Inorganic Chemistry
Article
NMR (300 MHz, CD OD): δ = 171.0, 170.3, 167.2, 164.4, 142.1,
EXPERIMENTAL SECTION
3
■
1
1
2
33.0, 120.2, 116.5, 113.4 ppm. IR (ν): 3384 (br), 1694 (s), 1579 (m),
Materials and Methods. Solvent and reagents were commercially
available and used without further purification. NMR spectra were
recorded on a Bruker DPX-300 spectrometer. Elemental analysis for C
and H was performed on a Perkin-Elmer 2400 series II analyzer. Mass
spectra were recorded using a Finnigan Aqua mass spectrometer (MS)
with electrospray ionization (ESI). IR spectra were recorded with a
Perkin-Elmer Paragon 1000 FTIR spectrophotometer equipped with a
Golden Gate ATR device. The excitation and emission spectra were
measured on a Shimadzu RF-5301PC spectrofluoriphotometer. X-ray
powder diffraction patterns were obtained on a Philips PW 1050
diffractometer using Cu Kα radiation (λ = 1.542 Å). Inductively
coupled plasma (ICP) emission spectroscopy was performed on a
VISTA-MPX Simultaneous TCP-OES with Varian SPS 3 sample
preparation system. Thermogravimetric analyses (TGA) spectra were
recorded on a NETZSCH STA 499 instrument under argon
atmosphere with heating rate of 3 K per minute. Luminescence
lifetime was determined using an Edinburg Instruments FLS920
spectrophotometer, with an OPOTEK Opolette 355 HR pulsed laser
as the excitation source. Temperature-dependent emission spectra
were recorded using an Oxford Instruments liquid helium flow
cryostat for the temperature range from 4.2 to 290 K; Hamamatsu
R928 PMT is used as a detector. Photoluminescence quantum yields
−1
327 (m), 1220 (s), 1137 (m), 859 (m), 757 (s), 635 (s) cm . Mp:
−
37 °C. ESI-MS found (calcd): 225.0 (225.0) [M − H] , 451.0
−
(451.0) [2M − H] .
Hydrothermal Synthesis of the Lanthanoid Compounds. A
mixture of H L (67.84 mg, 0.3 mmol), LnCl ·6H O (0.1 mmol, Ln =
4
3
2
Tb, Eu), 5 mL of water, and 5 mL of ethanol was brought into a 25 mL
Teflon lined stainless steel vessel; the vessel was closed, and a number
of reaction vessels together were placed in a big pan containing 15 kg
of sand. The reaction vessels were heated for 1 day in an oven set at
1
20 °C. The oven was slowly cooled down to room temperature at a
rate of 2.5 °C/h. Colorless crystals were collected on a glass frit and
washed with water and ethanol. Yield: 12 mg (23%) for TbHL and 13
mg (25%) for EuHL based on LnCl ·6H O.
3
2
TbHL analyzed as {[Tb (HL) (H O) ]·5.5H O} . Anal. Found
2
2
2
3
2
n
(Calcd) for C H O Tb : C, 23.54 (23.57); H, 2.61 (2.53). Selected
18 23 22.5 2
IR data (ν): 3175 (br), 1546 (s), 1387 (vs), 1264 (s), 884 (m), 805
−1
(
m), 656 (s), 566 (s), 475 (m) cm .
EuHL analyzed as {[Eu (HL) (H O) ]·5.5H O} . Anal. Found
2
2
2
3
2
n
(
Calcd) for C H Eu O22.5: C, 23.73 (23.93); H, 2.45 (2.57). Selected
18
23
2
IR data (ν): 3180 (br), 1544 (s), 1387 (vs), 1263 (s), 881 (m), 803
−1
(
m), 656 (s), 564 (s), 471 (m) cm .
The synthesis of mixed-lanthanoid compounds was carried out
2
6
at room temperature were determined using the absolute method.
An integrating sphere (Avantes AvaSphere 30REFL) was connected to
an irradiance-calibrated CCD spectrometer (Avantes AvaSpec-
048UA). A 1000 W xenon lamp (LOT) and a Spex monochromator
were used as the excitation source.
following the procedure described above, but mixtures of TbCl ·6H O,
3
2
EuCl ·6H O, and GdCl ·6H O were used instead of pure Ln salts.
3
2
3
2
Yields: 13 mg (28%) for Gd0.95Tb0.05HL; 12 mg (26%) for
Gd0.95Eu0.05HL; 12 mg (26%) for Tb0.95Eu0.05HL; 12 mg (26%) for
Tb Eu HL; 10 mg (22%) for Tb Eu HL; 11 mg (24%) for
2
0.8
0.2
0.6
0.4
Synthesis of 5-Hydroxy-1,2,4-benzenetricarboxylic Acid
Tb Eu HL; 12 mg (27%) for Tb Eu HL based on Ln salts.
0.4
0.6
0.2
0.8
(
H L). The ligand was synthesized using a procedure that was slightly
4
27,28
analysis for Tb, Eu, and Gd (Table S3), and elemental analyses for C
and H were used to determine the chemical composition of the
compounds.
modified from that of the literature.
Details for 2,4,5-
trimethylbenzenesulfonic acid (1) follow. With stirring, concentrated
sulfuric acid (40 mL, 736 mmol) was added to 1,2,4-trimethylbenzene
20 mL, 146 mmol). After stirring for 30 min, 60 g of ice was added,
resulting in the immediate formation of white solid. The product was
(
Gd0.95Tb0.05HL analyzed as {[Gd1.88Tb0.12(HL) (H O) ]·5H O} .
2
2
3
2
n
Anal. Found (Calcd) for C H Gd O Tb0.11: C, 23.85 (23.93); H,
1
8
22
1.88 22
collected by filtration, and recrystallized from 200 mL of 20%
−1
2
.18 (2.45). Selected IR data (ν, cm ): 3185 (br), 1547 (s), 1390
hydrochloric acid to give a light blue crystalline solid. Yield: 21.5 g
(
vs), 1265 (s), 883 (m), 805 (m), 656 (s), 566 (s), 475 (m).
1
(
2
1
(
(
(
74%). H NMR (300 MHz, D O): δ = 7.58 (s, 1H), 7.11 (s, 1H),
2
Gd Eu0.05Tb0.05HL analyzed as {[Gd Eu0.08Tb0.12(HL) (H O) ]·
0.9
1.8
2
2
3
13
.47 (s, 1H), 2.21 ppm (s, 2H). C NMR (300 MHz, D O): δ =
2
5H O} . Anal. Found (Calcd) for C H Eu Gd O Tb0.12: C,
2 n 18 22 0.08 1.8 22
40.2, 137.6, 133.9, 133.2, 132.8, 132.7, 127.3, 18.7, 18.2, 18.0 ppm. IR
2
3.96 (23.88); H, 2.18 (2.45). Selected IR data (ν): 3185 (br), 1548
ν): 2976 (br), 1691 (br), 1148 (s), 1048 (s), 973 (s), 655(m), 559
(
s), 1391 (vs), 1265 (s), 884 (m), 803 (m), 657 (s), 566 (s), 475 (m)
−1
−1
m), 491 (m) cm . Mp: 109 °C. ESI-MS found (calcd): 199.1
cm .
Gd0.95Eu0.05HL analyzed as {[Gd1.82Eu0.18(HL) (H O) ]·5H O} .
Anal. Found (Calcd) for C H Eu Gd O : C, 23.73 (23.92); H,
−
199.1) [M − H] .
2
2
3
2
n
Details for 5-sulfo-benzene-1,2,4-tricarboxylic acid (2) follow. Solid
1
8
22
0.18
1.82 22
−1
potassium permanganate (47 g, 159 mmol) was added slowly to a
stirred solution of 1 (10 g, 50 mmol) and NaOH (4 g, 100 mmol) in
2
.27 (2.45). Selected IR data (ν, cm ): 3185 (br), 1547 (s), 1390
(
vs), 1263 (s), 883 (m), 803 (m), 657 (s), 566 (s), 478 (m).
2
50 mL of H O at 90 °C. The solution was refluxed for 1 day. Then,
2
Tb0.95Eu0.05HL analyzed as {[Tb1.87Eu0.13(HL) (H O) ]·5.5H O} .
2
2
3
2
n
ethanol (10 mL) was added carefully to discolour the reaction
Anal. Found (Calcd) for C H Eu
O22.5Tb1.87: C, 23.58 (23.59); H,
18
23
0.13
−1
solution. Solid MnO was removed by filtration and was washed with
2.34 (2.53). Selected IR data (ν, cm ): 3187 (br), 1548 (s), 1391
(vs), 1262 (s), 885 (m), 805 (m), 657 (s), 567 (s), 475 (m).
Tb Eu HL analyzed as {[Tb1.55Eu0.45(HL) (H O) ]·5H O} .
2
hot water (2 × 100 mL). The filtrate was evaporated in vacuo. The
residue was taken up in 40 mL of H O, and concentrated hydrochloric
2
0.8
0.2
2
2
3
2
n
acid was added to pH = 1, resulting in the formation of white solid.
After stirring for an additional 20 min, the white solid was collected by
filtration and dried in vacuo. Yield: 11.9 g (82%). H NMR (300 MHz,
D O): δ = 8.14 (s, 1H), 7.73 ppm (s, 1H). C NMR (300 MHz,
D O): δ = 172.2, 171.9, 171.1, 141.0, 136.5, 135.7, 133.8, 127.9, 127.7
Anal. Found (Calcd) for C H Eu O Tb1.55: C, 23.83 (23.89);
18 22 0.45 22
−1
H, 2.25 (2.45). Selected IR data (ν, cm ): 3183 (br), 1546 (s), 1388
(vs), 1264 (s), 884 (m), 804 (m), 657 (s), 565 (s), 479 (m).
Tb Eu HL analyzed as {[Tb1.09Eu0.91(HL) (H O) ]·5.5H O} .
1
13
2
0.6
0.4
2
2
3
2
n
2
Anal. Found (Calcd) for C H Eu
18 23
0.91
O22.5Tb1.09: C, 23.93 (23.73); H,
−1
ppm. IR (ν): 3473 (br), 1710 (w), 1450 (m), 1383 (m), 1277 (m),
241 (m), 1204 (vs), 1039 (vs), 767 (s), 634 (s), 589 (s) cm . ESI-
2.36 (2.55). Selected IR data (ν, cm ): 3173 (br), 1545 (s), 1388
(vs), 1264 (s), 883 (m), 804 (m), 656 (s), 565 (s), 474 (m).
Tb Eu HL analyzed as {[Tb0.72Eu1.28(HL) (H O) ]·5.5H O} .
−1
1
−
MS found (calcd): 289.0 (289.0) [M − H] , 144.1 (144.0) [1/2(M −
0.4
0.6
2
2
3
2
n
−
2
H)] .
Anal. Found (Calcd) for C H Eu
O22.5Tb0.72: C, 23.96 (23.80); H,
18
23
1.28
−1
Details for 5-hydroxy-1,2,4-benzenetricarboxylic acid (H L) follow.
2.39 (2.55). Selected IR data (ν, cm ): 3167 (br), 1545 (s), 1388
(vs), 1264 (s), 882 (m), 804 (m), 656 (s), 564 (s), 474 (m).
Tb Eu HL analyzed as {[Tb0.35Eu1.65(HL) (H O) ]·5.5H O} .
4
Compound 2 (11 g, 38 mmol) and KOH (39 g, 695 mmol) were
mixed together with 7 mL of water in a 50 mL Teflon vessel. The
vessel without cap was put in an oven set at 200 °C for 7 h. Then, the
mixture was added to 200 mL of water, and concentrated hydrochloric
acid was added to pH = 1. The reaction mixture was heated to boiling
for 30 min, and then put in the refrigerator. The white solid formed
0.2
0.8
2
2
3
2
n
Anal. Found (Calcd) for C H Eu O Tb0.35: C, 24.14 (24.11); H,
18
22
1.65 22
−
1
2.42 (2.47). Selected IR data (v, cm ): 3183 (br), 1545 (s), 1387
(vs), 1264 (s), 882 (m), 804 (m), 656 (s), 564 (s), 474 (m).
Single Crystal Structure Determination. X-ray quality single
crystals of TbHL and EuHL were isolated from the procedure
described above. The crystals were mounted to a glass fiber using the
1
was collected by filtration and dried in vacuo. Yield: 6.7 g (78%). H
1
3
NMR (300 MHz, D O): δ = 8.43 (s, 1H), 7.05 ppm (s, 1H).
C
2
B
Inorg. Chem. XXXX, XXX, XXX−XXX