Supporting Information

Sensitized Near IR Luminescence of Ln3+ ion in Lanthanide Complexes Based on Push-Pull Diketone Derivatives: Synthesis and Photophysical Behaviors Nam Seob Baek, a Yong Hee Kim, a Yu Kyung Eom,b Jung Hwan Oh,b Hwan Kyu Kim,*b Annina Aebischer,c Frédéric Gumy,c Anne-Sophie Chauvinc and Jean-Claude Bünzli*c

300 400 500 600 700

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4 1 / 0 1 / 1 1 / 2

A

λ / nm

CNPD / ACN

250 300 350 400 450 500 550 600 650 7000.0

0.2

0.4

0.6

0.8

1.0

1.2 1 / 0 1 / 1 1 / 2

CTPD / ACN

A

λ / nm

Fig. S1 UV-Vis absorption spectra of CNPD-Na and CTPD-Na as a function of the composition ratio of ligand/sodium ratio (ACN, Conc.= 2.0 × 10-5 M).

400 450 500 550 600 650 700 7500

50000

100000

150000

200000

250000

1 / 0 1 / 1 1 / 2

CNPD / ACN

Cts

λ / nm

λexc. = 390 nm

400 450 500 550 600 650 700 7500

20000

40000

60000

80000

100000

λexc. = 400 nm

CTPD / ACN

1 / 0 1 / 1 1 / 2

Cts

λ / nm

Fig. S2 Photoluminescence spectra of CNPD-Na and CTPD-Na as a function of the composition ratio of ligand/sodium ratio (ACN, Conc.= 2.0 × 10-5 M).

Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2010

0 2 4 6 8 10

Fluo

resc

ence

Inte

nsity

(log

)

Time (ns)

CTPD at 500 nm(λex = 400 nm)

MeCN = 1.5 ns

CHCl3= 0.5 ns

Cyclohexane = 150 ps

0 2 4 6 8 10

Fluo

resc

ence

Inte

nsity

(log

)

Time (ns)

CNPD at 500 nm(λex = 390 nm) ACN = 1.5 ns

CHCl3= 0.5 ns Cyclohexane = 150 ps

Fig. S3 UV-Vis absorption spectra of CNPD-Na and CTPD-Na (ACN) 2.0 × 10-5 M

400 500 600 1400 16000

1x105

2x105

3x105

4x105

5x105

6x105

0

2000

4000

6000 ligand Complex

PL In

tens

ity (a

.u.)

Wavelength (nm)

1500

Fig. S4 Near-IR emission spectra of Er3+-[CNPD]3(tpy) in MeCN (λex = 390 nm, Conc. = 2.0 × 10-5 M).

0.000 0.005 0.010 0.015 0.0201

10

100

1000

Er3+-[CTPD]3(terpy)

Inte

nsity

Time (ns)0.000 0.005 0.010 0.015 0.020

10

100

1000

Nd3+-[CNPD]3(terpy)

Inte

nsity

Time (ns)0.000 0.002 0.004 0.006 0.008 0.010 0.012 0.014 0.016

10

100

1000

Er3+-[CNPD]3(terpy)

Inte

nsity

Time (ns)

Fig. S5 NIR luminescence decays of [Er(CTPD)3(tpy)], [Nd(CNTD)3(tpy)], and [Er(CNPD)3(tpy)] 2.0 × 10-5 M in MeCN at 10 K and upon excitation at 355 nm with a pulse width of 10 ns.

Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2010

400 500 600 700 800

0.0

0.4

0.8

1.2

1.6

2.0

delay = 0 ms delay = 0,05 msno

rmal

ized

Wavelength (nm)

λexc. = 390 nm T = 295 K

T = 77 K

Fig. S6. Emission spectra of [Gd(CNPD)3(tpy)] : 2.0 × 10-5 M in MeCN at 295 K (Top) and 77 K (Bottom) without and with time delay.

Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2010