Journal of Molecular Structure 1145 (2017) 10e17

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Solvothermal synthesis and spectroscopic characterization of three

lanthanide complexes with high luminescent properties
[H2NMe2]3[Ln(III)(2,6-pyridinedicarboxylate)3] (Ln ¼ Sm, Eu, Tb): In
the presence of 4,40 -Bipyridyl
Alan G. Viveros-Andrade a, Raúl Colorado-Peralta a, Marcos Flores-Alamo b,

n-Herna
Silvia E. Castillo-Blum b, Jesús Dura
María Rivera a, *

ndez b, Jose
a
n Oriente 6, No. 1009, Colonia Rafael Alvarado, C.P.94340, Orizaba, Veracruz, Mexico
Facultad de Ciencias Químicas, Universidad Veracruzana, Prolongacio
b
Facultad de Química, Departamento de Química Inorga
nica, Universidad Nacional Auto
noma de M
exico, Ciudad Universitaria, C.P. 04510, M

exico DF,
Mexico

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

Article history: Three lanthanide complexes, [H2NMe2]3[Ln(III)(2,6-pyridinedicarboxylate)3] (Ln ¼ Sm, Eu, Tb) have been
Received 1 August 2016 successfully synthesized using a solvothermal method in the presence of a base and they were prepared
Received in revised form from inexpensive and readily available reactants. Infrared, ultravioletevisible absorption spectroscopies,
12 May 2017
elemental analyses and thermogravimetric analysis were employed for the characterization. Crystals
Accepted 13 May 2017
Available online 17 May 2017
suitable for X-ray diffraction were isolated in good yields by a simple filtration, their crystal structures
were analyzed; the samarium structure has orthorhombic symmetry with space group Pbcn, exhibiting
three-dimensional supramolecular architecture through hydrogen bonding interactions. The metal
Keywords:
Crystal growth
center is coordinated to nine atoms corresponding to three pyridine-2,6-dicarboxylic acid molecules.
Luminescence These compounds are thermally stable up to 270  C.
Solvothermal Published by Elsevier B.V.
X-ray diffraction
Crystal structure

1. Introduction shows several coordination modes, such as O-unidentate, O,N-

bidentate, O,N,O-tridentate, (O,N) O-bidentate bridging, (O,N,O) O
In recent years, the number of publications related with lan- and O,N, m-O-tridentate bridging [8]. Moreover, when coordinating
thanides coordination complexes has increased due not only to to 4f metal ions, PDA2- adopts a tridentate mode: the N atom co-
their attractive structures but to their potential applications in ordinates together with two O atoms from two adjacent carboxylic
catalysis, magnetic devices, organic light emitting diodes (OLEDs) groups (each carboxylic group provides one O atom) [9e13]. In
and optical fibers for data transition, amongst others [1e3]. Lan- addition, a very important characteristic of Ln(PDA)3 luminescence
thanides, with high and variable coordination numbers and flexible complexes are the applications in many fields, such as, chemical
coordination environments, have led to a partial success in the and biological activity [14e18] and heterometallic lanthanide
design of molecular architectures with predetermined structures; organic frameworks (LOF) [19e27].
the complexes containing lanthanide ions, such as SmIII, EuIII and Lanthanide aromatic carboxylates have not only shown good
TbIII usually display intense luminescence arising from f-f transi- luminescence properties, but also suitable absorption characteristic
tions [4e7]. in the near-UV region. The creation of luminescent complex ma-
Pyridine-2,6-dicarboxylate acid (H2PDA) has been well known terials based on lanthanide pyridine dicarboxylates has been
to be a perfect ligand to encapsulate lanthanide ions, creating co- described in the literature [28e36]. However, the synthesis and
ordination compounds with unique optical properties [4]. H2PDA published data on spectroscopic research are comparatively scarce.
In this article, lanthanide complexes with very strong luminescence
and excellent thermal stability were successfully obtained using
* Corresponding author.
the nitrate lanthanides in the presence of 4,40 -Bipyridyl. The details
E-mail address: [email protected] (J.M. Rivera). of the structure and properties of the complex analyzed by the IR,

http://dx.doi.org/10.1016/j.molstruc.2017.05.055
0022-2860/Published by Elsevier B.V.
 A.G. Viveros-Andrade et al. / Journal of Molecular Structure 1145 (2017) 10e17 11

UV, absorption and emission spectra and TG-DTA are discussed. vacuum. Crystals were insoluble in water and common organic
solvents (acetonitrile, methanol, DMF, acetone). Mp > 350  C. Yield:
2. Experimental 61.0 mg, 73%. IR (ATR, ʋ cm1): 3541 (NeH), 1466, 1429 (C]C)arom,
1599 (C]O), 1570 (C]N), 1385 (CeO), 1369 (CeN), 727 (CeH)arom.
2.1. Materials and instrumentation Anal. Calc. for C27H33SmN6O12: C, 41.4; H, 4.2; N, 10.7. Found: C,
41.6; H, 4.1; N, 10.6%.
All reactants and solvents were purchased from Sigma-Aldrich
Chemical Co. and were used without previous purification; re- 3.2. [H2NMe2]3[Eu(PDA)3] (2)
agent grade solvents were dried and distilled according to previ-
ously reported procedures established in the literature [37]. Single Compound 2 was prepared by following the general procedure,
crystals were obtained using spectroscopic grade solvents. Melting from europium(III) nitrate pentahydrate (68.5 mg 0.16 mmol), 4,40 -
points were measured in sealed capillaries on an IAe9100 model bipyridine (50.0 mg 0.32 mmol) and pyridine-2,6-dicarboxylate
10034137/01 Thermo Scientific electrothermal apparatus and are acid (53.5 mg 0.32 mmol); colorless prism-shaped crystals of 2
uncorrected. Elemental analyses were performed on a Perkin Elmer were filtered off, washed with distilled water, and dried in vacuum.
Series II CHNS/O model 2400 analyzer using cystine as standard. IR Crystals are insoluble in water and common organic solvents
spectra in the range 4000e400 cm1 were recorded in a Perkin (acetonitrile, methanol, DMF, acetone). Mp > 350  C. 63.7 mg, Yield:
Elmer FT-IR Spectrum 400 spectrophotometer with a universal ATR 76%. IR (ATR, ʋ cm1): 3540 (NeH), 1466, 1430 (C]C)arom, 1599 (C]
sampling accessory at 298 K. The solid photoluminescence spectra O), 1570 (C]N), 1386 (CeO), 1369 (CeN), 727 (CeH)arom. Anal. Calc.
were obtained with a Horiba FluoroMax-4p spectrofluorometer, for C27H33EuN6O12: C, 41.3; H, 4.2; N, 10.7. Found: C, 41.4; H, 4.2; N,
with a 150 W continuous emission xenon lamp. UVeVis electronic 10.6%.
absorption spectrum was measured in diffuse reflectance mode in
the 200e1200 nm wavelength range with an Ocean-optics HR4000 3.3. [H2NMe2]3[Tb(PDA)3] (3)
spectrometer with Toshiba TCD1304AP detector. Thermograms
were obtained with a Mettler-Toledo Star Thermal Analysis System Compound 3 was prepared by following the general procedure,
(DSC 821 differential scanning calorimeter and TGA/SDTA 851e from terbium(III) nitrate pentahydrate (69.6 mg 0.16 mmol), 4,40 -
thermogravimetric analyzer) with STAR 8.10 software at a heating bipyridine (50.0 mg 0.32 mmol) and pyridine-2,6-dicarboxylate
rate of 10  C/min under air within the temperature interval of acid (53.5 mg 0.32 mmol); colorless prism-shaped crystals of 3
25e600  C. were filtered off, washed with distilled water, and dried in vacuum.
The crystals were mounted on glass fiber and studied with an Crystals are insoluble in water and common organic solvents
Oxford Diffraction Gemini “A” diffractometer with a CCD area de- (acetonitrile, methanol, DMF, acetone). Mp > 350  C. Yield: 60.9 mg,
tector, with radiation source of lMoKa ¼ 0.71073 Å using graphite- 72%. IR (ATR, ʋ cm1): 3543 (NeH), 1467, 1431 (C]C)arom, 1600 (C]
monochromatized radiation. CrysAlis Pro and CrysAlis RED soft- O), 1572 (C]N), 1387 (CeO), 1371 (CeN), 729 (CeH)arom. Anal. Calc.
ware packages [38] were used for data collection and data inte- for C27H33TbN6O12: C, 40.9; H, 4.2; N, 10.6. Found: C, 40.8; H, 4.1; N,
gration. Final cell constants were determined by a global 10.5%.
refinement; collected data were corrected for absorbance by using
analytical numeric absorption correction [39] using a multifaceted 4. Results and discussion
crystal model based on expressions upon the Laue symmetry using
equivalent reflections. Structure solution and refinement were 4.1. Synthesis of lanthanide complexes
carried out with the program(s): SHELXS97, SHELXL97 [40]; for
molecular graphics: ORTEP-3 for Windows [41] and the software Three lanthanide complexes were synthesized (1e3) from the
used to prepare material for publication: WinGX 1.80.05 [42]. Full- reaction of the tridentate ligand pyridine-2,6-dicarboxylate acid
matrix least-squares refinement was carried out by minimizing (F2o (H2PDA) with lanthanide(III) nitrates in solvothermal conditions,
e F2c)2. All non-hydrogen atoms were refined anisotropically. H Scheme 1. One of these structures is new (1), while 2 and 3 had
atoms attached to C atoms were placed in geometrically idealized been previously reported and obtained by a different procedure to
positions and refined as riding on their parent atoms, with the one described herein [10,11]. Interestingly, the double depro-
CeH ¼ 0.93 and 0.97 Å with Uiso(H) ¼ 1.2 Ueq(C) for aromatic tonation of the ligand is most likely facilitated by the dimethy-
groups, positions of H(N) have been refined freely. lammonium cations formed from decomposition of DMF to carbon
monoxide [10]. The addition of a second organic building unit to the
3. Synthesis reaction mixture could give place to the formation of different

3.1. [H2NMe2]3[Sm(PDA)3] (1)

General procedure: A solution of Samarium(III) nitrate hexahy-

drate (71.0 mg, 0.16 mmol) in 5 mL of deionized water was added
dropwise to 5 mL of a methanol solution of 4,40 -bipyridine (50.0 mg
0.32 mmol). The reaction mixture was refluxed for 90 min and left
to reach room temperature. Then, a solution of pyridine-2,6-
dicarboxylic acid (53.5 mg, 0.32 mmol) in 5 DMF (5 mL) was
slowly added.
The reaction mixture was then transferred into a teflon-lined
stainless-steel vessel. The solution was heated at 120  C for 4
days under autogenous pressure; the reaction was slowly cooled
down to room temperature and then, it was heated at 45  C for 2
days. From the reaction mixture, colorless prism-shaped crystals of
1 were filtered off, washed with distilled water, and dried in Scheme 1. Reaction of H2PDA with samarium, europium and terbium nitrates.
12 A.G. Viveros-Andrade et al. / Journal of Molecular Structure 1145 (2017) 10e17

coordination polymers [43,44], however, in the synthesis of com-

pounds (1e3) the 4,40 -bipyridine acts as base, allowing the for-
mation of carboxylate units corresponding to the tridentate ligand
pyridine-2,6-dicarboxylate which facilitates its coordination to the
lanthanides. The same results were obtained using pyrazine and
4,40 -trimethylenedipyridine. The absence of a base yields clear so-
lutions and not any crystalline or amorphous materials were
observed after 3 days of reaction at 60  C.

4.2. Structural analyses by X-ray diffraction

The single-crystal X-ray diffraction analysis reveals that anion 1

has the same molecular structure as those deposited in the Cam-
bridge Structural Database for europium and terbium [10,11]. The
compound crystallizes orthorhombic, space group Pbcn, Table 1.
Samarium(III) is nine-coordinated by six carboxylate oxygen atoms
and three pyridine ring N atoms from three PDA ligands. The local
coordination environment around SmIII in compound 1 is depicted
in Fig. 1, where dimethylammonium ions are omitted for clarity.
The coordination geometry is best described as a distorted tricap-
ped trigonal prism, a geometry which is commonly observed for Fig. 1. Molecular structure of anion 1; H-atoms and dimethylammonium cations are
lanthanide(III) complexes. The corners of the trigonal prism are omitted for clarity. Anisotropic displacement ellipsoids are drawn at the 50% proba-
formed by the six carboxylate oxygen atoms. The three pyridine bility level.
nitrogen atoms form the three caps on the prism, Fig. 2. The SmeO
(2.457e2.476 Å), SmeN (2.549e2.552 Å) bond lengths reveal a
saturation of the metal coordination sphere with the PDA chro-
mophore, Table 2.
In the coordination environment around SmIII the nitrogen
atoms came from three pyridine rings, this is one of the common
coordination patterns for complexes with a coordination number of
nine; there are three independent planes of pyridine rings, which
orient approximately orthogonally to the plane of the three coor-
dinated nitrogen atoms. Since the amine is more basic than the

Table 1
Crystal data, data collection and refinement details(a) for 1.

Compound 1

Chemical formula C27 H33 N6 O12 Sm

Formula weight 783.94
Space group Orthorhombic
Crystal system Pbcn Fig. 2. Geometry distorted tricapped trigonal prism for 1.
Crystal size (mm3) 0.35  0.26  0.21
Crystal color and shape Violet prism
a(Å) 16.9864(6) Å Table 2
b(Å) 10.7249(4) Å Selected bond distances (Å) and bond angles ( ) for 1.
c(Å) 18.5761(11) Å
Bond lengths (Å)
a(  ) 90.0000
b(o) 90.0000 N(1)eSm(1) 2.549(5)
g( ) 90.0000 N(2)eSm(1) 2.552(7)
Volume (Å3) 3384.1(3) O(1)eSm(1) 2.457(5)
Formula units per cell, Z 4 O(3)eSm(1) 2.476(5)
dcalc (Mg cm3) 1.539 O(5)eSm(1) 2.455(4)
m (mm1) 1.801 Bond angles ( )
R (int) 0.0813 O(5)eSm(1)eO(3) 88.31(16)
F(000) 1580 O(1)eSm(1)eO(3) 126.13(16)
Temperature of measurement (K) 298(2) O(5)eSm(1)eN(1) 74.96(15)
q Limits (o) 3.765e29.491 O(1)eSm(1)eN(1) 62.86(17)
No. of reflections collected 11746 O(5)eSm(1)eO(1) 78.21(16)
No. of independent reflections 4135 O(3)eSm(1)eN(1) 63.28(16)
No. of observed reflections, 2727 O(5)eSm(1)eN(2) 63.07(10)
R [F2 > 2 s(F2)] 0.0486 [I > 2s(I)] O(1)eSm(1)eN(2) 136.41(14)
wR (F2) 0.1427 O(3)eSm(1)eN(2) 74.22(10)
Goodness of fit, S 1.041 N(1)eSm(1)eN(2) 120.05(11)
No. of parameters 221
Drmin (e Å3) 2.31
Drmax (e Å3) 1.15
a
carboxylate group, the protons are located on the dimethylamine
Rint ¼ SjF2oe{F2o}j/SF2o; R1 ¼ SjjFojejFcjj/SjFoj.
molecules, giving an anionic character to the three-negative
 A.G. Viveros-Andrade et al. / Journal of Molecular Structure 1145 (2017) 10e17 13

Fig. 3. Hydrogen bonding interactions between one dimethylammonium cation and two oxygen atoms of two different anions.

samarium compound. This charge distribution is confirmed by the room-temperature, Fig. 4.

CeO distances for the oxygen atoms coordinated to the metal ion
(1.258e1.261 Å) and by the shorter CeO distances for the depro- 4.4. Spectroscopic characterization
tonated oxygen atoms (1.218e1.239 Å). The shortest SmeSm dis-
tance in 1 is 9.698 Å; this makes any direct communication The emission spectra obtained from the three complexes (1e3)
between the metal centers very unlikely, thus preventing concen- principally arise from transitions originating at the 4G5/2, 5D0 and
tration quenching, which so often occurs in oxide materials. The 5
D4 levels for SmIII, EuIII and TbIII ions, respectively. For complex 1,
stability of compounds (1e3) can be deduced from the crystal the four intense peaks at 489.3, 542.2, 583.1 and 621.1 nm corre-
packing. Each anion has in total six hydrogen bonding interactions, sponds to the 4G5/2 / 6F5/2, 4G5/2 / 6F7/2, 4G5/2 / 6F9/2 and 4G5/
we can observe that each dimethylammonium cation forms two 6 III
2 / F11/2 transitions of Sm ion. Complex 2 emits strong red light
hydrogen bonding interactions with two oxygen atoms of two when excited at 200 nm and exhibits the characteristic transitions
different anions, with bond lengths between H1eO1 of 1.89 Å and of the Eu(III) ions. The spectra of 2 show one weak band originated
H2eO2 of 1.69 Å see Fig. 3. from the 5D0 / 7F4 transition in 673.5 nm; the stronger transitions
in 540 nm is attributed to 5D0 / 7F1 and the most intense bands in
4.3. Stability studies 612 nm correspond to the 5D0 / 7F3 transition, which belongs to
the hypersensitive transition. The band at 487 nm corresponding to
5
The thermal stability was investigated using thermogravimetric D0 / 7F0 is weak, and the 5D0 / 7F2 transition around 588 nm
analysis to confirm the stability of 1e3 materials, when heating consists of an intense peak with one weak shoulder. The emission
gradually to 10  C per minute, a weight loss of 3% is observed be- spectra for (3) reveals the green-luminescence with typical emis-
tween 63 and 129  C, this decrease is ascribed to residual lattice sion of TbIII ions at 515, 567, 607 and 635 nm respectively, attrib-
water molecules; On heating the sample at 272  C a weight loss is uting to 5D4 / 7FJ (J ¼ 6e3) transitions. The dominant band is the
observed which corresponds to (CH3)2NH2, while at 331  C a sec- hypersensitive transition 5D4 / 7F3 and is made up of a single
ond loss of (CH3)2NH2 is observed, indicating that the thermal intense peak. The stronger luminescent band corresponds to
5
stability of the complex is related with intermolecular hydrogen D4 / 7F6 transition and two less intense bands ascribe to
bonding interactions. Only around 425  C these compounds start to 5
D4 / 7F4 and 5D4 / 7F5 transitions.
decompose, it suggests that these compounds are highly stable at Comparison of the IR (ATR) spectra of the PDA with those of the

Fig. 4. Thermogravimetric analysis of compounds (1) Sm (orange line), (2) Eu (red line) and (3) Tb (green line). (For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.)
14 A.G. Viveros-Andrade et al. / Journal of Molecular Structure 1145 (2017) 10e17

Table 3
Selected stretching vibrations (cm1) for H2PDA and luminescence complexes 1e3.

Compound ʋ (C]C)arom ʋ (C]O) ʋ (C]N) ʋ (CeO) ʋ (CeN) €

a (CeH)arom ʋ (NeH)

H2PDA 1455, 1411 1690 1574 1296 1256 750 e

(1) 1466, 1429 1599 1570 1385 1369 727 3541
(2) 1466, 1430 1599 1570 1386 1369 727 3540
(3) 1467, 1431 1600 1572 1387 1371 729 3543

lanthanide complexes indicate the deprotonation of eCOOH with

4,40 -bipyridine confirming their tridentate nature. Spectra of
lanthanide compounds show the characteristic vibrations assigned
to the stretching bands such as ʋ (C]C)arom at 1411e1467 cm1, ʋ
(C]N) at 1572e1570, cm1, ʋ (CeH)arom at 729e727 cm1 for 1e3
compounds. A significant change is observed in the ʋ (C]O)
stretching band of compounds, the spectra of all complexes show
the ʋ (C]O) vibration, shifted to lower energies at 1599e1600,
cm1, Table 3.

4.5. Absorption and luminescence spectra

The solution absorption spectrum of H2PDA in methanol

(1  103 M) shows three absorption bands with maxima at 204 nm
(50251 cm1, ε ¼ 36315 M1 cm1) p/p* (pyridine ring), 222 nm
(49020 cm1, ε ¼ 1330 M1 cm1) p/p* and at 280 nm
(37037 cm1, ε ¼ 290 M1 cm1) see Fig. 5, assigned to the
HOMO / LUMO [45] (S0 to S1 transition). TD-DFT calculations help
to elucidate the nature of this transition [46]. It has been assigned in
the literature as a ligand centered p to p * transition and TD-DFT
calculations carried out for our ligand confirm this assignment.
Plots of the HOMO and LUMO orbitals are given in Fig. 6.
A weak band at 341 nm (29326 cm1) is assigned to the S1 / T1
transition and it was confirmed by DFT calculations (calculated
value of 349 nm).
Calculated UVeVis absorption spectra are in good agreement
with the experimental solution absorption spectrum, a comparison Fig. 6. Selected molecular orbitals of H2PDA in methanolic solution.
also given in Fig. 7.
The solid-state diffuse reflectance spectra of all compounds
show intense absorption in the UV-region. The spectra of coordi-
nation compounds 1, 2 and 3 show similar features. It is worth
mentioning that the diffuse reflectance spectrum of the samarium
compound shows the characteristic absorption peaks for samar-
ium(III), see Fig. 8 and Table 4, where the assignments are given

Fig. 7. Electronic absorption spectrum of H2PDA in methanol (1  103 M) at RT (vi-

olet), calculated absorption spectrum in methanol (blue) by TD-DFT, PCM, B3LYP/6-31G
(d, p). (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

[47].
Luminescence is observed from H2PDA (1). The band maximum
is at ca. 400 nm (ca. 25000 cm1) when the sample was excited at
Fig. 5. UVeVis absorption spectrum of a 1  103 M solution of H2PDA in methanol at
330 nm. Fig. 9 shows a typical mirror image relationship between
RT. Inset. 5  103 M solution of H2PDA in methanol at RT.
 A.G. Viveros-Andrade et al. / Journal of Molecular Structure 1145 (2017) 10e17 15

absorption and luminescence bands of H2PDA [48].

Figs. 10e12 show emission and excitation spectra of compounds
1, 2 and 3, where the data of either the emission or excitation
spectrum has been multiplied by a factor to have both spectra on
the same scale, as indicated in the figures. Characteristic emission
bands are observed for the PDA coordination compounds with SmIII
(see Fig. 10), EuIII (see Fig. 11) and TbIII (see Figs. 6 and 12) and
Table 5. It can be concluded that energy transfer from PDA to the
lanthanide(III) metal ions takes place as indicated by their excita-
tion spectra, where the characteristic absorption bands for samar-
ium(III), europium(III) and terbium(III) are observed when the
compounds were irradiated at 562, 600 and 542 nm, respectively
(emission maxima), see Figs. 8 and 10 and Table 6. Additionally,
emission of DPA can also be observed in the excitation spectra.
Emission and excitation spectra of Na3Tb(PDA)3,8H2O have
been reported in the literature, together with its IR and 1H and 13C
NMR spectra [49].

Fig. 8. Diffuse Reflectance spectrum of [H2NMe2]3[Sm(PDA)3], see Table 4 for

assignment.

Table 4
Diffuse reflectance transitions of [H2NMe2]3[Sm(PDA)3].

Transition l (nm) Wavenumbers (cm1)

1
S0 / S1 267 37453
6 4
H5/2 / F9/2 þ 4D3/2 368 27174
6 4
H5/2 / L17/2 þ 4K17/2 377 26525
6 4
H5/2 / G11/2 391 25575
6 4
H5/2 / F7/2 þ 4G7/2 405 24691
6 4
H5/2 / M19/2 418 23923
6 4
H5/2 / G9/2 þ 4M17/2 443 22573
6 4
H5/2 / F5/2 þ 4G5/2 454 22026
6 4
H5/2 / I13/2 þ 4K13/2 466 21459
6 4
H5/2 / I11/2 þ 4M15/2 480 20833
6 4
H5/2 / I9/2 490 20408
6 4
H5/2 / G7/2 þ 4F7/2 502 19920
6 4
H5/2 / F3/2 532 18797
6 4
H5/2 / G5/2 þ 4F5/2 564 17730
6 6
H5/2 / F11/2 953 10493
6
H5/2 / 6
F9/2 1093 9149 Fig. 10. Solid state excitation (blue) and emission (orange) spectra of
6
H5/2 / 6
F7/2 1258 7949 [H2NMe2]3[Sm(PDA)3], see Tables 5 and 6 for assignment. (For interpretation of the
6
H5/2 / 6
F5/2 1402 7133 references to colour in this figure legend, the reader is referred to the web version of
6
H5/2 / 6
F3/2 1509 6627 this article.)
6 6
H5/2 / F1/2 1513 6609
6 6
H5/2 / H15/2 1658 6031

Fig. 11. Solid state excitation (blue) and emission (orange) spectra of
[H2NMe2]3[Eu(PDA)3], see Tables 5 and 6 for assignment. (For interpretation of the
3
Fig. 9. Solution absorption (violet, 5  10 M, MeOH) and solid state emission spectra references to colour in this figure legend, the reader is referred to the web version of
(blue) of H2PDA. this article.)
16 A.G. Viveros-Andrade et al. / Journal of Molecular Structure 1145 (2017) 10e17

Table 6
Excitation Spectra Data for compounds 1, 2 and 3.

Compound Transition l (nm) Wavenumbers

(cm1)
1
[H2NMe2]3[Sm(PDA)3] S0 / 1S1 295 33898
6
H5/2 / 4L17/2þ 4K17/2 345 28985
6
H5/2 / 4H7/2 356 28090
6
H5/2 / 4D3/2 362 27624
6
H5/2 / 4L17/2þ 4K17/2 376 26596
6
H5/2 / 4L15/2þ 4K15/2 390 25641
6
H5/2 / 4F7/2þ 4G7/2 404 24752
6
H5/2 / 4M19/2 417 23981
6
H5/2 / 4I15/2þ 4M15/2 442 22624
6
H5/2 / 4F5/2þ 4G5/2 450 22222
6
H5/2 / 4I13/2þ 4K13/2 466 21459
6
H5/2 / 4I11/2þ 4M15/2 474 21097
6
H5/2 / 4I11/2þ 4M15/2 478 20920
6
H5/2 / 4I9/2þ 4M15/2 491 20367
6
H5/2 / 4F7/2þ 4G7/2 500 20000
6
H5/2 / 4F7/2þ 4G7/2 513 19493
1
Fig. 12. Solid state excitation (blue) and emission (orange) spectra of [H2NMe2]3[Eu(PDA)3] S0 / 1S1 298 33557
7
[H2NMe2]3[Tb(PDA)3], see Tables 5 and 6 for assignment. (For interpretation of the F0 / 5D4 361 27701
7
references to colour in this figure legend, the reader is referred to the web version of F0 / 5D4 375 26667
7
this article.) F0 / 5G4 380 26316
7
F0 / 5G2 388 25773
7
F0 / 5L6 395 25316
7
Table 5 F0 / 5L7 416 24038
7
Emission bands of compounds 1, 2 and 3. F0 / 5D3 464 21552
7
F0 / 5D1 473 21142
Compound Transition l (nm) Wavenumbers (cm1) 7
F0 / 5D0 486 20576
1
[H2NMe2]3[Tb(PDA)3] S0 / 1S1 330 29586
[H2NMe2]3[Sm(PDA)3] 4G5/ 562 17794 7
6 F6 / 5L10 367 27248
2 / H5/2 7
4 F6 / 5D3 379 26385
G5/ 593, 601, 614 16863, 16639, 16287 7
6 F6 / 5D4 488 20492
2 / H7/2
4
G5/ 642 15576
6
2 / H9/2
[H2NMe2]3[Eu(PDA)3] 5D0 / 7F1 592 16892 Table 7
5
D0 / 7F2 613, 614, 615 16313, 16287, 16260 Effective Magnetic Moments of compounds 1, 2 and 3.
5
D0 / 7F3 648 15432
5
D0 / 7F4 686, 693, 701 14577, 14430, 14265 Compound meff (BM) Observed meff (BM)(Ref)
[H2NMe2]3[Tb(PDA)3] 5D4 / 7F6 486, 490 20576, 20408
5
[H2NMe2]3[Sm(PDA)3] 1.67 1.4e1.7
D4 / 7F5 541, 544, 547 18484, 18382, 18281
5
[H2NMe2]3[Eu(PDA)3] 3.21 3.3e3.5
D4 / 7F4 577, 581, 585, 17331, 17212, 17094,
[H2NMe2]3[Tb(PDA)3] 9.74 9.5e9.8
590 16949
5
D4 / 7F3 619, 622 16155, 16077

theory (TD-DFT) with the aforementioned functional and basis set.

A comparison with Dieke's diagram [50] indicates Sm , Eu and III III The calculation was carried out in solution (methanol) with a
TbIII luminescence could be observable. These transitions for 1, 2 polarizable continuum model (PCM) [55] using the optimized
and 3 are listed in Table 5 and can be assigned by comparisons with structure in this media with the same optimization method
literature spectra [51]. described earlier. The calculated absorption spectrum was then
obtained by arbitrarily setting the full-width-at-half-maximum
(FWHM) of the calculated transitions to 129049 cm1.
4.6. Magnetic moments of the coordination compounds

The effective magnetic moments of all coordination compounds 5. Conclusions

were obtained by the Gouy method and correspond to the expected
values for the lanthanide(III) ions, see Table 7. A novel synthetic route for the preparation of
[H2NMe2]3[Ln(PDA)3] is presented herein. Energy transfer from the
4.7. Computational details ligand to the lanthanides was very good, thus the H2PDA can be
considered as a sensitizer for these metal ions. TD-DFT calculations
All the calculations were performed with the Gaussian 09 data agreed well with the experimental values for the first singlet
package (Gaussian Inc.) [52] using methods as they are imple- and the triplet states of the ligand. It was possible to observe
mented in the software. Initially, a ground-state geometry optimi- several absorption bands for samarium(III) in the diffuse reflec-
zation was performed in the gas-phase on a single molecule with tance spectrum. The crystal packing observed by x-ray diffraction
the B3LYP exchange correlation functional [53,54] and the 6- and the thermogravimetric analysis could explain the great sta-
31G(d,p) basis set. bility of compounds (1e3), been the principal reason of the sta-
Molecular orbitals were also calculated for this optimized bility, the multiple hydrogen bonding interactions between the
structure and were visualized with the 5.08 release of the Gauss- complexes and the (CH3)2NH2 cation. The complexes have mono-
View software (Gaussian Inc.) [52] with an isovalue of 0.02 atomic nuclear structures with distorted tricapped trigonal prismatic ge-
units. Furthermore, excitation energies were evaluated for the ometry of their Ln center which is the preferred one in solid state
discussed ligand by mean of the time dependent density functional for PDA complexes; these structural features are not surprising,
 A.G. Viveros-Andrade et al. / Journal of Molecular Structure 1145 (2017) 10e17 17

since several comparable structures for Sm(III), Eu(III) and Tb(III) 126 (2004) 15394e15395.
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