Pt-Ag Clusters and their Neutral Mononuclear Pt(II) Starting Complexes: Structural and Luminescence Studies.

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Pt-Ag Clusters and their Neutral Mononuclear Pt(II) Starting Complexes: Structural and Luminescence Studies. Juan Forniés* a, Violeta Sicilia *b, José Mª Casas a, Antonio Martín a, José A. López a, Carmen Larraz a, Pilar Borja a and Carmen Ovejero b a Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Facultad de Ciencias, Universidad de Zaragoza-CSIC, Plaza. S. Francisco s/n, 50009, Zaragoza, Spain. E-mail: juan.fornies@unizar.es; Fax: +34 976-761159 b Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Escuela Universitaria de Ingeniería Técnica Industrial, Universidad de Zaragoza-CSIC, Campus Universitario del Actur, Edificio Torres Quevedo, 50018, Zaragoza, Spain. E-mail: sicilia@unizar.es; Fax: +34 976-762189

103,6 100 95 90 85 80 75 70 %T 65 60 55 50 ν 1691 C = O 45 40 35 1097 νclo - 4 1039 30 1077 23,6 180 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400 300 25 cm-1 Figure S1. IR spectra of powdered solid (black) and crystals (blue) of compound 3. Figure S2.- DFT-Optimized structure of complex [Pt(bzq)(S 2 CNC 4 H 8 )] (1)

Table S1.- DFT-Optimized structure of complex 1 Center Coordinates (Å) x y z Pt -0.01976 0.03119-0.01015 S 1.71296 1.81858-0.03754 S 1.75781-0.74876 1.30148 N -1.55192 0.78706-1.17749 N 3.8063 0.99964 1.46211 C -1.29656-1.51551 0.12349 C -1.19313-2.72888 0.79332 H -0.30288-2.96385 1.36757 C -2.23437-3.67831 0.7443 H -2.11578-4.61446 1.28076 C -3.39968-3.44953 0.03296 H -4.18818-4.19384 0.00878 C -3.55787-2.23529-0.66512 C -4.72305-1.89221-1.43414 H -5.53657-2.60883-1.48505 C -4.82756-0.70279-2.09196 H -5.71752-0.46776-2.66551 C -3.76802 0.2656-2.0434 C -3.78649 1.51603-2.68822 H -4.64961 1.8079-3.27686 C -2.69989 2.36205-2.56368 H -2.6831 3.33035-3.04707 C -1.59617 1.96521-1.79883 H -0.73109 2.60493-1.68243 C -2.61892-0.06163-1.29073 C -2.49959-1.29843-0.60115 C 2.59966 0.73422 0.97553 C 4.57298 0.07048 2.3148 H 4.55989-0.93223 1.88433 H 4.11126 0.01844 3.30675

C 5.96994 0.70079 2.36285 H 6.56762 0.34829 1.51745 H 6.50324 0.44671 3.27982 C 5.68828 2.20515 2.22242 H 5.36844 2.62056 3.18234 H 6.55488 2.77411 1.88303 C 4.53306 2.2601 1.21686 H 3.86537 3.11085 1.35904 H 4.88925 2.28128 0.18133

L+1 (96) LUMO(95) HOMO (94) H-1 (93) Figure S3. Representative frontier orbitals involved in the absorption of [Pt(bzq)(pdtc)](1).

Table S2. Absorption data for compounds 1 and 2 in solutions 10-4 M at room temperature. Compound Solvent λ abs / nm (10 3 ε M -1 cm -1 ) Toluene 298 (13.7), 316 (15.8), 336 (14.2), 350 (13.2), 360 (12.3), 400 (12.7), 448 (1.7) 2-MeTHF 308sh (9.3), 318 (12.4), 336 (12.1), 348sh (11.3), 360sh (10.3), 397 (10.3), 446 (1.3) 1 CH 2 Cl 2 292sh (15.8), 308 (18.9), 320 (17.7), 332 (12.8), 350 (12.5), 391 (9.9), 444 (1.5) DMF 294sh (11.3), 312 (12.9), 332 (11.2), 350 (10.7), 364sh (7.5), 390 (8.8), 438 (1.4) NCMe 294sh (11.4), 308 (12.6), 328 (11.0), 348 (11.1), 386 (8.4), 434 (1.2) Toluene 238(9.0), 246 (9.1), 256 (9.6), 264 (9.7), 276 (10.0), 298 (10.1), 318 (11.9), 338 (11.3), 350sh (10.6), 360 (9.7), 398 (9.8), 450 (1.2) 2 2-MeTHF 240 (20.9), 256 (26.5), 274sh (8.1), 282 (6.4), 316 (11.2), 336 (11.2), 350sh (10.2), 360 (9.4), 397 (9.3), 448 (0.4) CH 2 Cl 2 222 (56.1), 238sh (56.1), 256 (34.1), 294 (11.8), 312 (12.7), 332 (12.1), 352 (11.9), 391 (9.3), 438 (1.9) DMF 292 (11.8), 310 (12.9), 332 (11.6), 350 (11.0),390 (8.8), 436 (1.6) NCMe 220 (50.0), 236 (36.7), 252 (33.7), 290 (12.6), 308 (13.6), 330 (12.4), 348 (12.3), 354sh (11.1), 386 (9.1), 430 (1.8)

Toluene, 2-MeTHF, CH 2 Cl 2, DMF, MeCN Absorbance (u.a.) 300 400 500 600 (a) 4 10-2 M, 2x10-3 M, 10-3 M, 8x10-4 M, 5x10-4 M 2x10-4 M, 10-4 M, 8x10-5 M, 5x10-5 M, 2x10-5 M 1,8 1,6 3 1,4 Absorbance (a.u.) 2 1 Absorbance (a.u.) 1,2 Y = A + B * X Parameter Value Error ------------------------------------------------------------ A 4,55757E-4 0106 B 172,03 0,32603 ------------------------------------------------------------ R SD N P 0 ------------------------------------------------------------ 0,99999 0299 10 <0.0001 ------------------------------------------------------------ 400 450 500 550-00 02 04 06 08 10 C (mol.l -1 ) (b) (c) Figure S4. a) UV-visible absorption spectra of 1 in different solvents (10-4 M) showing negative solvatochromism. b) Expansion of the low-energy region of the UV-visible spectra of 1 in CH 2 Cl 2 at 298K at different concentrations. c) Representation of the linear fit of the absorbance at 444 nm (A 444 ) vs. concentration.

1, 2 1,2 Intensity (a.u) 200 300 400 500 600 700 Figure S5. Normalized Diffuse Reflectance UV-vis (DRUV) spectra of 1 and 2 in solid state at room temperature. λ exc = 490nm, 1, λ exc = 450nm, 2, λ em = 630nm, 1, λ em = 510nm, 2 2,0 1,8 1,6 1,4 Intensity (a.u.) 1,2 300 350 400 450 500 550 600 650 700 750 800 Figure S6. Normalized emission and excitation spectra of 1 and 2 in 2-Me-THF (10-3 M) at 298 K

λ exc = 420nm, λ em = 480nm, λ em = 550nm, λ em = 620nm Intensity (a.u.) 250 300 350 400 450 500 550 600 650 700 750 800 850 λ(nm) Figure S7. Normalized emission and excitation spectra of 1 in 2-Me-THF (10-3 M) at 77 K. 3,5 3, 4, 5, 6 3,0 2,5 Absorbance (a.u.) 2,0 1,5 0,5-0,5 200 250 300 350 400 450 500 550 600 Figure S8. Absorption spectra of compounds 3-6 in acetonitrile solution 5x10-4 M

1, 3, 5 3 Absorbance (a.u.) 2 1 0 200 250 300 350 400 450 500 550 600 Figure S9. Absorption spectra in acetonitrile solution of 1 (10-4 M), 3 (5x10-4 M) and 5 (5x10-4 M ) at room temperature. 2, 4, 6 3,5 3,0 2,5 Absorbance 2,0 1,5 0,5-0,5 200 250 300 350 400 450 500 550 600 Figure S10. Absorption spectra in acetonitrile solution of 2 (10-4 M), 4 (5x10-4 M) and 6 (5x10-4 M ) at room temperature.

1, 3, 5 1,2 Absorbance 200 300 400 500 600 700 Figure S11. Normalized Diffuse Reflectance UV-vis (DRUV) spectra of 1, 3, 5 in solid state. 2, 4, 6 Absorbance (a.u.) 200 300 400 500 600 700 Figure S12. Normalized Diffuse Reflectance UV-vis (DRUV) spectra of compounds 2, 4, 6 in solid

state. λ exc = 510nm, 298K; λ exc = 475nm, 77K; λ exc = 520nm, 77K; λ em = 615nm, 298K; λ em = 625nm, 77K 100000000 90000000 Intensity (a.u.) 80000000 70000000 60000000 50000000 40000000 30000000 20000000 10000000 0 Intensity (a.u.) -10000000 500 550 600 650 700 750 800 850 350 400 450 500 550 600 650 700 750 800 850 Figure S13. Normalized excitation and emission spectra of 4 in the solid state at 298K (Orange) and 77 K(Grey). Inset: Unnormalized spectra.

λ exc = 400nm (298K); λ exc = 500nm (77K); λ exc = 550nm (77K); λ em = 620nm (298K); λ em = 580nm (77K); λ em = 650nm (77K); λ em = 700nm (77K) 1,20E+008 0E+008 1,2 Intensity (a.u.) 8,00E+007 6,00E+007 4,00E+007 2,00E+007 0E+000 Intensity (a.u.) 400 450 500 550 600 650 700 750 800 300 350 400 450 500 550 600 650 700 750 800 Figure S14. Normalized excitation and emission spectra of 5 in the solid state at 298K (yellow) and 77K (Grey). Inset: Unnormalized spectra.

λ exc = 510nm, 298K; λ exc = 440nm, 77K; λ exc = 510nm, 77K; λ em = 620nm, 298K; λ em = 510nm, 77K; λ em = 640nm, 77K 1,1 60000000 0,9 Intensity (a.u.) 50000000 40000000 30000000 20000000 Intensity (a.u.) 0,7 0,5 0,3 0,1-0,1 10000000 0 450 500 550 600 650 700 750 800 850 300 350 400 450 500 550 600 650 700 750 800 850 Figure S15. Normalized excitation and emission spectra of 6 in the solid state at 298K (yellow) and 77K (grey). Inset: Unnormalized emission spectra.

λ exc = 400nm, λ em = 480nm, λ em = 500nm, λ em = 570nm, λ em = 620nm Intensity (a.u.) 250 300 350 400 450 500 550 600 650 700 750 800 Figure S16. Normalized emission and excitation spectra of a saturated solution of 3 in 2-Me-THF at 77K.

16 Experimental Section Full IR and NMR data of complexes 1-6 [Pt(bzq)(pdtc)] (1): IR data, υ max (cm -1 ): 1615 m, 1564 m, 1508 vs (υ C-N ), 1443 vs, 1398 s, 1326 s, 1164 m, 940 m (υ C-S ), 825 vs, 815 vs, 750 s, 710 vs, 365 s (υ Pt-S ), 310 s (υ Pt-S ). 1 H NMR (400 MHz, CD 2 Cl 2, 298 K) δ H : 8.81 (1H, dd, 3 J 2,3 = 5.2 Hz, 4 J 2,4 = 1.2 Hz, 3 J Pt-H = 40.4 Hz, 2-H bzq), 8.40 (1H, dd, 4 J 4,2 = 1.2 Hz, 3 J 4,3 = 8.1 Hz, 4-H bzq), 7.81 (1H, AB, 3 J 5,6 = 8.8 Hz, 5-H bzq), 7.65 (1H, dd, 3 J 7,8 = 7.8 Hz, 4 J 7,9 = 0.9 Hz, 7-H bzq), 7.62 (1H, AB, 3 J 6,5 = 8.8 Hz, 6-H bzq), 7.47 (2H, m, 3-H, 8-H bzq), 7.42 (1H, dd, 4 J 9,7 = 0.9 Hz 3 J 9,8 = 7.0 Hz, 3 J Pt-H = 48 Hz, 9-H bzq), 3.90 (4H, m, CH a 2 ), 2.10 (4H, m, CH 2 b ) ppm. 1 H NMR (300 MHz, Acetonitrile-d 3, 298 K) δ H : 8.86 (1H, dd, 3 J 2,3 = 5.3 Hz, 4 J 2,4 = 1.2 Hz, 3 J Pt-H = 39.4 Hz, 2-H bzq), 8.54 (1H, dd, 4 J 4,2 = 1.2 Hz, 3 J 4,3 = 8.1 Hz, 4-H bzq), 7.86 (1H, AB, 3 J 5,6 = 8.8 Hz, 5-H bzq), 7.72 (1H, AB, 3 J 6,5 = 8.8 Hz, 6-H bzq), 7.68 (1H, dd, 3 J 7,8 = 7.8 Hz, 4 J 7,9 = 0.8 Hz, 7-H bzq), 7.55 (1H, dd, 3 J 3,2 = 5.3 Hz, 3 J 3,4 = 8.1 Hz, 3-H bzq), 7.48 (1H, dd, 3 J 8,7 = 7.8 Hz, 4 J 8,9 = 7.2 Hz, 8-H bzq), 7.37 (1H, dd, 3 J 9,7 = 0.8 Hz, 4 J 9,8 = 7.2 Hz, 3 J Pt-H = 55.4 Hz, 9-H bzq), 3.87 (4H, m, CH a 2 ), 2.10 (4H, m, CH b 2 overlapped with solvent signals) ppm. 13 C NMR (100.58 MHz, CD 2 Cl 2, 298K) δ C : 149.00 (s, 2 J Pt-C = 34.6 Hz, 2-C bzq), 144.15 (s), 137.15 (s, 4-C bzq), 134.21 (s), 130.28 (s, 3-C bzq), 130.20 (s, 8-C bzq), 129.78 (s, 5-C bzq), 127.42 (s), 123.53 (s, 6-C bzq), 122.27 (s, 2 J Pt-C 37.1 Hz, 9-C bzq), 121.40 (7-C bzq), 50.78 (s), 50.10 (s), 25.08 (s), 24.93 (s) ppm; [Pt(bzq)(dmdtc)] (2): IR data, υ max (cm -1 ): 1618 m, 1543 vs (υ C-N ), 1446 s, 1397 vs, 1328 s, 1244 m, 1155 s, 1135 s, 963 s (υ C-S ), 821 s, 810 vs, 738 s, 707 vs, 502 m, 436 s, 382 m (υ Pt-S ), 320 m (υ Pt-S ). 1 H NMR (400 MHz, CD 2 Cl 2, 298 K) δ H : 8.82 (1H, dd, 3 J 2,3 = 5.2 Hz, 4 J 2,4 = 1.3 Hz, 3 J Pt-H = 39.6 Hz, 2-H bzq), 8.40 (1H, dd, 4 J 4,2 = 1.3 Hz, 3 J 4,3 = 8.1 Hz, 4-H bzq), 7.81 (1H, AB, 3 J 5,6 = 8.7 Hz, 5-H bzq), 7.65 (1H, dd, 3 J 7,8 = 7.7 Hz,

17 4 J 7,9 = 1.0 Hz, 7-H bzq), 7.62 (1H, AB, 3 J 6,5 = 8.7 Hz, 6-H bzq), 7.48 (3H, m, 3-H, 8-H, 9-H bzq), 3.40 (3H, s, CH 3 ), 3.39 (3H, s, CH 3 ) ppm. 1 H NMR (300 MHz, Acetonitriled 3, 298 K) δ H : 8.86 (1H, dd, 3 J 2,3 = 5.2 Hz, 4 J 2,4 = 1.3 Hz, 3 J Pt-H = 39.6 Hz, 2-H bzq), 8.54 (1H, dd, 4 J 4,2 = 1.3 Hz, 3 J 4,3 = 8.1 Hz, 4-H bzq), 7.86 (1H, AB, 3 J 5,6 = 8.8 Hz, 5-H bzq), 7.72 (1H, AB, 3 J 6,5 = 8.8 Hz, 6-H bzq), 7.68 (1H, dd, 3 J 7,8 = 7.9 Hz, 4 J 7,9 = 0.9 Hz, 7-H bzq), 7.56 (1H, dd,, 3 J 3,2 = 5.2 Hz, 3 J 3,4 = 8.1 Hz, 3-H bzq), 7.51 (1H, dd, 3 J 8,7 = 7.8 Hz, 4 J 8,9 = 7.0 Hz, 8-H bzq), 7.39 (1H, dd, 3 J 9,7 = 0.9 Hz, 4 J 9,8 = 7.0 Hz, 3 J Pt-H = 55.1 Hz, 9-H bzq), 3.38 (3H, s, CH 3 ), 3.37 (3H, s, CH 3 ) ppm. 13 C NMR (75.43 MHz, CD 2 Cl 2, 298K) δ C : 148.68 (s, 2 J Pt-C = 34.3 Hz, 2-C bzq), 144.25 (s), 136.85 (s, 4-C bzq), 133.87 (s), 129.94 (s, 3-C bzq), 129.70 (s, 8-H bzq), 129.45 (s, 5-C bzq), 127.08 (s), 123.16 (s, 6-C bzq), 121.89 (s, 2 J Pt-C = 37.9 Hz, 9-C bzq), 121.08 (7-C bzq), 38.99 (s), 40.08 (s) ppm. [{Pt(bzq)(pdtc)} 2 Ag 2 ](ClO 4 ) 2 (3): IR data, υ max (cm -1 ): 1618 w, 1531 s (υ C-N ), 1446 m, 1405 m, 1335 m, 1097 vs (ClO - 4 ), 1039 vs (ClO - 4 ), 923 m, 909 m, 843 m, 763 m, 712 s, 618 vs (ClO - 4 ), 362 m (υ Pt-S ). 1 H NMR (300 MHz, Acetonitrile-d 3, 298 K) δ H : 8.68 (2H, m, 3 J Pt-H = 40.5 Hz, 2-H bzq), 8.49 (2H, dd, 4 J 4,2 = 0.9 Hz, 3 J 4,3 = 8.1 Hz, 4-H bzq), 7.82 (2H, AB, 3 J 5,6 = 8.8 Hz, 5-H bzq), 7.68 (4H, 6-H bzq (AB), 7-H bzq), 7.51 (2H, dd, 3 J 3,2 = 5.3 Hz, 3 J 3,4 = 8.1 Hz, 3-H bzq), 7.44 (2H, dd, 3 J 8,7 = 7.9 Hz, 4 J 8,9 = 7.1 Hz, 8-H bzq), 7.28 (2H, d, 4 J 9,8 = 7.1 Hz, 3 J Pt-H = 55.2 Hz, 9-H bzq), 3.75 (8H, m,ch a 2 ), 2.03 (8H, m, CH b 2 overlapped with solvent signals) ppm. [{Pt(bzq)(dmdtc)} 2 Ag 2 ](ClO 4 ) 2 (4): IR data, υ max (cm -1 ): 1620 w, 1575 s (υ C-N ), 1449 m, 1405 s, 1080 vs (ClO - 4 ), 832 s, 815 m, 762 m, 709 s, 620 vs (ClO - 4 ), 435 m, 386 m (υ Pt-S ), 330 m (υ Pt-S ). 1 H NMR (300 MHz, Acetonitrile-d 3, 298 K) δ H : 8.74 (2H, dd, 3 J 2,3 = 5.1 Hz, 4 J 2,4 = 0.9 Hz, 3 J Pt-H = 39.1 Hz, 2-H bzq), 8.51 (2H, dd, 4 J 4,2 = 0.9 Hz, 3 J 4,3 = 8.2 Hz, 4-H bzq), 7.83 (2H, AB, 3 J 5,6 = 8.8 Hz, 5-H bzq), 7.70 (2H, AB, 3 J 6,5 = 8.8 Hz,

18 6-H bzq), 7.68 (2H, dd, 3 J 7,8 = 7.9 Hz, 4 J 7,9 = 0.7 Hz, 7-H bzq), 7.54 (2H, dd,, 3 J 3,2 = 5.2 Hz, 3 J 3,4 = 8.1 Hz, 3-H bzq), 7.48 (2H, dd, 3 J 8,7 = 7.9 Hz, 4 J 8,9 = 7.1 Hz, 8-H bzq), 7.32 (2H, dd, 3 J 9,7 = 0.7 Hz, 4 J 9,8 = 7.1 Hz, 3 J Pt-H = 53.5 Hz, 9-H bzq), 3.34 (6H, s, CH 3 ), 3.31 (6H, s, CH 3 ) ppm. [{Pt(bzq)(pdtc)} 2 Ag]ClO 4 (5): IR data, υ max (cm -1 ): 1618 w, 1522 s (υ C-N ), 1447 s, 1403 m, 1331 m, 1080 vs (ClO - 4 ), 935 m (υ C-S ), 910 m, 831 vs, 816 m, 762 m, 711 vs, 621 vs (ClO - 4 ), 369 m (υ Pt-S ), 303 m (υ Pt-S ). 1 H NMR, (400 MHz, CD 2 Cl 2, 298 K) δ H : 8.26 (2H, d, 3 J 2,3 = 4.7 Hz, 3 J Pt-H = 39.1 Hz, 2-H bzq), 8.08 (2H, d, 3 J 4,3 = 8.3 Hz, 4-H bzq), 7.61 (2H, AB, 3 J 5,6 = 8.8 Hz, 5-H bzq), 7.50 (2H, d, 3 J 7,8 = 7.9 Hz, 7-H bzq), 7.40 (2H, AB, 3 J 6,5 = 8.8 Hz, 6-H bzq), 7.15 (2H, m, 8-H bzq), 7.03 (4H, m, 3-H, 9-H bzq), 3.84 (8H, m, CH 2 a ), 2.07 (8H, m, CH 2 b ) ppm. 1 H NMR (300 MHz, Acetonitrile-d 3, 298 K) δ H : 8.79 (2H, dd, 3 J 2,3 = 5.3 Hz, 4 J 2,4 = 1.0 Hz, 3 J Pt-H = 40.2 Hz, 2-H bzq), 8.52 (2H, dd, 4 J 4,2 = 1.0 Hz, 3 J 4,3 = 8.1 Hz, 4-H bzq), 7.84 (2H, AB, 3 J 5,6 = 8.8 Hz, 5-H bzq), 7.70 (2H, AB, 3 J 6,5 = 8.8 Hz, 6-H bzq), 7.67 (2H, dd, 3 J 7,8 = 7.9 Hz, 4 J 7,9 = 0.8 Hz, 7-H bzq), 7.54 (2H, dd, 3 J 3,2 = 5.3 Hz, 3 J 3,4 = 8.1 Hz, 3-H bzq), 7.46 (2H, dd, 3 J 8,7 = 7.9 Hz, 4 J 8,9 = 7.1 Hz, 8- H bzq), 7.34 (2H, dd, 3 J 9,7 = 0.8 Hz, 4 J 9,8 = 7.1 Hz, 3 J Pt-H = 55.3 Hz 9-H bzq), 3.82 (8H, m, CH a 2 ), 2.06 (8H, m, CH b 2 overlapped with solvent signals) ppm. [{Pt(bzq)(dmdtc)} 2 Ag]ClO 4 (6): IR data, υ max (cm -1 ): 1618 m, 1554 s (υ C-N ), 1447 m, 1401 s, 1331 m, 1241 m, 1080 vs (ClO - 4 ), 949 m (υ C-S ), 831 vs, 816 m, 760 m, 712 vs, 622 vs (ClO - 4 ), 434 m, 387 m (υ Pt-S ), 327 m (υ Pt-S ); 1 H NMR (300 MHz, Acetonitrile-d 3, 298 K) δ H : 8.76 (2H, dd, 3 J 2,3 = 5.1 Hz, 4 J 2,4 = 0.8 Hz, 3 J Pt-H = 39.8 Hz, 2-H bzq), 8.51 (2H, dd, 4 J 4,2 = 0.8 Hz, 3 J 4,3 = 8.1 Hz, 4-H bzq), 7.83 (2H, AB, 3 J 5,6 = 8.8 Hz, 5-H bzq), 7.70 (2H, AB, 3 J 6,5 = 8.8 Hz, 6-H bzq), 7.67 (2H, dd, 3 J 7,8 = 7.8 Hz, 4 J 7,9 = 0.8 Hz, 7-H bzq), 7.53 (2H, dd,, 3 J 3,2 = 5.2 Hz, 3 J 3,4 = 8.1 Hz, 3-H bzq), 7.48 (2H, dd, 3 J 8,7 = 7.8 Hz,

19 4 J 8,9 = 7.1 Hz, 8-H bzq), 7.34 (2H, dd, 3 J 9,7 = 0.8 Hz, 4 J 9,8 = 7.1 Hz, 3 J Pt-H = 54.5 Hz 9-H bzq), 3.34 (6H, s, CH 3 ), 3.32 (6H, s, CH 3 ) ppm. 1 General procedures and materials. The starting material [Pt(bzq)(NCMe 2 ) 2 ]ClO 4 was prepared as described elsewhere. Ammonium pyrrolidinedithiocarbamate (NH 4 S 2 CNC 4 H 8 ), sodium dimethyldithiocarbamate dihidrate (NaS 2 CNMe 2 2H 2 O), and silver perchlorate (AgClO 4 ) were purchased from commercial suppliers. Elemental analyses were carried out with a Perkin Elmer 2400 CHNS analyzer. IR spectra were recorded on a Perkin-Elmer Spectrum 100 FT-IR Spectrometer (ATR in the range 250-4000 cm -1 ). Mass spectral analyses were performed with a Microflex MALDI-TOF Bruker or an Autoflex III MALDI-TOF Bruker instruments. NMR spectra were recorded on a Bruker 300 or 400 spectrometer using the standard references: SiMe 4 for 1 H and 13 C. All of the 13 C were proton-decoupled, J are given in Hz and assignments are based on 1 H- 1 H COSY and 1 H- 13 C g-hsqc experiments. UV-visible spectra were obtained on a Thermo electron corporation evolution 600 spectrometer. Diffuse reflectance UV-vis (DRUV) spectra were recorded on a Thermo electron corporation evolution 600 spectrophotometer equipped with a Praying Mantis integrating sphere. The solid samples were homogeneously diluted with silica. The mixtures were placed in a homemade cell equipped with quartz window. Steady-state photoluminescence spectra were recorded on a Jobin-Yvon Horiba Fluorolog FL-3-11 Tau 3 spectrofluorimeter using band pathways of 3 nm for both excitation and emission. Phosphorescence lifetimes were recorded with a Fluoromax phosphorimeter accessory containing a UV xenon flash tube with a flash rate between 0.05 and 25 Hz. Phase shift and modulation were recorded over the frequency range of 0.1-100 MHz. Nanosecond lifetimes were recorded with an IBH 5000F Coaxial nanosecond flahlamp. The lifetime data were fitted using the Jobin-Yvon software package and the Origin Pro 8 program.

20 Computational Details. The computational method used was density functional theory (DFT) with the B3LYP exchange-correlation functional, 2-4 using the Gaussian 03 5 program package. The basic set used was the LanL2DZ effective core potential for the platinum atom, and 6-31G(d,p) for the remaining atoms. Time-dependent densityfunctional theory (TD-DFT) calculation were carried out using the polarized continuum model approach implemented in the Gaussian 03 software. References (1) Forniés, J.; Fuertes, S.; López, J. A.; Martín, A.; Sicilia, V. Inorg. Chem. 2008, 47, 7166. (2) Becke, A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, 3098. (3) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, 785. (4) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. (5) Gaussian 03, Revision E.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford,

21 J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.

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