S1

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: chemisufarm@yandex.ru (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.