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Photosensitized Near-Infrared Luminescence of Yb(III) Complexes Containing Phenanthroline

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2008 Jpn. J. Appl. Phys. 47 1192

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Japanese Journal of Applied Physics
Vol. 47, No. 2, 2008, pp. 1192–1195
#2008 The Japan Society of Applied Physics

Photosensitized Near-Infrared Luminescence of Yb(III) Complexes

Containing Phenanthroline Derivatives
Yasuchika H ASEGAWA1
, Takuma Y ASUDA1 , Kazuki N AKAMURA2 , and Tsuyoshi K AWAI1
1
Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan
2
Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering,
Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan
(Received April 2, 2007; revised June 30, 2007; accepted July 31, 2007; published online February 15, 2008)

Near-IR emission of novel Yb(III) complexes with phenanthroline derivertives, bis(phenanthroline)-tris(bis-perfluorometha-

nesurfonyliminate)ytterbium [Yb(pms)3 (phen)2 ] and dipyridophenazine-tris(bis-perfluoromethanesurfonyliminate)ytterbium
[Yb(pms)3 (dip)] are studied in dimethylsulfoxide [DMSO-d6 ]. The emission quantum yields of Yb(pms)3 (phen)2 and
Yb(pms)3 (dipy-phenazine) excited at 940 nm (2 F7=2 –2 F5=2 transition) were found to be 7.4 and 9.1%, respectively. We
successfully observed the photosensitized near-infrared emission from the Yb(III) complexes upon excitation of the aromatic
ligands. The energy transfer efficiencies of Yb(pms)3 (phen)2 and Yb(pms)3 (dip) excited at 310 nm (
–

transition) were
evaluated to be 9.1 and 4.0%, respectively. [DOI: 10.1143/JJAP.47.1192]
KEYWORDS: lanthanide, ytterbium, emission, luminescence, near-infrared region, quantum yield

1. Introduction
Near-infrared (IR) luminescent materials containing lan-
thanide(III) complexes have become the focus of consid-
erable interest from the viewpoint of fiber-optic telecommu-
nication systems, laser systems, electroluminescence de-
vices, and biosensing engineering.1–4) Near-IR luminescence
in Yb(III), Nd(III), and Er(III) complexes has recently been Yb(pms)3(phen)2
reported.5–10) However, an emission quantum yield more
than 5% has never been observed in the near-IR region.11)
The significant relaxation process coupled with the vibra-
tional mode of the ligands seems to be one of the origins of a
relatively low emission quantum yield.12) For construction of
strong luminescent lanthanide(III) complexes in near-infra-
red region, lanthanide(III) complexes should be designed to
meet two criteria: (1) an efficient formation of the excited Yb(pms)3(dip)
state and (2) high emission quantum yield of f–f transitions.
To increase emission quantum yield, it is first necessary to Fig. 1. (Color online) Chemical structures of Yb(pms)3 (phen)2 and
suppress radiationless transition caused by vibrational Yb(pms)3 (Dip).
relaxation. In earlier studies, we found the suppression of
radiationless quenching in fluid Nd(III) systems by com-
plexing Nd(III) with perfluoromethanesurfonyliminate (pms)
composed only of the moieties of low-vibrational mode.11) and Yb(III) ions. The novel Yb(pms)3 (phen)2 and Yb(pms)3 -
Yb(III) complexes coordinated with the pms ligands are also (dip) will likely generate applications in near-IR devices.
expected to show increased emission quantum yields.
Second, enhanced emission might also be expected in the 2. Experimental Procedure
lanthanide(III) complexes with rigid
-conjugated organic 2.1 Apparatus
antenna ligands because of a large extinction coefficient and IR spectra used to identify synthesized materials were
a low-vibrational coupling cross section with the metal ions. obtained using a JASCO FT/IR-420 spectrometer. Elemen-
Here, we report on novel Yb(III) complexes with the low- tal analyses were performed with a Perkin Elmer 2400II
vibrational ligands pms and organic
-conjugated chromo- CHNS/O. 1 H NMR data were obtained using a JEOL AL-
phores of phenanthroline derivatives, Yb(pms)3 (phen)2 and 300 (300 MHz) spectrometer and were determined using
Yb(pms)3 (dip) (phen: phenanthrorine, dip: dipyridophena- tetramethylsilane (TMS) as an internal standard. MALDI
zine; Fig. 1). Prepared Yb(pms)3 (phen)2 and Yb(pms)3 (dip) time-of-flight mass spectroscopy (TOF-MS) spectra were
show strong luminescence in the near-infrared region, and obtained using a Applied Biosystems DE-STR voyager.
their emission quantum yields were found to be 7.4 and
9.1%, respectively. These are the first evaluations of the 2.2 Materials
emission quantum yields of Yb(III) complexes excited at Bis(perfluoromethanesulfonyl)imide (pms-H), phenan-
940 nm (f–f transition). Furthermore, we estimated the throline, and ytterbium oxide were purchased from Fluka
energy transfer efficiencies between photosensitized ligands Chemie. DMSO-d6 (CD3 SOCD3 , 99.8%) was obtained from
Aldrich Chemical. All other chemicals were of reagent grade


E-mail address: hasegawa@ms.naist.jp and were used as received.
1192
Jpn. J. Appl. Phys., Vol. 47, No. 2 (2008)
2.3 Preparation of Yb(III) complexes
Dipyridophenazine (dip) was prepared according to the
procedure described in the literature.13) Yb(pms)3 was
obtained by treating pms-H with ytterbium oxide in water.
Yb(pms)3 (phen)2 and Yb(pms)3 (dip) were synthesized by
the chelation of Yb(pms)3 with phenanthroline (phen) in
methanol, respectively. The reaction mixture was concen-
trated and the obtained concentrated mixture was washed
with hot ethanol several times. The ethanol solutions were
separated, and concentrated. Reprecipitation by adding
excess hexane solution produced white powders. Yb(pms)3 -
(phen)2 : IR(KBr): 1658 (st, C=O), 1630, 1346, 1192, 1136,
1051, and 991 cm1 . 1 H NMR (CD3 SOCD3 )  ¼ 9:39
(2H, s), 8.79 (2H, s), 8.17 (4H, m) ppm. Anal. Calcd for
YbC30 H16 O12 F18 N7 S6 (C2 H5 OH): C, 27.07; H, 1.56; N:
6.90%. Found: C, 26.60; H, 1.93; N, 6.73%. Yb(pms)3 (dip):
IR(KBr): 1630, 1336, 1190, 1120, and 1043 cm1 . 1 H NMR
(CD3 SOCD3 )  ¼ 9:55 (1H, s), 9.22 (1H, s), 8.40 (2H, m),
7.69 (1H, s) ppm. Anal. Calcd for YbC20 H10 O12 F18 -
N7 S6 (3H2 O): C, 21.61; H, 1.21; N: 7.35%. Found: C,
21.60; H, 1.87; N, 6.95%.
2.4 Optical measurements
DMSO-d6 solutions (0.02 M) of the Yb(III) complexes in
quartz cells were prepared by nitrogen bubbling for optical
measurements.14) Measurements of absorption spectra were
performed using a JASCO V-660 spectrophotometer at room
temperature. In order to measure the emission spectra
excited at the absorption band of f–f transition, solutions
in quartz cells (optical path length, 10 mm) were excited at
940 nm (2 F5=2 –2 F7=2 ) using a spectrometer (Jobin Yvon
SPEX fluorolog) at room temperature. A photomultiplier
(Hamamatsu R5509-72) cooled at 193 K was used to detect
emission in the near-IR region. The spectra presented here
were corrected for detector sentitivity and lamp intensity.
The emission quantum yield of the reference sample
(ytterbium acetate in DMSO-d6 ) was determined using a
standard integrating sphere (diameter 6 cm) mounted on a
spectrofluorometer (Jobin Yvon SPEX fluorolog).15) The
optical path length of a cell was 5 mm. Quantum yield, ,
was estimated using the following equation.
Z

Iem ðÞ d
Nemission hc
¼ ¼Z :
Nabsorption 
fIex ðref Þ  Iex ðsam Þg d
hc
The corrected profiles of light absorption from the above-
mentioned equation [Iex ðref Þ: without sample (DMSO-d6 )
and Iex ðsam Þ: with sample (solution of ytterbium acetate in
DMSO-d6 : 0.1 M)] were determined from the excitation
spectra of the system (900 – 980 nm), whereas the corrected
intensity profile of the emission, Iem ðÞ, was determined
from the emission spectra (960 –1100 nm). The emission
quantum yields of Yb(III) complexes were calculated by
comparing the emission and excitation spectra of ytterbium
acetate with those of corresponding Yb(III) complexes
[Yb(pms)3 (phen)2 : 0.02 M, Yb(pms)3 (dip): 0.005 M].
Emission spectra and emission quantum yields for
excitation at the absorption band of
–

transitions were
measured at room temperature using an ACTON research
corporation SpectraPro 2300i system with a charge-coupled
1193
Y. HASEGAWA et al.
device (CCD) detector (Roper PIXIS 100). The spectra were
corrected for detector sensitivity and lamp intensity varia-
tions. The corrected intensity profiles of light absorption
[Iex ðref Þ: without sample (DMSO-d6 ) and Iex ðsam Þ: with
Yb(III) complexes (in DMSO-d6 : 6:0  104 M)] were
determined from the excitation spectra of the system
(208 – 491 nm), whereas the corrected profile of the emission
Iem ðÞ was determined from the emission spectra (900 –
1080 nm).
The shape of the emission spectrum excited at f–f
transition was the same as that excited at
–

transition.
The emission quantum yield was independent of measure-
ment condition and slit width. The quantum yields of
references [rodamine 6G, terphenylene and Eu(III) complex]
determined in the procedure agreed well with the reported
values. The energy transfer efficiencies were estimated using
the emission quantum yields excited at
–

transition and
excited at f–f transition.
3. Results and Discussion
The absorption spectra of Yb(pms)3 (phen)e in DMSO-d6
is shown in Fig. 2. Absorption bands in UV and visible
regions are assigned to
–

and n–

transitions of the
-
conjugated organic ligands [Fig. 2(a)]. The absorption band
of Yb(pms)3 (dip) at about 380 nm is due to the
-conjugated
phenazine structure. The molar absorption coefficients of
Yb(pms)3 (phen)e and Yb(pms)3 (dip) in DMSO-d6 were
found to be 5:0  104 (260 nm) and 4:9  104 (267 nm)
M1 cm1 , respectively. On the other hand, the absorption
bands in the near-IR region was attributed to the f–f
transition 2 F7=2 –2 F5=2 [Fig. 2(b)]. We also observed the stark
splitting of 2 F7=2 in the absorption spectra. The molar
60,000
Molar absorption coefficient
a
40,000
/ mol-1 cm-1
20,000
0
250 300 350 400 450
Wavelength / nm
4
Molar absorption coefficient
b
/ mol-1 cm-1
2
0
850 900 950 1000 1050 1100
Wavelength / nm
Fig. 2. (a) UV–vis and (b) near-IR absorption spectra of Yb(pms)3 (phen)2
(solid lines) and Yb(pms)3 (dip) (dot lines) in DMSO-d6 .
Jpn. J. Appl. Phys., Vol. 47, No. 2 (2008)
Emission intensity / arb. unit
4
2
0
940 980 1020
Wavelength / nm
Emission intensity / arb. unit
4 method and optical conditions as those for corresponding
2 310 nm were found to be 0:67  0:1 and 0:36  0:1%,
0 between the triplet state of the ligands and Yb(III) ions.
940 980 1020
Wavelength / nm
Fig. 3. Emission spectra of Yb(pms)3 (phen)2 excited at (a) 910 nm (f–f
transition) and (b) 310 nm (
–

transition) in DMSO-d6 .
absorption coefficient of Yb(pms)3 (phen)2 at 977 nm (2.7
mol1 cm1 ) is on the same order as that of Yb(pms)3 (dip)
in DMSO-d6 (2.5 mol1 cm1 ). The oscillator strengths and
spectral shapes in f–f transitions of Yb(III) complexes in
DMSO-d6 might be not affected, markedly.
The emission spectrum of Yb(pms)3 (phen)2 excited at
940 nm (f–f transition) is shown in Fig. 3(a) (slit width >
10 mm). Yb(pms)3 (dip) showed similar emission spectra in
the near-IR region. The emission bands with stark splitting
in the near-IR region was assigned to the f–f transition
2
F7=2 –2 F5=2 . The emission quantum yields of Yb(pms)3 -
(phen)2 and Yb(pms)3 (dip) excited at 940 nm were found to
be 7:4  0:1 and 9:1  0:1%, respectively. The difference in
emission quantum yield between the two complexes is
significant, and is explained as being due to radiationless
transition via vibrational relaxation of C–H bonds in Yb(III)
complexes.11) The numbers of C–H bonds in Yb(pms)3 -
(phen)2 and Yb(pms)3 (dip) are 16 and 10, respectively.
Those chemical structures indicate that the vibrational
harmonic bands of Yb(pms)3 (dip) at about 1000 nm is
smaller than those of Yb(pms)3 (phen)2 . We propose that
Yb(pms)3 (dip) can suppress vibrational relaxation more
efficiently because of its smaller vibrational harmonic bands.
To our knowledge, these are the first evaluations of the
emission quantum yields of Yb(III) complexes excited at f–f
transition. The emission quantum yields of Yb(III) com-
plexes excited at f–f transition are larger than those of the
corresponding Nd(III) complex (3.2%).11) The higher quan-
tum yields of Yb(III) complexes may be due to a larger
energy gap, which is related to the transition probability of
vibtational relaxation [Yb(III): 10,000 cm1 , Nd(III): 5,880
cm1 ]. We successfully observed the near-IR luminescence
Y. HASEGAWA et al.
of Yb(III) complexes having higher emission quantum yields
a (10%).
The emission spectrum of Yb(pms)3 (phen)2 excited at
310 nm (
–

transition) is shown in Fig. 3(b). The spectral
difference between Figs. 3(a) and 3(b) is due to the meas-
urement conditions [Fig. 3(a): slit width > 10 mm;
Fig. 3(b): slit width 1 mm]. We successfully observed strong
photosensitized luminescence of Yb(III) complexes with
high-resolution spectrum (slit width, 1 mm). The strong
emission of Yb(pms)3 (phen)2 might be caused by the
1060 efficient photosensitized energy transfer from the ligands
having larger absorption coefficients at 310 nm (> 1000
mol1 cm1 ). The emission quantum yields for excitation at
b 310 nm (
–

transition) were measured using the same
excitation at 940 nm (f–f transition). The emission quantum
yields of Yb(pms)3 (phen)2 and Yb(pms)3 (dip) excited at
respectively. The difference in emission quantum yield
might come from the difference energy transfer efficiency
Here, we estimated the energy transfer efficiencies from the
1060 organic ligands to Yb(III) ions for the first time. The energy
transfer efficiency, energy transfer , is given by
excited at
{

transition
energy transfer ¼ ;
excited at f{f transition
where excited at
{

transition and excited at f{f transition are
emission quantum yields of the Yb(III) complex excited at

–

transition and f–f transition, respectively. The eval-
uated energy transfer efficiency of Yb(pms)3 (phen)2 , 9.1%,
was larger than that of Yb(pms)3 (dip), 4.0%. These results
also suggest that the energy transfer efficiency of Yb(III)
complexes depends on the chemical structure of the photo-
sensitized ligands. From the absorption spectra [Fig. 2(a)],
we can find that the
-conjugated structure of the dip ligand
is more extensive than that of the phen ligand. The extended

-conjugated structure of the dip ligand leads to the
formation of lower-energy states of singlet and triplet states.
The gap between Yb(III) ion and triplet state of the ligand in
Yb(pms)3 (dip) is smaller than that in Yb(pms)3 (phen)2 . In
Dexter’s energy transfer mechanism, smaller gap between
the energy levels of energy donor and acceptor promotes a
more efficient energy transfer. However, we observed a
more efficient energy transfer of Yb(pms)3 (phen)2 . These
results suggest that the energy transfer in Yb(III) complex is
promoted by an especial factor. According to the energy
transfer between organic ligands and Yb(III) ions, Horrocks
et al.16) and Bünzli et al.17) have suggested recently that the
photosensitized luminescence of Yb(III) complexes is due to
the remarkable energy transfer mechanism promoting the
electron transfer. Our estimations of the energy transfer
efficiencies of Yb(pms)3 (phen)2 and Yb(pms)3 (dip) may
provide an important aspect of the energy transfer mecha-
nism of Yb(III) complexes.
4. Conclusions
We successfully synthesized strong luminescent Yb(III)
complexes having higher emission quantum yields,
Yb(pms)3 (phen)2 and Yb(pms)3 (dip). Luminescent Yb(III)
complexes are promising materials with applications in near-
1194
Jpn. J. Appl. Phys., Vol. 47, No. 2 (2008)
IR optic and sensing devices. Futhermore, the energy
transfer efficiencies from the organic ligands to Yb(III) ions
were estimated for the first time. The estimations of the
energy transfer efficiencies of Yb(III) complexes are
expected to be useful in molecular designs for development
of strong luminescent materials.
Acknowledgement
This work was supported partly by a Grant-in-Aid for
Scientific Research on Priority Area A of ‘‘Panoscopic
Assembling and High Ordered Functions for Rare Earth
Materials’’ from the Ministry of Education, Culture, Sports,
Science, and Technology, MEXT, Japan.
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