Inorganic Chemistry Communications 13 (2010) 12531258

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Inorganic Chemistry Communications

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i n o c h e

Synthesis and visible light luminescence of mononuclear nine-coordinate lanthanide

complexes with 2,4,6-tris(2-pyridyl)-1,3,5-triazine
Zubair Ahmed, K. Iftikhar
Department of Chemistry, Jamia Millia Islamia, New Delhi-110 025, India

a r t i c l e i n f o a b s t r a c t

Article history: Synthesis of four nine-coordinate lanthanide (III) complexes of the type, [Ln(hfaa)3(tptz)], where Ln = La,
Received 9 June 2010 Nd, Sm and Tb; hfaa = the anion of 1,1,1,5,5,5-hexauoro-2,4-pentanedione and tptz = 2,4,6-tris(2-pyridyl)-
Accepted 6 July 2010 1,3,5-triazine, by a new modied one pot in situ method is reported. The lanthanide ions are coordinated to
Available online 14 July 2010
three N-atoms of three 2-pyridyl units of tptz besides six O-atoms of three hfaa units. The formation of these
volatile complexes is conrmed by molecular ion peak in ESI-MS, IR and NMR. The hypersensitive 4G5/2,
Keywords: 2
Lanthanide
G7/2 4I9/2 transition displays distinct band shape which is different from the band shape of known eight-
2,4,6-tris(2-pyridyl)-1,3,5-triazine and ten-coordinate complexes. The samarium and terbium complexes emit pink and green luminescence
NMR due to 4G5/2 6Hj (j = 5/2, 7/2, 9/2) and 5D4 7Fj (j = 3-6) transitions, respectively.
4f4f absorption 2010 Elsevier B.V. All rights reserved.
Luminescence

The design and synthesis of the complexes of Ln(III) ions with
chelating ligands offer many potential applications such as in
uoroimmunoassay [1], spectroscopic structural probes in biological-
ly important systems [2], laser systems [3], optical amplications [4]
and emitting materials in multilayer organic light emitting diodes
(OLEDs) [5]. Shielding of the f-orbitals by the 5 s and 5p shells result in
narrow linelike emissions of optically pure colours and long radiative
lifetimes. However, the 4f4f transitions that result in light emission
from the lanthanide are spin- and parity-forbidden, thus requiring the
use of organic chromophore or antenna that possess a reasonably
large molar absorption cross section to indirectly excite the metal
centre [6]. The -diketone ligand has strong absorption within a large
wavelength range for its * transition and consequently has been
targeted for its ability to sensitize the luminescence of the Ln(III) ions
[710]. Furthermore, it has the ability to form stable and strong
adducts with Ln(III) ions, which can have practical usage [3,11]. The
lanthanide tris(-diketonates) are coordinatively unsaturated and are
known to expand their coordination sphere by coordinating with
neutral heterocyclic NN diimine [7] or NN bis diimine [8]. The 1, 10-
phenanthroline (phen) and 2,2-bipyridyl (bpy) are the ligands which
This research was supported, in part, by the UGC Special Assistance Programme of
the Department of Chemistry (No. F.540/17/DRS/2007/SAP-1).
Corresponding author. Tel.: +91 11 26837297; fax: +91 11 26980229/26982489.
E-mail address: kiftikhar.ch@jmi.ac.in (K. Iftikhar).
have been exploited the most [1215]. In our recent papers we have
investigated the antenna effect of these bidentate and tetradentate
neutral diimines and have reported their absorption and luminescent
properties [710]. In continuation of our research programme it was
thought worthwhile to investigate 2,4,6-tri(2-pyridyl)-1,3,5-triazine
(tptz) as ancillary ligand. The tptz, a tridentate ligand, is a bulky
aromatic compound featuring three 2-pyridyl rings xed on a central
1,3,5-triazine platform with large -systems for stabilization and with
strong coordinating ability [16]. There are a few structurally
characterized lanthanide complexes in which tptz acts as a tridentate
ligand [1721]. Silva et al. in an attempt to synthesize [Eu(hfaa)3
(tptz)], where hfaa is the anion of 1,1,1,5,5,5-hexaouro-2,4-penta-
nedione, adapted to two routes [20]. The rst route which was a one
pot in situ synthesis could not give the desired product. However, the
second route which was a two step reaction (isolation of chelate rst
and then its reaction with tptz) did yield the desired product with 67%
yield. We have used an alternate, one pot in situ, method to synthesize
[Ln(hfaa)3(tptz)] complexes, using ammonium hydroxide (instead of
potassium butoxide used in Ref. 20) and have isolated the complexes
in very good yield (N80%). In this communication we report (i) a
modied route for the synthesis of the complexes of the type [Ln
(hfaa)3(tptz)] (Ln = La, Nd, Sm and Tb) which gives higher yield and
(ii) the solution properties of these complexes. These include NMR,
photoluminescence, 4f4f absorption and hypersensitivity.
Nine-coordinate complexes of La(III), Nd(III), Sm(III) and Tb(III)
of the type [Ln(hfaa)3(tptz)] were synthesized by a modied one pot

1387-7003/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2010.07.009
1254 Z. Ahmed, K. Iftikhar / Inorganic Chemistry Communications 13 (2010) 12531258
Scheme 1. Pathway for the synthesis of the complexes (Ln = La, Nd, Sm and Tb).
in situ method1 in high yield in which hexauoroacetylacetone,
ammonium hydroxide (25% ammonia), tptz and LnCl3nH2O were
mixed in a single pot in 3:3:1:1 molar ratio in ethanol at room
temperature. There are following three advantages of the method
we employed: (i) the reaction is carried out in air, (ii) the reaction
temperature was ambient and (iii) it gives the product in very high
yield (N 80%). These complexes were characterized by melting point,
elemental analysis, IR, TGA/DTA, ESI-MS and NMR studies. The
stoichiometry was based on the assumption that tptz will act as a
tridentate ligand and nine-coordinate hexauoroacetylacetonate
tptz complexes would be formed. For all the lanthanides used in this
study, this assumption was found true (Scheme 1) as clearly shown
by the elemental analysis. Air and moisture stable nine-coordinate
complexes were isolated in more than 80% yield. These complexes
are readily soluble in acetone, chloroform and dichloromethane and
are soluble in alcohols upon heating. Although tptz is a exible
ligand, the thermal stability of its complexes is at par with those of
their phen analogues. Moreover, in the cases of Sm and Tb the tptz
complexes are thermally more stable [14]. The IR spectra of the
complexes gave a strong absorption as an asymmetric doublet at
15511522 cm 1 which is attributed to the stretching vibrations of
(C = C) + (C = N) of tptz (ca. 1530 cm 1 as a strong singlet in free unit has coordinated to the lanthanum. Coordinated tptz is expected
tptz) [22]. The ESI-MS spectrum of the lanthanum complex (Fig. S1
in Supporting information) shows molecular ion peak at m/z ratio of
1071.7 due to the parent ion [La(hfaa)3(tptz) + H+]+. It is important
to note that no peak corresponding to m/z ratio (m/z = 774) of the
complex [La(hfaa)3 + H]+ is observed. The other peaks observed in
the spectrum may account for the diverse ionic species formed due
1 the signals of all protons of metal-bound pyridyl rings of tptz is
Synthesis of the complexes All the complexes were synthesized by a similar in situ
method. The synthesis of [La(hfaa)3(tptz)] given here is representative. [La(hfaa)3
(tptz)]. A solution of Hhfaa (1.486 g, 7.1 mmol) in 5 mL ethanol was added to 0.53 mL
(0.1216 g, 7.1 mmol) 25% ammonia solution. This mixture was covered in 50 mL
beaker until all the ammonia vapours dissolved. To this mixture was added 5 mL
ethanol solution of tptz (0.4718 g, 2.3 mmol) and 5 mL ethanol solution of LaCl3.6H2O
(0.8684 g, 2.3 mmol). The reaction mixture was stirred at room temperature for 5 h. A
white precipitate appeared during stirring which was ltered off repeatedly. The
ltrate was covered and left for slow evaporation. Colourless crystals appeared after
three days, which were ltered off and washed with CCl4. The compound was
recrystallized twice from ethanol and dried under vaccum over P4O10. Colour (white).
Yield (82%); elemental analysis (found: C, 36.50; H, 1.23; N, 7.53. C33H15O6F18N6 La
requires C, 36.96; H, 1.40; N, 7.83. % ). mp 192 C. Similar procedure was employed to
synthesize other lanthanide complexes. [Nd(hfaa)3(tptz)]. Colour (Lilac). Yield (83%);
elemental analysis (found: C, 37.01; H, 2.01; N, 8.09. C33H15O6F18N6Nd requires C,
36.78; H, 1.40; N, 7.79. %). mp 194 C. [Sm(hfaa)3(tptz)]. Colour (white) yield (81%);
elemental analysis (found: C, 36.60; H, 1.51; N, 7.62. C33H15O6F18N6Sm requires C,
36.57; H, 1.39; N, 7.75. %). mp 197 C. [Tb(hfaa)3(tptz)]. Colour (pale yellow) yield
(83%); elemental analysis (found: C, 36.29; H, 1.28; N, 7.66. C33H15O6F18N6Tb requires
C, 36.45; H, 1.37; N, 7.69. %). mp 199 C.
to the fragmentation, ligand exchange and redistribution in the
vapour phase [23,24]. The thermograms of the complexes are similar
in shape consistent with one step volatilization (Fig. 1). The DTA
curve of the complexes displays two endothermic peaks; one peak at
lower temperature (between 192 and 200 C) corresponds to the
melting of the complexes and the other peak at higher temperature
(between 320 and 330 C) is consistent with volatilization of the
complexes. The TGA/DTA shows that the complexes are stable up to
190 C.
The NMR spectrum of the diamagnetic lanthanum complex, [La
(hfaa)3tptz], recorded in CDCl3 (Fig. 2) is a rst order spectrum and
displays eight signals; one due to methine protons of -diketone and
seven signals due to tptz in the intensity ratio of 3:2:1:3:2:1:2:1. The
assignment of NMR signals is based on comparison of the spectrum of
the complex with the spectrum of free tptz and relative intensities and
spinspin splittings. The signal at 6.09 ppm, which integrates for 3
protons is assigned to the methine (CH) group. The aromatic region
of the spectrum is integrated for 12 protons as expected for two
magnetically equivalent coordinated pyridyl rings and one inequi-
valent uncoordinated pyridyl ring. The intensity ratio between the
methine protons and tptz protons is 3:12, indicating that only one tptz
to display eight resonances, four due to metal-bound pyridyl units and
four due to uncoordinated pyridyl unit. However, only seven distinct
resonances are observed. The resonances at 9.10(d), 9.03(d), 8.88(q),
8.19(t), 8.18(t), 7.77(t) and 7.66(t) ppm are assigned to H6, H6, H3,3,
H4, H4, H5 and H5 respectively. The H3' resonance due to the
uncoordinated pyridyl ring is not very well resolved and has
overlapping appearance with H3,3. A signicant downeld shift of
observed with respect to their positions in free tptz. These shifts are
consistent with the ligand binding to metal ion.
The absorption spectra of the neodymium complex and the
ligands (hfaa and tptz), in chloroform, are shown in Fig. 3. The
absorption spectrum is dominated by spin allowed * transi-
tions of -diketone, hfaa and tptz in the ultraviolet region (200
400 nm). The tptz shows a strong absorption band at 278 nm,
whereas a strong absorption is observed at 275 nm for Hhfaa [20].
The spectrum of complex contains essentially the combined ligand
absorptions (max = 295 nm), this band in the spectrum of the
complex is shifted to longer wavelength (red-shift) (Fig. 3) as
compared to free tptz and or Hhfaa due to coordination of the
ligands to the neodymium. In the visible region, the complex
shows typical parity-forbidden narrow 4f4f absorption bands
originating from the 4I9/2 ground state to the various exited states
of Nd(III) ion. The transitions observed are 4F3/2 (NdI, 1.71 106);
 Z. Ahmed, K. Iftikhar / Inorganic Chemistry Communications 13 (2010) 12531258 1255

Fig. 1. TG/DTA plots of (1)[La(hfaa)3(tptz)], (2)[Nd(hfaa)3(tptz)], (3)[Sm(hfaa)3(tptz)] and (4)[Tb(hfaa)3(tptz)].

2
H9/2, 4F5/2 (NdII, 6.72 106); 4S43/2,F7/2 (NdIII, 6.66 106); 4F9/2
(NdIV, 0.50 106); 2H11/2 (NdV, 0.15 106); 4G5/2,2G7/2 (NdVI,
49.10 106); 2K413/2,G47/2,G9/2 (NdVII, 10.44 106) and 2K15/2, 2G29/2,(D,
P)43/2,G11/2 (NdVIII, 0.65 106). These transitions are given in order of
increasing frequency (energy). The values given in the parentheses
are the oscillator strength of the transitions determined from the
spectra (Fig. 3) using standard equation [25] and procedure outlined
in our previous papers [7,8,26]. The transition 4G5/2 4I9/2 (NdVI)
located near the middle of the visible region (16,38917,770 cm 1) is
hypersensitive [26,27]. It is overlapped by a less intense transition
2
G7/2 4I9/2. The relatively high intensity of this transition and its
unusual sensitivity to the chemical environment about the
neodymium ion have lead to its classication as hypersensitive;
its behavior is in sharp contrast to many other typically weak and
consistently unvaried, normal ff transitions [27]. This pair of
transitions exhibits greatest sensitivity to the environment in the
neodymium complex.
The band shape (Fig. 3) of hypersensitive transition 4G5/2,
2
G7/2 4I9/2 in the present complex is distinctively different than
those reported for eight- and ten-coordinate complexes [14]
(Fig. 4). The hyperne splitting in the NdVI band of the complex
(Figs. 3, 4) is prominent, which is due to a highly asymmetric eld
around Nd(III). The change in the band shape of NdVI transition
is accompanied by a change in the oscillator strength. The
oscillator strength of the hypersensitive transition of the present
complex (49.10 106) is higher than the oscillator strength of the
ten-coordinate, [Nd(hfaa)3(phen)2] complex (23.69 106) [14]
while it is lower than the oscillator strength of the eight-
coordinate, [Nd(hfaa) 3phen] complex (61.74 106 ) [14]. The
higher value of the oscillator strength of the present complex as

Fig. 2. 400 MHz 1H NMR spectrum of [La(hfaa)3(tptz)] in CDCl3. Inset (a); resolution of region from 7. 5 to 9.5 ppm (). *impurity.
1256 Z. Ahmed, K. Iftikhar / Inorganic Chemistry Communications 13 (2010) 12531258
Fig. 3. (A) Absorption spectra of (a) tptz, (b) Hhfaa and (c) [Nd(hfaa)3(tptz)] complex (green), high resolution spectrum of (c) is shown in inset (i) and band shape of hypersensitive
transition, 2G47/2,G5/2 4I9/2 is shown in inset (ii). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)
compared to the ten-coordinate is consistent with the low
molecular symmetry of a nine-coordinate structure. This suggests
the premise that hypersensitivity depends upon symmetry of the
eld. However, the lower value of the oscillator strength as
compared to the eight-coordinate complex could not be related to
the asymmetry of the eld, but could be explained by the
structure and basicity of the ancillary ligands. The rigidly planar
phen ligand being more basic (pka = 4.86) than tptz (pka = 3.10),
would lead us to expect a greater deal of covalency in its bonding,
since it could result in some change in extent of overlap and,
therefore, in the degree of covalency of NdN(phen) bonds. The
rigid planar structure of the phen ligand is an additional factor for
promoting 4f4f absorption intensities [26]. Therefore, the lower
basicity and exible structure of tptz are responsible for lower
oscillator strength of the transition although the present complex
is more asymmetric than the eight-coordinate phen complex.
The room temperature excitation and emission spectra of Sm
(III) and Tb(III) complexes are recorded in chloroform. The
excitation spectrum of the samarium complex (obtained by
monitoring the 646 nm line of the 4G5/2 6H9/2 emission) consists
of a broad band which corresponds to the excitation of the organic
chromophores (S0 S1) and several weak peaks corresponding to
intracongurational ff transitions from the ground state of Sm
(III) (Fig. 5). The excitation of a chloroform solution of this
complex produces characteristic pink Sm(III)-luminescence and is
indicative of an effective match between the ligand-centered
triplet state and Sm(III) emissive levels. The emission spectrum, of
the complex, displays four characteristic Sm(III) emission peaks in
the region 525660 nm corresponding to 4G5/2 6H5/2 (zerozero
band; 563 m), 4G5/2 6H7/2 (magneticdipole transition; 607 nm),
and 4G5/2 6H9/2 (electricdipole transition; 646 nm) transitions.
Of the three transitions the most intense peak is the hypersen-
sitive electric-dipole transition, 4 G 5/2 6 H 9/2 followed, by
4
G5/2 6H7/2 [28]. The fourth peak, which is least intense, arises
from the higher emissive level 4F3/2 to ground state 6H5/2.
A broad band with no ff transitions dominates the excitation
spectrum of the Tb(III) complex, thus reecting an efcient ligand
to metal energy transfer. The emission spectrum of the Tb(III)
complex displays ve emission peaks under the excitation 370 nm.
The typical Tb(III) emissions are observed at 489, 545, 581, and
618 nm corresponding to the deactivation of the excited state 5D4
to the ground states 7FJ (J = 3, 4, 5, and 6) (Fig. 6). Among the
transitions, the intense and narrow emission band at 545 nm due
to the 5D4 7F5 transition exhibits the strongest green emission
and, is hypersensitive [29]. A moderately strong emission band
due to 5D4 7F6 at 489 nm shows the second strong green
emission. The emission bands at 581 and 618 nm (due to the
transitions 5D4 7F4 and 5D4 7F3, respectively) are weak and
comparable in intensity. The least intense emission band is due to
5
D4 7F2 (652 nm) transition.
 Z. Ahmed, K. Iftikhar / Inorganic Chemistry Communications 13 (2010) 12531258 1257

Fig. 6. Emission spectrum of [Tb (hfaa)3(tptz)] complex in chloroform.

could be related to the rigid planar structure of phen since it

would allow better energy transfer.
The mononuclear lanthanide complexes containing 1,1,1,5,5,5-
hexaouro-2,4-pentanedione and 2,4,6-tris(2-pyridyl)-1,3,5-trizine
Fig. 4. 4G5/2, 2G7/2 hypersensitive transition of (a) nine-coordinate, [Nd(hfaa)3(tptz)] ligands are isolated in high yield by a modied new in situ method
(green) (this work); (b) ten-coordinate, [Nd(hfaa)3(phen)2] (red); and (c) eight-
at room temperature in air atmosphere. Although tptz is a exible
coordinate, [Nd(hfaa)3(phen)] (blue) in chloroform. (For interpretation of the
references to colour in this gure legend, the reader is referred to the web version of
ligand the thermal stability of its complexes are at par with the
this article.) analogous complexes of the rigid planar phen ligand. Inspite of the
fact that these nine-coordinate complexes are more asymmetric than
symmetric eight-coordinate complexes, their oscillator strength and
The intense emissions for the Sm(III) and Tb(III) complexes emission intensities are lower.
may be the result of a better match between the ligand singlet and
triplet exited states and/or a better energy match between the
Acknowledgments
ligand triplet exited states and metal ion emissive states, with
the tptz ligand providing additional advantage of site-protection.
ZA thanks UGC, for a fellowship. Thanks are also due to USIC, Delhi
The emission intensity of the tptz complexes is lower than the
University, for providing micro analysis.
analogous eight-coordinate [Ln(hfaa)3phen] complexes [15], al-
though nine-coordinate tptz complexes are more asymmetric and
would be expected to enhance the luminescence intensity. The Appendix A. Supplementary data
higher emission transitions in the case of the phen complexes
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.inoche.2010.07.009.

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