Multifunctionality in two families of dinuclear lanthanide(III) complexes with a tridentate schiff-base ligand

Article abstract of DOI:10.1021/acs.inorgchem.9b01524

The employment of N-(2-carboxyphenyl)salicylideneimine in 4f metal chemistry has led to two families of dinuclear complexes depending on the lanthanide(III) used. Representative members exhibit interesting magnetic, optical, and catalytic properties.

Full text of DOI:10.1021/acs.inorgchem.9b01524

Communication
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Multifunctionality in Two Families of Dinuclear Lanthanide(III)
Complexes with a Tridentate Schiff-Base Ligand
†
‡
§
∥
Nikolaos C. Anastasiadis, Carlos M. Granadeiro, Julia Mayans, Catherine P. Raptopoulou,
⊥
‡
,∥
,§
,‡
Vlasoula Bekiari, Luís Cunha-Silva, Vassilis Psycharis,* Albert Escuer,* Salete S. Balula,*
,
†
,†
Konstantis F. Konidaris,* and Spyros P. Perlepes*
†
Department of Chemistry, University of Patras, 26504 Patras, Greece
‡
REQUIMTE/LAQV and Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto,
Portugal
§
2
Departament de Quimica Inorgan
̀
ica i Organ
1−11, 08028 Barcelona, Spain
Institute of Nanoscience and Technology, National Centre of Scientific Research “Demokritos”, 15310 Aghia Paraskevi, Attikis,
Greece
ica, Seccio Inorganica and Institut de Nanociencia (IN UB) i Nanotecnologia,
̀ ́ ̀ ̀
Universitat de Barcelona, Marti i Franques
̀
∥
⊥
School of Agriculture Sciences, University of Patras, Messolonghi, 30200 Messolonghi, Greece
S Supporting Information
*
25
The reactions of Ln(NO ) ·xH O (x = 5 or 6) and LH in
3
3
2
2
ABSTRACT: The employment of N-(2-carboxyphenyl)-
salicylideneimine in 4f metal chemistry has led to two
families of dinuclear complexes depending on the
lanthanide(III) used. Representative members exhibit
interesting magnetic, optical, and catalytic properties.
1
(
:2 molar ratios in methanol (MeOH)−acetonitrile (MeCN)
1 : 1 , v / v ) p r o v i d e d a c c e s s t o c r y s t a l s o f
[Ln (NO ) (LH) (MeOH) ]·MeOH [Ln = Nd (1·MeOH),
2 3 4 2 4
Gd (2·MeOH), Tb (3·MeOH)], [Ln (NO ) (LH) ]·6MeCN
2
3 2
4
[
[
Ln = Dy (4·6MeCN), Y (6·6MeCN)], and
Yb (NO ) (LH) ]·1.4MeCN (5·1.4MeCN) in typical yields
2
3 2
4
of 45−55%. The product identity from the Pr(NO ) ·6H O/
3
3
2
he chemistry and properties of multifunctional molecule-
based materials are currently a “hot” topic in inorganic
LH (1:2) reaction system in MeOH−MeCN (1:1, v/v)
2
T
depends on the absence or presence of an external base. In the
chemistry because of their importance in high-technology
presence of 1 equiv of triethanolamine per 1 equiv of LH , the
2
1
,2
applications. Lanthanide(III) [Ln(III)] complexes are ideal
product is [Pr (NO ) (LH) (MeOH) ]·MeOH (7·MeOH);
2
3 4
2
4
2
−4
candidates for the construction of such molecular materials
because of the unique and diverse reactivity and electronic
the absence of an external base leads to crystallization of the
mononuclear complex [Pr(NO ) (LH)(LH )(MeOH)]·
3
2
2
III
5
characteristics of the Ln ions, resulting in impressive
MeCN (8·MeCN).
6
−8
9,10
11,12
13,14
magnetic,
optical,
catalytic,
medicinal,
and
The crystal structure of the representative complex 2·MeOH
contains two crystallographically independent, centrosymmet-
ric [Gd (NO ) (LH) (MeOH) ] molecules (Figures 1 and S1
1
5
biological properties. Dinuclear Ln(III) complexes represent
one of the simplest systems for the study of multifunctional
2
3 4
2
4
16
III
molecular materials. Schiff-base ligands play a key role in this
and Table S1). The two Gd atoms are bridged by the syn,syn-
carboxylate groups of two η :η η μ (or 2.111 using Harris
notation; Scheme S1b) LH ligands. Two bidentate chelating
1
1 1
area, for example, in luminescent Ln(III) single-molecule
2
2
−
magnets (SMMs).
As a continuation of our interest in the areas of (a) the
nitrato groups, two terminal MeOH molecules, and one
terminal phenolate O atom complete 9-coordination at each
chemistry of dinuclear Ln(III) complexes exhibiting more than
1
7,18
−
one property
and (b) the coordination chemistry of Schiff
metal ion. The H atom of the phenol −OH group of LH has
bases resulting from the condensation of salicylaldehyde (or its
derivatives) and aniline (neat or functionalized with other
“emigrated” to the imine N atom, and the latter is thus
protonated and not coordinated. Complexes 1−3·MeOH have
molecular structures rather similar to that of
1
8−20
donor groups),
we report herein the synthetic inves-
tigation of the reaction system Ln(NO ) ·xH O/LH , where
[Dy
2
(NO ) (sacbH) (H O) (MeCN) ], where sacbH is N-
3 4 2 2 2 2 2
3
3
2
2
26
LH2 is the potentially tetradentate Schiff base N-(2-
carboxyphenyl)salicylideneimine (Scheme S1a). Our efforts
have led to two families of complexes depending on the metal
ion used; preliminary studies on representative members of the
families reveal a triple functionality concerning slow magnetic
relaxation, light emission, and homogeneous catalysis. The
salicylidene-2-amino-5-chlorobenzoic acid.
The two Dy atoms in the representative centrosymmetric
III
molecule 4 (Figures 2 and S7) are bridged by the syn,syn-
1
1 1
carboxylate groups of the four η :η η μ (2.111; Figure 1b)
2
−
LH ligands. A bidentate chelating nitrato group and two
terminal phenolate O atoms complete 8-coordination, resulting
Schiff base LH is a rather well-known ligand in 3d metal
2
2
1,22
chemistry;
negligible.
however, its use in 4f metal chemistry is
Received: May 23, 2019
2
3,24
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.9b01524
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
are observed at low temperatures under a dc field of 1500 G
only for 4 [Figure S27 (right)], providing evidence of field-
induced slow magnetic relaxation for this complex, assigned to
the whole dinuclear molecule (see the Supporting Informa-
tion). Analysis of the experimental data afforded an effective
−
1
barrier for the magnetization reversal (U ) of 8.0 cm and a
eff
−
6
τ0 value of 3.5 × 10 s. It is evident that magnetic relaxation
through strong quantum tunneling of magnetization occurs,
27
thus diminishing the SMM behavior of 4.
The catalytic activities of 2 and 4 for Baeyer−Villiger
28−30
oxidation
of the model substrate cyclohexanone (9) were
examined at 70 °C using “green” hydrogen peroxide (H O ;
2
2
aqueous 30%) as the oxidant (Figure 3, top). Attempts to
Figure 1. Partially labeled plot of the structure of the Gd2/2″-
containing dinuclear molecule that is present in 2·MeOH. Symmetry
operation: (″) −x + 2, −y + 1, −z + 1.
Figure 3. Catalytic transformations studied in this work.
apply transition-metal catalysis to this significant organic
2
8−33
transformation have met with some success,
of 4f metal ions has been confined to simple lanthanide(III)
but the use
34
triflates. In the absence of catalyst or in the presence of only
Ln(NO ) ·xH O (Ln = Gd, Dy), practically no conversion was
Figure 2. Partially labeled plot of the structure of the dinuclear
molecule that is present in 4·6MeCN. Symmetry operation: (′) −x,
3
3
2
−y + 1, −z + 2.
verified under conditions similar to those of the catalytic
reactions. The catalytic performances of 2 and 4 in MeCN or
α,α,α-trifluorotoluene (TFT; this is the first use of the TFT/
H O combination in oxidation catalysis) were similar, and
in a square-antiprismatic geometry for the metal ion (Figure
S10).
2
2
The crystal structure of 8·MeCN contains two crystallo-
100% selectivity to caprolactone (10) was observed. The
choice of TFT as the solvent is due to its immiscibility with the
aqueous H O oxidant (contrary to MeCN), poor coordina-
graphically independent, slightly different [Pr(NO ) (LH)-
(
3
2
LH )(MeOH)] molecules (Figures S15 and S16). The
2
2
2
III
coordination sphere of both 9-coordinate Pr atoms contains
a strongly hydrogen-bonded (LH ···LH) pair that behaves as
tion ability, lower polarizability, low volatility, and reduced
−
35
toxicity. However, an important influence of the solvent on
2
a tetradentate chelating 1.11110000 “ligand” (Figure S17).
An identical room-temperature photoluminescence behavior
is observed for solid samples of 3 and 4. Upon maximum
excitation at 450 or 330 nm, a broad green emission at ∼555
the activity was observed. In Figure 4, the catalytic activities of
2 in MeCN and TFT are compared. When the oxidation of 9
was catalyzed by 2 using MeCN as the solvent, only 11%
conversion was achieved (27% by 4), instead of 70%
conversion obtained with TFT as the solvent (71% by 4).
The different catalytic conversions of 9 in the two solvents
must be related to the different reaction media provided. The
higher conversion in TFT is due to the fact that the aqueous
H O oxidant is in a separate phase from the catalyst and
III
nm was recorded; no significant Ln emission was detected
1
7,18
(
Figures S21−S26).
Solid-state direct-current (dc) molar magnetic susceptibility
(
χ ) data on 2−4 were collected at 0.03 T in the temperature
Μ
range 300−2.0 K and are plotted as χ T versus T in Figure
S27 (left); a full discussion is provided in the Supporting
Information (text and Figures S27−S29). The Ln centers in
2
Μ
2
2
substrate. This favors less decomposition of the oxidant,
increasing its efficiency for catalytic oxidation and at the same
time preventing catalyst deactivation caused by the presence of
the water content of the oxidant. In general, the tested
compounds 2 and 4 exhibit higher activities than Re(III),
Re(IV), Re(V), and Re(VII) complexes with various donors
III
and 3, which are bridged by two carboxylate groups, are not
interacting. A weak intramolecular ferromagnetic interaction is
III
observed in 4, where the two Dy centers are bridged by four
carboxylate groups. Alternating-current (ac) magnetic suscept-
ibility studies were performed on polycrystalline samples of 3
and 4 in the 2.0−12 K range in a 4.0 G ac field oscillating at
31,33
for the transformation of 9 to 10 in the presence of H O .
2
2
The catalytic activity of 2, which possesses two labile
III
1
490−10 Hz. Frequency-dependent out-of-phase (χ ″) signals
terminal MeOH molecules per Gd atom, for aminolysis
M
B
DOI: 10.1021/acs.inorgchem.9b01524
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
multifunctionality in terms of photoluminescence, magnetism,
and homogeneous catalysis. We are currently trying to extend
and optimize the above-mentioned preliminary results.
Particular emphasis is given on the introduction of appropriate
ring substituents in LH in order to achieve visible and near-IR
2
III
emission based on the Ln ions (and not ligand-based as in
the present study), slow magnetic relaxation at zero field (and
III
not under a bias field), and Ln -based asymmetric catalysis,
with our long-term goal being the design of systems in which
such functionalities will strongly interact.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b01524.
■
Figure 4. Conversion data obtained using 2 as the catalyst and MeCN
or TFT as the solvent in the (1) Baeyer−Villiger oxidation of 9 to 10
after 24 h, (2) aminolysis of 11 to 13 after 30 min, and (3) aminolysis
of 14 to 15 (see the Supporting Information for experimental details).
All reactions were performed using a catalyst (3.0 μmol), a substrate
*
S
(
1.0 mmol), and a solvent (1.5 mL). Baeyer−Villiger oxidation was
Full experimental, synthetic, structural, photolumines-
cence, and magnetic and catalytic details in the forms of
text, tables (Tables S1−S6), and figures (Figures S1−
S29) (PDF)
carried out at 70 °C using 30% H O (4.5 mmol), while aminolysis
reactions were carried out at 80 °C with aniline (0.9 mmol).
2
2
3
6
reactions of the model substrates cyclohexene oxide (11) and
styrene oxide (14) was also examined in MeCN and TFT
using aniline (12) at 80 °C (Figure 3); an optimal substrate-to-
aniline ratio of 1:0.9 was used. The products of the aminolysis
reactions of β-epoxides, i.e., β-amino alcohols, are useful
synthetic intermediates and are widely used in the preparation
Accession Codes
CCDC 1917908−1917913 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
3
7
of various pharmacologically important compounds. Several
homogeneous acid catalysts, including lanthanide(III) tri-
3
8,39
40,41
flates
and complexes involving binaphtholates,
have
AUTHOR INFORMATION
Corresponding Authors
been reported to catalyze these reactions. In the absence of
■
catalyst or in the presence of only Gd(NO ) ·6H O, only a
3
3
2
*
*
*
*
*
9
E-mail: v.psycharis@inn.demokritos.gr (V.P.).
E-mail: albert.escuer@qi.ub.es (A.E.).
E-mail: sbalula@fc.up.pt (S.S.B.).
E-mail: konidaris@upatras.gr (K.F.K.).
E-mail: perlepes@patreas.upatras.gr (S.P.P.). Tel: +30-2610-
96730.
negligible amount of 13 or 15 was detected. In each of the two
reactions performed, 2 gave a selective and clean trans-
formation, resulting in a unique product (Figure 3). The yield
of the reaction between 14 and 12 to produce 15 was almost
1
00% in both solvents after 30 min (Figure 4). The yield of the
reaction between 11 and 12 to give 13 is influenced by the
solvent used. After 30 min of reaction, complete formation of
ORCID
1
3 is observed using TFT; for the same reaction time, the yield
decreases to 48% when MeCN is used as the solvent (Figure
), probably suggesting a different mechanism in the two
Nikolaos C. Anastasiadis: 0000-0002-8361-8054
Carlos M. Granadeiro: 0000-0002-0986-6607
Luís Cunha-Silva: 0000-0001-9229-1412
Salete S. Balula: 0000-0002-8984-0473
Konstantis F. Konidaris: 0000-0002-7366-5682
Spyros P. Perlepes: 0000-0002-3378-6228
4
solvents. This indicates the great potential of TFT, which has
been used as the solvent for the first time in this study, for
catalytic aminolysis reactions. The good-to-excellent catalytic
effects of 2 in the studied aminolyses of epoxides may
38
III
Notes
reasonably be attributed to the strong oxophilicity of Gd in
, which allows the metal ion to strongly coordinate to the
oxirane O atom, thus favoring the nucleophilic opening
The authors declare no competing financial interest.
2
3
8
ACKNOWLEDGMENTS
process. The catalytic performance of 2 for the conversion
of 11 to 13 is superior to that of lanthanum(III) and
samarium(III) iodobinaphtholate complexes, but catalysis by
the La(III) and Sm(III) complexes takes place at room
temperature. Similarly, the performance of 2 for the conversion
of 14 to 15 is better than that of heterogeneous catalysts at
■
This research has been carried out in the context of the Action
“Reinforcement of Postdoctoral Researchers” (MIS:5001552
to N.C.A.) of the Operational Program “Development of
Human Resources, Education and Lifelong Learning”, 2014−
2020, realized by IKY and cofunded by the European Social
Fund and National Resources. A.E. and J.M. thank the
42
37,42
temperatures above room temperature.
́
Complexes 2 and 4 seem to retain their gross structural
Ministerio de Economia y Competitividad (Project CTQ2015-
features in MeCN and TFT, as evidenced by their negligible
63614-P) for funding. S.P.P. is grateful to the COST Action:
CA15128-Molecular Spintronics (MOLSPIN). C.M.G., L.C.-
S., and S.S.B. acknowledge financial support by national funds
̃
̂
(OE) through the Fundac a̧ o para a Ciencia e Tecnologia, IP
(FCT) and when appropriate by FEDER (Fundo Europeu de
Desenvolvimento Regional) under the PT2020 Partnership
Agreement within the scope of Projects UID/QUI/50006/
molar conductivity in the two solvents. Preliminary para-
1
magnetic H NMR spectra of 4 in CD CN indicate that no
3
−
LH leaching phenomena appear.
In conclusion, a synthetic investigation of the Ln(NO ) ·
3
3
xH O/LH reaction system has resulted in two families of
2
2
dinuclear complexes, representative members of which exhibit
C
DOI: 10.1021/acs.inorgchem.9b01524
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
019 (REQUIMTE/LAQV) and GlyGold (PTDC/CTM-
CTM/31983/2017). C.M.G. and L.C.S. also thank the FCT
by national funds (OE) in the ambit of the framework contract
foreseen in Nos. 4−6 of Article 23 of Decree Law 57/2016, of
August 29, 2016, changed by Law 57/2017, of July 19, 2017.
Communication
2
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