Supporting Information

Silver(I) and gold(I) complexes with tris[2-(2-pyridyl)ethyl]phosphine

Andrey Yu. Baranov,a Mariana I. Rakhmanova,a,b Denis G. Samsonenko,a,b Svetlana F. Malysheva,c Nataliya A. Belogorlova,c Irina Yu. Bagryanskaya,b,d Vladimir P. Fedin,a,b Alexander V. Artem’ev*a,b

aNikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Acad. Lavrentiev Ave., Novosibirsk 630090, Russian Federationb Novosibirsk State University, 2, Pirogova Str., Novosibirsk 630090, Russian FederationcA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian FederationdN. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences, 9, Acad. Lavrentiev Ave., Novosibirsk 630090, Russian Federation

*Author for correspondence: chemisufarm@yandex.ru (Alexander V. Artem’ev)

Table of Contents

Pages

S2–5 §1. X-Ray crystallography

S5–7 §2. Thermogravimetry

S7 §3. FT-IR spectra

S8–9 §4. Photophysical data

S1

§1. X-Ray crystallography

Table S1. Data collection and selected refinement parameters for 1–5.

1·CH3CN 2 3 4·CH2Cl2 5CCDC number 1897340 1897341 1897342 1897339 1901175

Chemical formula

C23H24AgClN4O4P

C21H24AgN4O3P

C22H24AgF3N3O3PS

C21.5H25Ag2Cl3N3P

C21H24AuClN3P

Mr 597.78 519.28 606.34 678.50 581.82Crystal system, space group

Triclinic, P–1 Triclinic, P–1 Triclinic, P–1 Triclinic, P–1Monoclinic,

P21

Temperature (K) 130 130 135 135 200

a, b, c (Å)10.033(4),

11.7718(5),13.0207(5)

9.6519(4),9.9851(5),12.3745(6)

9.9265(5),10.5108(5),13.0517(5)

9.3136(6),12.1097(7),12.7202(7)

18.384(2), 23.184(2), 20.380(2)

α, β, γ (°)101.356(3),106.739(3),113.817(4)

69.419(4), 83.705 (4), 68.895 (4)

86.225(3),73.571(4),67.903(4)

111.580(5),104.570(5),99.163(5)

90.0094.873(4)

90.00V (Å3) 1258.30(10) 1041.39(9) 1208.96(10) 1239.63(14) 8654.6(16)Z 2 2 2 2 16μ (mm-1) 1.01 1.08 1.04 1.98 7.01Crystal size (mm)

0.36 × 0.11 × 0.06

0.31 × 0.09 × 0.05

0.36 × 0.28 × 0.07

0.32 × 0.15 × 0.03

0.60 × 0.08 × 0.02

Tmin, Tmax 0.966, 1.000 0.830, 1.000 0.867, 1.000 0.893, 1.000 0.632, 0.928No. of measured, independent and observed [I> 2(I)] reflections

10127, 5462, 4867

7309, 4244, 3794

9288, 5261, 4712

9230, 5368, 4277

165636, 37471, 26682

Rint 0.023 0.025 0.026 0.027 0.074(sin θ/λ)max (Å-1) 0.680 0.625 0.680 0.684 0.653

R[F2> 2(F2)], wR(F2), S

0.029, 0.064, 1.09

0.029, 0.066, 1.03

0.033, 0.080, 1.07

0.034, 0.072, 1.02

0.050, 0.089, 1.03

No. of reflections 5462 4244 5261 5368 37471

No. of parameters 308 271 307 298 1946

ρmax, ρmin (e Å-3) 0.47, –0.43 0.77, –0.42 0.94, –1.04 0.78, –0.59 3.12, –2.31

S2

Figure S1. The simulated and experimental XRPD patters of 2 (a) and 3 (b).

Figure S2. Overplayed fragments of CPs 1·CH3CN and 2 (the H atoms and anionic parts are omitted).

Figure S3. Overplayed fragments of CPs 2 and 3 (the H atoms and anionic parts are omitted).

S3

(a) (b)

Figure S4. Structure of complex 5: two of the six independent [Au(L)Cl] molecules (the H atoms are omitted). Selected bond lengths (Å) and angles (°): Au3⋯Au4 3.2325(8), Au3–P3 2.237(4), Au3–Cl3 2.296(4), Au4–P4 2.237(4), Au4–Cl4 2.302(4), P3–Au3–Cl3 173.55(16), P3–Au3–Au4 100.72(10), Cl3–Au3–Au4 84.53(11), P4–Au4–Cl4 176.44(15), P4–Au4–Au3 101.08(10), Cl4–Au4–Au3 82.42(12).

Figure S5. Structure of complex 5: two of the six independent [Au(L)Cl] molecules (the H atoms are omitted). Selected bond lengths (Å) and angles (°):Au5⋯Au6 3.1248(8), Au5–P5 2.234(4), Au5–Cl5 2.303(4), Au6–P6 2.232(4), Au6–Cl6 2.314(4), P5–Au5–Cl5 176.07(15), P5–Au5–Au6 99.51(10), Cl5–Au5–Au6 83.92(11), P6–Au6–Cl6 174.67 (14), P6–Au6–Au5 104.62(10), Cl6–Au6–Au5 80.31(10).

S4

Figure S6. Structure of complex 5: two of the six independent [Au(L)Cl] molecules (the H atoms are omitted). Selected bond lengths (Å) and angles (°):Au7⋯Au8 3.2735(10), Au7–P7 2.228(4), Au7–Cl7 2.300(4), Au8–P8 2.234(4), Au8–Cl8 2.302(4), P7–Au7–Cl7 172.12(19), P7–Au7–Au8 96.66(11), Cl7–Au7–Au8 91.19(15), P8–Au8–Cl8 175.59(18), P8–Au8–Au7 105.13(15), Cl8–Au8–Au7 78.80(12).

§2. Thermogravimetry

Figure S7. The TGA, c-DTA and DTG curves for 1.

S5

Figure S8. The TGA, c-DTA and DTG curves for 2.

Figure S9. The TGA, c-DTA and DTG curves for 3.

S6

Figure S10. The TGA, c-DTA and DTG curves for 4.

§3. FT-IR spectra

Figure S11. FT-IR spectra of compounds 1–5.

S7

§4. Photophysical data

Figure S12. Emission spectra of 4 recorded at the different excitation wavelengths (λex = 300–460 nm) at 300 K.

Figure S13. Excitation spectra for complex 4 recorded for 390 (left) and 450 nm (right) emission bands (298 K).

S8

?????? =390 nm, ?????? = 350 nmτ1 = 3.4*10-9 (41%), τ2 = 0.3*10-9 (59%)

?????? = 460 nm, ?????? = 390 nmτ1 = 3.8*10-9 (28%), τ2 = 12.7*10-9 (72%)

Figure S14. Photoluminescence decay curves for complex 1 recorded for 390 and 450 nm emission bands (298 K).

?????? =390 nm, ?????? = 350 nmτ1 =2.2*10-9 (43%), τ2 = 9.1*10-9 (57%)

?????? = 460 nm, ?????? = 390 nmτ1 = 37*10-9 (90%), τ2 = 5.2*10-9 (10%)

Figure S15. Photoluminescence decay curves for complex 4 recorded for 390 and 450 nm emission bands (298 K).

S9