Supplementary Material (ESI) for Chemical … · Valentina Calabrese, Silvio Quici, Ester Rossi, Elena Cariati, Claudia Dragonetti, Dominique Roberto, Elisa Tordin, Filippo De Angelis

1

Highly stable 7-N,N-Dibutylamino-2-azaphenanthrene and 8-N,N-dibutylamino-2-azachrysene as a new class of second order NLO-active chromophores Valentina Calabrese, Silvio Quici, Ester Rossi, Elena Cariati, Claudia Dragonetti, Dominique Roberto, Elisa Tordin, Filippo De Angelis and Simona Fantacci

ESI

Synthesis of the various compounds:

Synthetic schemea

Cl

NBu2

PPh3+Cl-

NBu2 NBu2

N

NBu2

N

1 2 3

NBu2

N

Ir(CO)2Cl

4 (L3)

2

NBu2

N

NBu2

N

5 (IrL3)

7 (L4)

NBu2

N

NBu2

N I-

Ir(CO)2Cl

6

(a) (b) (c) (d) (e)

(f) (g) (h)

8 (IrL4) 9 (L4MeI)

NMe2

N

Br

N

NMe2

B(OH)2

+HCl

10 (L1)

OH

NBu2

(i)

6

(l)

aReagents and conditions: (a) PPh3, CCl4, THF, 48 h, 95%; (b) PPh3, heptane, reflux, 24 h, 82%; (c) 3-pyridinecarboxaldehyde, tBuOK, dry MeOH, N2, reflux, overnight, 82%; (d) 2-Me-THF, hν, 1.5 h, -15 °C, 46%; (e) [Ir-(COT)2Cl]2, dry CH3CN, CO, 1 h, quantitative; (f) isoquinoline-5-carbaldehyde, tBuOK, dry MeOH, N2, reflux, overnight, 82%; (g) THF, hν, 8 h, 17 °C, 33.5%; (h) [Ir-(COT)2Cl]2, dry CH3CN, CO, 1 h, quantitative; (i) THF, MeI, RT, overnight, 85% (l) acqueous Na2CO3 tetrakis(triphenylphosphine)palladium(0), THF, 80 °C, 18 h, 79%.

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2010

2

Experimental section

N,N-dibutyl-3-(chloromethyl)aniline 1

To a solution of 3-(dibutylamino)benzyl alcohol (3.8 g, 16.15 mmol) in dry THF (30 mL) under

nitrogen atmosphere was added PPh3 (6.3 g, 24 mmol) and CCl4 (1.9 ml, 20 mmol) and the mixture

was refluxed for 48 h. After cooling at room temperature the white precipitate was filtered off and

the organic phase concentrated in vacuo. The crude product was purified by silica gel column

chromatography using pure CH2Cl2 as eluent affording compound 1 as a colourless oil (4.04 g,

95%). δH(400 MHz, CDCl3) 7.17 (t, 1 H, H5, J= 8 Hz), 6.64 (m, 2 H, H2, H6), 6.59 (dd, 1 H, H4, J=

8, 2.4 Hz), 4.54 (s, 2 H, CH2), 3.27 (t, 4 H, NCH2(CH2)2CH3, J= 7.6 Hz), 1.55 (m, 4 H,

CH2CH2CH2CH3), 1.37 (sexstet, 4 H, N(CH2)2CH2CH3, J= 7.6 Hz), 0.96 (t, 6 H, N(CH2)3CH3, J=

7.6 Hz); δC(100 MHz, CDCl3) 148.48, 138.33, 129.52, 115.16, 111.72, 111.61, 50.75, 47.27, 29.38,

20.36, 14.01; m/z (ESI) 254.2 [M + H+], calcd. 253.16.

(3-N,N-dibutylamino)benzyltriphenylphosphonium chloride 2

To a solution of N,N-dibutyl-3-chloromethylaniline (2.95 g, 11.6 mmol) in heptane (5 mL) was

added PPh3 (3.6 g, 13.7 mmol) and the mixture was refluxed for 24 h. After cooling at room

temperature the white precipitate was filtered and washed with heptane and Et2O, then concentrated

in vacuo affording pure 2 (4.9 g, 82%). δH(400 MHz, CDCl3) 7.76 (m, 15 H, PPh3), 6.90 (t, 1 H, H5,

J=8 Hz), 6.46 (dt, 1 H, H6, J=8.2 Hz), 6.28 (d, 1 H, H2, J=2 Hz), 6.16 (d, 1 H, H4, J=8 Hz), 5.15 (d,

2 H, CH2P, J=14 Hz), 3.02 (t, 4 H, NCH2(CH2)2CH3, J=7 Hz), 1.25 (m, 8 H, NCH2(CH2)2CH3),

0.87 (t, 6 H, N(CH2)3CH3, J=7 Hz); δC(100 MHz, CDCl3) 148.47, 134.82, 134.38 (d, JC-P= 10 Hz),

130.08 (d, JC-P= 12 Hz), 129.55 (d, JC-P= 3 Hz), 127.69 (d, JC-P= 8 Hz), 118.30 (d, JC-P= 85 Hz),

117.74 (d, JC-P=5 Hz), 114.52 (d, JC-P=5 Hz), 111.68 (d, JC-P=3 Hz), 50.46, 31.41 (d, JC-P= 43 Hz),

29.20, 20.24, 14.02; m/z (ESI) 480.4 [M+], calcd. 480.28.

(E,Z)-3-(3-N,N-dibutylaminostiryl)pyridine 3

(3-N,N-dibutylamino)benzyltriphenylphosphonium chloride (1.09 g, 2.12 mmol) was dissolved in

dry MeOH (30 mL) under nitrogen atmosphere, tBuOK (236 mg, 1.93 mmol) was added and the

solution was heated to reflux. After 4 h 3-pyridinecarboxaldehyde (206 mg, 1.93 mmol) was added

and the solution was refluxed overnight. The solvent was concentrated in vacuo, the residue was

dissolved in CH2Cl2 and washed twice with water. The organic phase was dried over Na2SO4 and

evaporated in vacuo, then 10 mL of hexane/AcOEt 1:1 v/v solution was added to the crude product

to allow the precipitation of triphenylphosphine oxide which was filtered off. The organic phase


3

was evaporated in vacuo and the crude product was purified by silica gel column chromatography

(hexane/AcOEt 8:2) affording 3 (488 mg, 82%) as E/Z isomers mixture. This product was generally

used as isomeric mixture. The two isomers were once isolated as pure compounds only for

characterization. Z isomer-δH(400 MHz, CDCl3) 8.52 (d, 1 H, PyH2, J=2.4 Hz), 8.40 (dd, 1 H,

PyH6, J=4.8, 2 Hz), 7.59 (dt, 1 H, PyH4, J=7.6, 1.6 Hz), 7.11 (m, 2 H, ArH5, PyH5), 6.72 (d, 1 H,

ArCH=CH, J=12 Hz), 6.50 (m, 4 H, ArCH=CH, ArH2, ArH4, ArH6), 3.11 (t, 4 H, NCH2(CH2)2CH3,

J=7.6 Hz), 1.42 (quint., 4 H, NCH2CH2CH2CH3, J=7.6 Hz), 1.25 (sextet, 4 H, N(CH2)2CH2CH3,

J=7.2 Hz), 0.90 ( t, 6 H, N(CH2)3CH3, J=7.2 Hz); δC(100 MHz, CDCl3) 150.34, 148.23, 147.84,

137.25, 135.92, 133.95, 133.43, 129.35, 125.59, 122.87, 115.75, 111.73, 111.18, 50.79, 25.34,

20.27, 13.95; m/z (ESI) 309.3 [M + H+], calcd: 308.23. E isomer-δH(400 MHz, CDCl3) 8.72 (d, 1

H, PyH2, J=2 Hz), 8.48 (dd, 1 H, PyH6, J=4.8, 1.6 Hz), 7.84 (dt, 1 H, PyH4, J=7.6, 1.6 Hz), 7.25 (m,

2 H, PyH5, ArH5), 7.14 (d, 1 H, ArCH=CH, J=16 Hz), 7.02 (d, 1 H, ArCH=CH, J=16 Hz), 6.85 (d,

1 H, ArH4, J=7.6 Hz), 6.75 (broad s, 1 H, ArH2), 6.61 (dd, 1 H, ArH6, J=8, 2.8 Hz), 3.31 (t, 4 H,

NCH2(CH2)2CH3, J=7.6 Hz), 1.59 (q, 4 H, NCH2CH2CH2CH3, J=8 Hz), 1.40 (sextet, 4 H,

N(CH2)2CH2CH3, J=8 Hz), 0.98 (t, 6 H, N(CH2)3CH3, J=7.2 Hz); δC(100 MHz, CDCl3) 148.56,

148.34, 137.49, 133.31, 132.61, 132.1, 129.56, 124.19, 123.48, 113.53, 112.00, 110.36, 50.82,

29.47, 20.41, 14.07; m/z (ESI) 309.3 [M + H+], calcd. 308.23.

8-(N,N-dibutylamino)benzo[f]isoquinoline 4

A magnetically stirred solution of E/Z-3-(3-N,N-dibutylaminostiryl)pyridine (468 mg, 1.52 mmol)

in 2-Me-THF (500 mL) was irradiated by a Hg high pressure lamp in a quartz reactor for 1.5 h at -

15 °C. The solvent was evaporated in vacuo and the brown oil residue was purified by silica gel

column chromatography (hexane/AcOEt 1:1) affording pure 4 (216 mg, 46%). δH(400 MHz,

CD3OD) 8.79 (d, 1 H, H4, J=0.7 Hz), 8.53 (d, 1 H, H10, J=9.2 Hz), 8.45 (d, 1 H, H1, J=6 Hz), 8.37

(d, 1 H, H2, J=6 Hz), 7.70 (m, 2 H, H5, H6, J=8.8 Hz), 7.22 (dd, 1 H, H9, J=9.2, 2.4 Hz ), 7.00 (d, 1

H, H7, J=2.4 Hz ), 3.47 (t, 4 H, NCH2(CH2)2CH3, J=7.6 Hz), 1.69 (m, 4 H, NCH2CH2CH2CH3),

1.46 (sextet, 4 H, N(CH2)2CH2CH3, J=7.6 Hz), 1.03 (t, 6 H, N(CH2)3CH3, J=7.6 Hz); δC(100 MHz,

CDCl3) 149.22, 148.94, 142.05, 136.57, 136.19, 128.85, 125.26, 124.98, 124.93, 117.84, 115.65,

114.43, 107.13, 50.86, 29.41, 20.37, 14.02; m/z (ESI) 307.21658 [M + H+], calcd. 306.21688;

λ(CHCl3)/278 nm (ε/dm3mol-1cm-1 28 626 ), 347 nm (14 397).

[Ir(CO)2Cl(8-(N,N-dibutylamino)benzo[f]isoquinoline)] 5

A sample of [Ir(COT)2Cl]2 (119.4 mg, 0.13 mmol) was suspended in dry CH3CN (50 mL) under

nitrogen atmosphere. After 2 min, the nitrogen was replaced by carbon monoxide and the


4

suspension turned yellow for the formation of [Ir(CO)2Cl]2 complex. 8-(N,N-

dibutylamino)benzo[f]isoquinoline (76.4 mg, 0.25 mmol) was added and after 1 h the solution was

evaporated to dryness in vacuo affording pure 5 (159.0 mg, quantitative yield) (Found: C, 46.83; H,

4.42; N, 4.74. C23H26N2O2IrCl requires: C, 46.81; H, 4.44; N, 4.75%); δH(400 MHz, CDCl3) 9.18 (s,

1 H, H4), 8.61 (d, 1 H, H2, J=6.5 Hz), 8.42 (d, 1 H, H10, J=9.2 Hz), 8.28 (d, 1 H, H1, J=6.5 Hz), 7.74

(d, 1 H, H5, J=9.2 Hz), 7.65 (d, 1 H, H6, J=9.2 Hz), 7.18 (dd, 1 H, H9, J=9.2, 2.8 Hz), 6.93 (d, 1 H,

H7, J=2.8 Hz), 3.47 (t, 4 H, NCH2(CH2)2CH3, J=6.5 Hz), 1.69 (m, 4 H, NCH2CH2CH2CH3), 1.47

(m, 4 H, N(CH2)2CH2CH3), 1.03 (t, 6 H, N(CH2)3CH3, J=7.6 Hz); λ(CHCl3)/279 nm (ε/dm3mol-

1cm-1 35 420), 390 nm (25 670); ν/cm-1 2073 (CO), 1994 (CO).

(E,Z)-5-(3-N,N-dibutylaminostiryl)isoquinoline 6

A solution of 2 (2.20 g, 4.2 mmol) in dry MeOH (50 mL) and tBuOK (513 mg; 4.2 mmol) was

refluxed for 4 h, then isoquinoline-5-carbaldehyde (609 mg, 3.8 mmol) dissolved in dry MeOH (5

mL) was added and the solution was refluxed overnight. The solvent was evaporated in vacuo and

the residue was dissolved in CH2Cl2 (50 mL) and washed with water. The organic phase was dried

over MgSO4 and evaporated in vacuo to give a brown residue. Then 10 mL of a 4:1 v/v

hexane/AcOEt solution was added to the crude product to allow the precipitation of

triphenylphosphine oxide which was filtered off. The organic phase was evaporated in vacuo and

the residue was purified by column chromatography on silica gel (hexane/AcOEt 1:1) to afford 6 as

mixture of E/Z isomers as yellow oil (1.12 g, 82%). This product was generally used as isomeric

mixture. The two isomers were once isolated as pure compounds only for characterization. Z

isomer-δH(400 MHz, CDCl3) 9.26 (s, 1 H, IsoquinH1), 8.50 (d, 1 H, IsoquinH3, J=6 Hz), 7.86 (m, 2

H, IsoquinH4, IsoquinH6), 7.65 (d, 1 H, IsoquinH8, J=7.2 Hz), 7.51 (t, 1 H, IsoquinH7, J=7.2 Hz),

7.02 (t, 1 H, ArH5, J=7.8 Hz), 6.90 (d, 1 H, ArCH=CH, J=12 Hz), 6.86 (d, 1 H, ArCH=CH, J= 12

Hz), 6.45 (br. s, 2 H, ArH4, ArH6), 6.26 (br. s, 1 H, ArH2,), 2.87 (t, 4 H, NCH2(CH2)2CH3, J=7.2

Hz), 1.20 (m, 4 H, NCH2CH2CH2CH3), 1.06 (sexstet, 4 H, N(CH2)2CH2CH3, J=7.2 Hz), 0.79 (t, 6

H, N(CH2)3CH3, J=7.2 Hz); δC(100 MHz, CDCl3) 152.60, 142.80, 136.95, 135.09, 134.41, 134.26,

130.92, 129.10, 128.80, 127.17, 126.81, 118.13, 116.86, 115.28, 50.90, 29.03, 20.25, 13.87. E

isomer-δH (400 MHz, CDCl3) 9.29 (s, 1 H, IsoquinH1), 8.60 (d, 1 H, IsoquinH3, J=6 Hz), 8.00 (m, 2

H, IsoquinH4, IsoquinH6), 7.93 (d, 1 H, IsoquinH8, J=8 Hz), 7.75 (d, 1 H, ArCH=CH, J=16 Hz),

7.64 (t, 1 H, IsoquinH7, J=7.6 Hz), 7.28 (t, 1 H, ArH5, J=8 Hz), 7.19 (d, 1 H, ArCH=CH, J=16 Hz),

6.97 (d, 1 H, ArH4, J=8 Hz), 6.85 (s, 1 H, ArH2), 6.67 (dd, 1 H, ArH6, J=8, 2.4 Hz), 3.36 (t, 4 H,

NCH2(CH2)2CH3, J=7.6 Hz), 1.65 (m, 4 H, NCH2CH2CH2CH3), 1.42 (sexstet, 4 H,

N(CH2)2CH2CH3, J=7.2 Hz), 1.20 (t, 6 H, N(CH2)3CH3, J=7.2 Hz); δC(100 MHz, CDCl3) 153.15,


5

148.60, 143.22, 137.97, 134.41, 134.13, 133.99, 129.60, 127.20, 127.10, 123.17, 116.73, 113.54,

111.95, 110.55, 50.84, 29.46, 20.41, 14.06.

8-N,N-dibutylaminonafto[2,1-f]isoquinoline 7

A magnetically stirred solution of E/Z-5-(3-N,N-dibutylaminostiryl)isoquinoline (600 mg, 1.67

mmol) in THF (500 mL) was irradiated by a Hg high pressure lamp in a quartz reactor for 8 h at 17

°C. After the evaporation of the solvent the residue was purified by column chromatography on

silica gel (hexane/AcOEt 1:1) then by crystallization from hexane to afford a pale yellow solid (200

mg, 33.5%). mp 211 °C (lit.,1 213 °C). δH(400 MHz, CDCl3) 9.28 (1 H, s, H1), 8.70 (1 H, d, H3, J=6

Hz), 8.64 (1 H, d, H11, J=9 Hz), 8.56 (1 H, d, H10, J=9 Hz), 8.46 (1 H, d, H6, J=8.8 Hz), 8.39 (1 H,

d, H4, J=6 Hz), 7.96 (1 H, d, H12, J=8.8 Hz), 7.85 (1 H, d, H5, J=8.8 Hz), 7.23 (1 H, dd, H9, J=8.8,

2.8 Hz), 7.01 (1 H, d, H7, J=2.8 Hz), 3.47 (4 H, t, NCH2(CH2)2CH3, J= 7.6 Hz), 1.70 (4 H, m,

NCH2CH2CH2CH3), 1.47 (4 H, sextet, N(CH2)2CH2CH3, J= 7.6 Hz), 1.04 (6 H, t, N(CH2)3CH3,

J=7.6 Hz); δC(100 MHz, CDCl3) 151.50, 147.43, 143.29, 135.27, 135.00, 131.29, 127.39, 126.32,

125.26, 124.67, 123.47, 122.55, 120.95, 120.94, 116.77, 115.12, 106.61, 50.85, 29.53, 20.43, 13.97;

m/z (ESI) 357.23204 [M + H+], calcd, 356.2325; λmax(CHCl3)/nm 305 nm, (ε/dm3mol-1cm-1 41

462), 361 (17 179).

[Ir(CO)2Cl(8-N,N-dibutylaminonafto[2,1-f]isoquinoline)] 8

A sample of [Ir(COT)2Cl]2 (53.3 mg, 0.42 mmol) was suspended in dry CH3CN (50 mL) under

nitrogen atmosphere. After 2 min, the nitrogen was replaced by carbon monoxide and the

suspension turned yellow for the formation of [Ir-(CO)2Cl]2 complex. Then 8-N,N-

dibutylaminonafto[2,1-f]isoquinoline (30.3 mg, 0.08 mmol) was added and after 1 h the solution

was evaporated to dryness in vacuo affording pure 8 (52.5 mg, quantitative) (Found: C, 50,60; H,

4.40; N, 4.38. C27H28N2O2IrCl requires: C, 50.65; H, 4.41; N, 4.38%); δH(400 MHz, CDCl3) 9.41 (s,

1 H, H1), 8.76 (d, 1 H, H11, J=9.2 Hz), 8.70 (d, 1 H, H3, J=6.5 Hz), 8.58 (d, 1 H, H10, J=9.2 Hz),

8.51 (d, 1 H, H4, J=6.5 Hz), 8.41 (d, 1 H, H12, J=9.0 Hz), 8.00 (d, 1 H, H11, J=9.0 Hz), 7.89 (d, 1 H,

H6, J=9.1 Hz), 7.25 (dd, 1 H, H9, J=9.6, 2.8 Hz), 7.00 (d, 1 H, H7, J=2.8 Hz), 3.47 (t, 4 H,

NCH2(CH2)2CH3, J=7.6 Hz), 1.69 (m, 4 H, NCH2CH2CH2CH3), 1.46 (m, 4H, N(CH2)2CH2CH3),

1.02 (t, 6 H, N(CH2)3CH3); λ(CHCl3)/nm 272 (ε/dm3mol-1cm-1 34 541), 420 (12 737); ν/cm-1 2074

(CO), 1995 (CO).

1 J.Phys. Chem. B 2003, 107, 7896-7902.


6

8-(N,N-dibutylamino)-2-methylnaphto[2,1-f]isoquinolinium iodide 9

8-N,N-dibutylaminonafto[2,1-f]isoquinoline (120 mg, 0.33 mmol) was dissolved in THF (10 mL)

and MeI was added (149 μl, 2.31 mmol) and the solution was reacted at room temperature

overnight. The resulting red precipitate was filtered, washed with few millilitres of THF and dried

under vacuum, affording the pure product 9 (140 mg, 85%). mp 259-260.7 °C. δH(400 MHz,

CD3OD) 9.55 (s, 1 H, H1), 9.03 (m, 2 H, H3, H11), 8.69 (d, 1 H, H10, J=9.2 Hz), 8.57 (m, 2 H, H4,

H6), 8.19 (d, 1 H, H12, J=9.2 Hz), 7.98 (d, 1 H, H5, J=9.2 Hz), 7.35 (dd, 1 H, H9, J=9.2, 2.4 Hz),

7.09 (d, 1 H, H7, J=2.4 Hz), 4.46 (s, 3 H, NCH3), 3.53 (t, 4 H, NCH2(CH2)2CH3, J=7.6 Hz), 1.68

(quintet, 4 H, NCH2CH2CH2CH34, J=7.6 Hz), 1.47 (sextet, 4 H, N(CH2)2CH2CH3, J=7.2 Hz), 1.03

(t, 6 H, N(CH2)3CH3, J=7.2 Hz); δC(100 MHz, CD3OD) 149.01, 147.36, 137.48, 136.84, 136.18,

134.76, 129.17, 126.66, 125.84, 125.44, 125.02, 122.09, 120.69, 120.54, 119.92, 115.58, 106.19,

50.33, 46.53, 29.21, 19.90, 12.96 ; λ(CHCl3)/nm 272 (ε/dm3mol-1cm-1 39 886), 285 (37 869), 315

(19 045), 364 (14 386), 473 (26 523); m/z (ESI) 371.24789 [M+], calcd. 371.24818.

N,N-dimetyl-4-(pyridin-4-yl)aniline 10

In a Schlenk tube a stirred mixture of 4-bromopyridine hydrochloride (593 mg, 3.05 mmol), 4-

(dimethylamino)phenylboronic acid (1.00 g, 6.10 mmol), aqueous Na2CO3 (15 mL, 15.3 mmol) and

tetrakis(triphenylphosphine)palladium(0) (176 mg, 0.153 mmol) in dry tetrahydrofuran (60 mL)

was heated at 80°C under nitrogen for 18 h. After cooling at room temperature, organic solvent was

removed in vacuo and the aqueous phase was extracted with CH2Cl2. The collected organic phases

were dried over Na2SO4 and the solvent removed in vacuo. The crude product was purified by

column chromatography on silica gel using pure chloroform as eluent to afford the product 10 (480

mg, 79%) as pale white solid. mp 231-233 °C. δH(400 MHz, CDCl3) 8.57 (d, 2 H, J= 6.2 Hz), 7.60

(d, 2 H, J= 8.9 Hz), 7.48 (d, 2 H, J= 6.2 Hz), 6.79 (d, 2 H, J= 8.9 Hz); δC(100 MHz, CDCl3)

151.17, 149.77, 147.50, 127.68, 124.96, 120.33, 112.46, 40.31; λ(CHCl3)/nm 417 (ε/dm3mol-1cm-1 46

500), 506 (9 160).


7

1H-NMR spectra

N,N-dibutyl-3-(chloromethyl)aniline 1


8

(3-N,N-dibutylamino)benzyltriphenylphosphonium chloride 2


9

(Z)-3-(3-N,N-dibutylaminostiryl)pyridine 3


10

(E)-3-(3-N,N-dibutylaminostiryl)pyridine 3


11

8-(N,N-dibutylamino)benzo[f]isoquinoline 4


12

[Ir(CO)2Cl(8-(N,N-dibutylamino)benzo[f]isoquinoline)] 5


13

(Z)-5-(3-N,N-dibutylaminostiryl)isoquinoline 6


14

(E)-5-(3-N,N-dibutylaminostiryl)isoquinoline 6


15

8-N,N-dibutylaminonafto[2,1-f]isoquinoline 7


16

[Ir(CO)2Cl(8-N,N-dibutylaminonafto[2,1-f]isoquinoline)] 8


17

8-(N,N-dibutylamino)-2-methylnaphto[2,1-f]isoquinolinium iodide 9


18

N,N-dimetyl-4-(pyridin-4-yl)aniline 10


19

UV-Visible Spectra

Compound 3

347 nm

278 nm

0

0,2

0,4

0,6

0,8

1

1,2

1,4

230 280 330 380 430 480 530 580

nm

Abs

orba

nce

Compound 4

279 nm

390 nm

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

230 260 290 320 350 380 410 440 470 500 530 560 590

nm

Abs

orba

nce

Compound 6

361 nm

305 nm

0

0,2

0,4

0,6

0,8

1

1,2

1,4

230 280 330 380 430 480 530 580

nm

Abs

orba

nce

NBu2

N

NBu2

N

Ir(CO)2Cl

NBu2

N


20

Compound 7

283 nm

420 nm

272 nm

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

230 280 330 380 430 480 530 580

nm

Abs

orba

nce

Compound 8

473 nm

364 nm

315 nm

285 nm272 nm

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

240 290 340 390 440 490 540 590

nm

Abs

orba

nce

Compound 9

251 nm

506 nm

417nm

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1

240 290 340 390 440 490 540 590

nm

Abs

orba

nce

NMe2

N

NBu2

N

Ir(CO)2Cl

NBu2

N I-


21

L3 optimized molecular structure in CHCl3 solution: N 6.334882 -0.498960 -0.117160 C 5.602164 -1.562032 -0.531317 C 5.653288 0.567533 0.280809 C 4.244304 0.662547 0.299568 C 3.482534 -0.459635 -0.137363 C 4.220759 -1.590193 -0.559264 C 3.578025 1.852577 0.744500 C 2.219412 1.924974 0.757406 C 1.404623 0.816994 0.328244 C 2.037458 -0.379412 -0.124332 C 0.001242 0.918839 0.348780 C -0.832005 -0.135390 -0.061087 C -0.182528 -1.326759 -0.510411 C 1.191148 -1.432920 -0.538782 H 6.241128 1.425493 0.615108 H 6.171752 -2.432646 -0.855985 H 3.721492 -2.489535 -0.908360 H 4.183080 2.696596 1.072384 H 1.719497 2.830749 1.097201 H -0.423364 1.858138 0.684077 H 1.620300 -2.368799 -0.887098 H -0.767592 -2.183097 -0.824863 N -2.209072 -0.040894 -0.030800 C -2.884171 1.121671 0.543068 C -3.074187 -1.081997 -0.584833 C -3.113041 2.274082 -0.449288 H -3.851673 0.781275 0.932119 H -2.319896 1.475973 1.413554 C -3.440336 -2.195323 0.410396 H -3.991723 -0.592728 -0.933915 H -2.608248 -1.509536 -1.479844 C -4.385519 -3.238999 -0.197554 H -2.523082 -2.684499 0.765116 H -3.909409 -1.742050 1.295279 C -4.769829 -4.347285 0.788270 H -5.295849 -2.738368 -0.557962 H -3.912656 -3.686164 -1.083968 H -5.443563 -5.076789 0.324425 H -3.883501 -4.888640 1.141314 H -5.278580 -3.935363 1.668536 C -3.834509 3.466143 0.192625 H -2.148210 2.599217 -0.860667 H -3.701024 1.900921 -1.299793 C -4.086706 4.614100 -0.790465 H -4.792407 3.127446 0.613265 H -3.241929 3.834982 1.042223 H -4.602059 5.450102 -0.303897 H -3.144730 4.996397 -1.202630 H -4.706808 4.284102 -1.633024


22

L4 optimized molecular structure in CHCl3 solution: C 5.236846 -0.924111 -0.275644 C 4.385856 -2.004439 -0.651952 C 4.664539 0.309008 0.149141 C 3.224623 0.447109 0.192113 C 2.402958 -0.646502 -0.190788 C 3.028334 -1.867546 -0.610360 C 2.601581 1.664811 0.612751 C 1.244198 1.797304 0.655118 C 0.377723 0.722278 0.278227 C 0.963102 -0.507658 -0.150943 C -1.022403 0.882374 0.321388 C -1.902256 -0.144954 -0.046050 C -1.304881 -1.373578 -0.470773 C 0.061066 -1.537400 -0.519404 C 5.580720 1.329963 0.505156 H 4.836819 -2.941807 -0.973877 H 2.412191 -2.711237 -0.904040 H 3.217948 2.508563 0.907791 H 0.798427 2.735750 0.981223 H -1.400263 1.847834 0.638096 H 0.435552 -2.501998 -0.848814 H -1.928286 -2.214888 -0.750587 N -3.275239 0.001462 0.000508 C -3.895255 1.206955 0.545964 C -4.185963 -1.009936 -0.534255 C -4.078205 2.342233 -0.475561 H -4.874636 0.920675 0.948719 H -3.309973 1.558395 1.403773 C -4.599135 -2.090389 0.478715 H -5.082368 -0.487649 -0.890641 H -3.741157 -1.472551 -1.422609 C -5.586018 -3.103373 -0.114927 H -3.703540 -2.611698 0.843042 H -5.050056 -1.603836 1.355336 C -6.014733 -4.181918 0.885377 H -6.475175 -2.571158 -0.482827 H -5.131545 -3.581336 -0.994905 H -6.717206 -4.889891 0.430857 H -5.150841 -4.753712 1.246008 H -6.506555 -3.738438 1.759899 C -4.742547 3.582107 0.136397 H -3.101784 2.613090 -0.898732 H -4.686071 1.973295 -1.313873 C -4.941985 4.715662 -0.875084 H -5.714795 3.299599 0.565615 H -4.132287 3.944219 0.976371 H -5.416681 5.586948 -0.409450 H -3.983647 5.042665 -1.297007 H -5.578235 4.394282 -1.708892 C 6.938736 1.096310 0.428095


23

N 7.490850 -0.077117 0.023652 C 6.647301 -1.040175 -0.311717 H 5.239419 2.304266 0.841064 H 7.643587 1.880981 0.701514 H 7.086672 -1.985575 -0.638088

Figure S1:Optimized molecular structure of L3 and L4.

Figure S2:Optimized molecular structure of IrL3 and IrL4 complexes with selected bond distances

and bond and dihedral angles.


24

Figure S3: Schematic representation of frontier molecular orbitals of L3 and L4

Figure S4. Isodensity plots of the electron density difference between S1-S5 excited states and the

ground state of L3 and L4 ligands. A red (blue) color indicates a decrease (increase) of the electron

density upon excitation. The excitation wavelengths, oscillator strengths are also reported.

Full reference 14:


25

Gaussian 03, Revision C.02, 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, 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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