model ExpDec1
Equationy = A1*exp(-x/t1) + y0
Reduced Chi-Sqr
3,23279E-5 2,22737E-5
Adj. R-Square 0,99888 0,99956Value Standard Error
Normalized1
y0 0,00471 3,83444E-5A1 1,03708 2,7728E-4t1 43,00425 0,01672y0 -0,00288 2,63602E-4A1 1,40932 0,00142t1 5,95905 0,00813
Figure S29. Emission decays for complex 6 in the solid state at 77 K and 300 К ( = 580 nm, = 355 nm).
S15
0 5000 10000 15000 20000 25000 300000
100
200
300
400
500
600
Inte
nsity
, cou
nts
t, ns
Model ExpDec1
Equationy = A1*exp(-x/t1) + y0
Reduced Chi-Sqr
200,28743
Adj. R-Square 0,98464Value Standard Error
C y0 56,72659 0,65602C A1 461,24175 0,93227C t1 7461,3588 41,16433
Figure S30. Emission decays for complex 7 in the solid state at 300 К ( = 560 nm, = 480 nm).
0 5000 10000 15000 20000 25000 300000
200
400
600
800
1000
1200
Inte
nsity
, cou
nts
t, ns
Model ExpDec1
Equationy = A1*exp(-x/t1) + y0
Reduced Chi-Sqr
196,80255
Adj. R-Square 0,99614Value Standard Error
C y0 36,6432 0,33142
C A1 1092,80672 1,4054
C t1 3722,43385 7,86749
Figure S31. Emission decays for complex 8 in the solid state at 300 К ( = 592 nm, = 450 nm).
Figure S32. Absorption, excitation and emission (λex = 400 mn) spectra of 6. The absorption spectrum is recorded for a MeCN solution, while excitation and emission spectra are given for a powder of 6.
S16
Figure S33. Absorption spectra of 3 (a), 4 (b) and 5 (c) measured for MeCN solution.
Figure S34. The solid-state UV–Vis absorption spectra of 1 (left) and 6 (right).
(a) (b)
(c)
S17
Figure S35. Comparison of excitation and solid-state UV–Vis absorption spectra for 1 (left) and 6 (right).
S18
Computation details
Figure S36. Near Fermi level molecular orbitals for T1 state of complex 1-Ci.
S19
Figure S37. Near Fermi level molecular orbitals for S0 state of complex 6.
S20
Figure S38. ELF map for S0 state of complex 6. Table S3. Selected optimized and experimental geometrical parameters for complex 6 and calculated energetic parameters for its different states. E (kcal/mol) is formation energy, ΔE (kcal/mol) is energy difference between ground state (S0) and exited states (S1 and T1), DCu–Cu (Å), DCu–N (Å), DCu–S (Å) and DC–N (Å) are Cu–Cu, Cu–N, Cu–S and C–N distances, α (°) is N–Cu–S angle.
Structure E ∆E DCu–Cu DCu–N DCu–S DC–N α N–Cu–S 6 S0 -10208.46 0 5.026 1.932 2.394 1.165 109.4 6 S1 -10166.17 42.29 5.267 1.929 2.403 1.163 99.1 6 T1 -10166.41 42.05 5.189 1.928 2.402 1.164 100.5 X-ray structure 6 (Fig. 4) n/a n/a 5.103 1.952 2.391 1.148 105.7
TGA/DTA curves for 1 and 6
Figure S39. The TGA/DTA curves for 1.
S21
Figure S40. The TGA/DTA curves for 6.