inorganics

Article
Homoleptic Lanthanide Complexes Containing a
Redox-Active Ligand and the Investigation of Their
Electronic and Photophysical Properties
Robin A. Taylor 1,2 , Nico M. Bonanno 2 , Mihaela Cibian 3 , Jeetika Yadav 3 ID ,
Harlyn J. Silverstein 1 , Christopher R. Wiebe 1,4,5 , Cole Mauws 1 ID , Alan J. Lough 6
and Martin T. Lemaire 1,2,7, * ID
1 Department of Chemistry, University of Manitoba, Winnipeg, MB R3T 2N2, Canada;
rob2235@hotmail.com (R.A.T.); harlyn.silverstein@gmail.com (H.J.S.); chris.r.wiebe@gmail.com (C.R.W.);
colemws@gmail.com (C.M.)
2 Department of Chemistry, Brock University, St. Catharines, ON L2S 3A1, Canada; nb15sz@brocku.ca
3 Department of Chemistry, Université de Montreal, Montreal, QC H3C 3J7, Canada;
cibian.mihaela@gmail.com (M.C.); jeetika.yadav@gmail.com (J.Y.)
4 Department of Chemistry, University of Winnipeg, Winnipeg, MB R3B 2G3, Canada
5 Canadian Institute for Advanced Research, Quantum Materials, MaRS Centre, West Tower,
661 University Ave., Suite 505, Toronto, ON M5G 1M1, Canada
6 Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON M5S 3H6, Canada;
alough@chem.utoronto.ca
7 Department of Chemistry, Brandon University, Brandon, MB R7A 6A9, Canada
* Correspondence: mlemaire@brocku.ca; Tel.: +1-905-688-5550




Received: 19 March 2018; Accepted: 18 May 2018; Published: 25 May 2018


Abstract: Herein, we describe the preparation, characterization and photophysical properties of

neutral lanthanide complexes containing a redox-active ligand 1-(2-pyridylazo)-2-phenanthrol
(papl). The complexes likely share similar structural features and bear the formulation Ln(papl)3
(Ln(III) = Gd, Dy, Tb), which is supported by electrospray ionization mass spectrometry, CHN
analysis, FT-IR and UV–Vis spectroscopy. The synthesis and structural properties of a related
complex, Ho(qapl)3 (where qapl = 10-(8-quinolylazo)-9-phenanthrol), is also reported. The complexes
feature ligand-centered redox activity, similar to other reported transition metal complexes with
papl. Variable temperature magnetic susceptibility measurements (DC and AC) suggest typical
free-ion magnetism without any slow-relaxation dynamics. The photophysical properties of
the ligand and complexes were investigated and the results of emission spectroscopy indicate
ligand-centered processes.

Keywords: redox active ligands; arylazo ligands; lanthanide ions; photophysical properties

1. Introduction
Lanthanide ion complexes are of interest for the production of luminescent and magnetic materials,
including as diagnostic agents in magnetic resonance imaging (MRI) [1–3], biosensors [4,5], and single
molecule (or ion) magnets (SMMs and SIMs, respectively) [6,7]. The contracted nature of the 4fn
valence orbitals of lanthanide ions results in little to no perturbation of the electronic structure within
the lanthanide ion upon ligand binding. Very often, the observed luminescence in these complexes
is the result of transitions within the energy level manifold of the lanthanide ion and this generally
results in the characteristic sharp emission spectra observed for these complexes. Another result of the
isolation of the f -orbitals from the ligand field is that lanthanide ion complexes often exhibit unique

Inorganics 2018, 6, 56; doi:10.3390/inorganics6020056 www.mdpi.com/journal/inorganics

Inorganics 2018, 6, 56 2 of 13

Inorganics 2018, 6, x FOR PEER REVIEW 2 of 13

magnetic properties generally easy to interpret as free ion magnetism by consideration of the total
of the total
angular angular momentum
momentum of the ion of in the
the ion
form in of
thethe
form freeofion
theterm
free ion term symbol.
symbol. Depending Depending on the
on the energy
energy level structure and depopulation of higher lying J states, a
level structure and depopulation of higher lying J states, a temperature dependence of the magnetic temperature dependence of the
magnetic moment is observed. Under the right set of conditions that
moment is observed. Under the right set of conditions that include symmetry, coordination number, include symmetry, coordination
number,
geometrygeometry
and ligand and ligand
field field electrostatics,
electrostatics, strong magnetoanisotropy
strong magnetoanisotropy is observed is resulting
observedinresulting
barriers in
to
barriers to magnetization relaxation and the observation
magnetization relaxation and the observation of single ion magnetism [8]. of single ion magnetism [8].
We
We have
have been
been interested
interested in in the
the coordination
coordination chemistry
chemistry of of redox-active
redox-active ligands,ligands, including
including those
those
in
in the arylazo family [9]. Arylazo ligands feature low-lying π* azo-centered molecular orbitals and
the arylazo family [9]. Arylazo ligands feature low-lying π* azo-centered molecular orbitals and
often
often exhibit
exhibit intense
intense visible
visible absorption
absorption bands
bandsresulting
resultingfrom fromelectronic
electronictransitions
transitionsinto intothese
theseorbitals.
orbitals.
The
The tridentate
tridentate 1-(2-pyridylazo)-2-phenanthrol
1-(2-pyridylazo)-2-phenanthrol (papl) (papl) ligand
ligand hashas been
been investigated
investigated since since the
the 1960s
1960s [10]
[10]
and we have recently taken another look at the coordination chemistry
and we have recently taken another look at the coordination chemistry of this structurally diverse of this structurally diverse
ligand
ligand and
and other
other derivatives.
derivatives. The The papl
papl structure
structure (Chart
(Chart 1) 1) contains
contains pyridyl,
pyridyl, azo, azo, and
and phenanthrol
phenanthrol
fragments
fragments and and is is susceptible
susceptible to to either reduction or
either reduction or oxidation.
oxidation. Of Of note,
note, first
first row
row transition
transition metal
metal
complexes containing papl exhibit very intense ligand-centered absorption
complexes containing papl exhibit very intense ligand-centered absorption bands in the visible region, bands in the visible
region, reversible
reversible cathodiccathodic electrochemistry
electrochemistry and we haveand we have recently
recently observedobserved
thermallythermally induced spin-
induced spin-crossover
crossover in Co(papl)
in Co(papl)2 [11,12]. Iron complexes containing other arylazo substituted ligands have alsohave
2 [11,12]. Iron complexes containing other arylazo substituted ligands also
recently
recently been shown to exhibit spin-crossover and there is the potential
been shown to exhibit spin-crossover and there is the potential to create multifunctional materials to create multifunctional
materials
using these using these
ligands ligands
with with interesting
interesting magnetic, magnetic,
optical andoptical and properties
electronic electronic properties
[13]. To date,[13]. To
there
date, there are no reported lanthanide ion complexes containing
are no reported lanthanide ion complexes containing papl. However, given the interest in both papl. However, given the interest in
both redox-active ligands and lanthanide ion complexes, we believe
redox-active ligands and lanthanide ion complexes, we believe the coordination chemistry of papl the coordination chemistry of
papl
with with lanthanide
lanthanide ions ions potentially
potentially has much
has much to offer
to offer multifunctional
multifunctional materials
materials research.
research. Herein,
Herein, we
we
present the preparation and characterization of three lanthanide complexes containing papl in
present the preparation and characterization of three lanthanide complexes containing papl in an
an
effort
effort to
to unearth
unearth the the details
details regarding
regarding the the electronic
electronic structures
structures and and photophysical
photophysical properties
properties in in these
these
interesting
interesting complexes.
complexes. We We also
also report
report onon the
the structural
structural properties
properties of of aa holmium
holmium complexcomplex withwith the
the
related
related ligand qapl. To our knowledge, this is the first report focused on the emission properties of
ligand qapl. To our knowledge, this is the first report focused on the emission properties of
homoleptic
homoleptic lanthanide
lanthanide complexes
complexes containing
containing arylazo
arylazo ligands
ligands and and also
also thethe first
first reported
reported lanthanide
lanthanide
complexes
complexes with with papl.
papl.

Chart 1.
Chart Arylazoligands
1. Arylazo ligandsused
used in
in the
the present
present study.
study.

2. Results
2. Results and
and Discussion
Discussion

2.1. Preparation
2.1. Preparation and
and Characterization
Characterization of
of Ln(papl)
Ln(papl)33 Ln
Ln ==Gd,
Gd,Tb,
Tb,Dy
Dyand
andHo(qapl)
Ho(qapl)33Complexes
Complexes
The Ln(papl)
The Ln(papl)33 complexes
complexes werewere easily
easily prepared
prepared by
by combination
combination ofof the
the appropriate
appropriate amount
amount of of
lanthanide nitrate
lanthanide nitrate salt
salt in
in methanol
methanol with
with aa chloroform
chloroform solution
solution containing
containing three
three equivalents
equivalents of of papl
papl
and triethylamine (Scheme 1). Stirring at room temperature precipitated out dark microcrystalline
and triethylamine (Scheme 1). Stirring at room temperature precipitated out dark microcrystalline
materials that
materials that are
are air/moisture
air/moisturestable.
stable.Unfortunately,
Unfortunately, multiple
multiple attempts
attempts to
to grow
grow single
single crystals
crystals of
of the
the
complexes for
complexes for X-ray
X-ray diffraction
diffraction experiments
experiments werewere unsuccessful. Often, microcrystalline
unsuccessful. Often, microcrystalline clusters
clusters oror
microspherical particles were formed by slow evaporation or diffusion experiments.
microspherical particles were formed by slow evaporation or diffusion experiments. However, it isHowever, it is
clear from the results of combustion analysis and ESI mass spectrometry that complexes
clear from the results of combustion analysis and ESI mass spectrometry that complexes 1–3 bear the 1–3 bear the
formulation Ln(papl)
formulation Ln(papl)33. .Dominant
Dominantpeakspeaksare
areobserved
observedbybyESI
ESI(Figures
(Figures S1–S6)
S1–S6) in
in all
all cases
cases at
at high m/z
high m/z
that represent [Ln(papl) H] + with isotope distributions that match the theoretical calculated isotopic
that represent [Ln(papl)33H] with isotope distributions that match the theoretical calculated isotopic
+

patterns; combustion analysis results are also consistent with this formulation (with the addition of
chloroform for Tb3+ complex only). The FT-IR and UV–Vis spectra of 1–3 are identical, and similar
Inorganics 2018, 6, 56 3 of 13

Inorganics 2018, 6, x FOR PEER REVIEW 3 of 13

patterns; combustion analysis results are also consistent with this formulation (with the addition of
electrochemical
chloroform for Tbdata are observed
3+ complex only).(videThe infra),
FT-IR and strongly UV–Vissuggesting
spectra thatof 1–31–3areshare similar
identical, structural
and similar
properties.
electrochemical It is likely that the molecular structure of complexes 1–3 consist of nine-coordinate Ln3+
Inorganics 2018, data
6, x FORare observed
PEER REVIEW (vide infra), strongly suggesting that 1–3 share similar 3structural of 13
ions in tricapped
properties. It is likely trigonal
that the prismatic
molecular geometries,
structure which have been
of complexes observed
1–3 consist previously for other
of nine-coordinate Ln3+
tridentate NNO
ions electrochemical ligands,
in tricapped trigonal where
data are prismatic each
observed (vide papl ligand
infra), strongly
geometries, is binding
whichsuggesting the
have been lanthanide
thatobserved ion through
1–3 share previously pyridyl
similar structuralfor other N,
azo Nproperties.
tridentate and NNO
anionic It isphenanthrol
likely that the molecular
ligands, whereOeach atoms papl
structure
[14]. Usingisof
ligand
complexes
abinding
related 1–3 consist
ligand, of nine-coordinate
qapl (Chart
the lanthanide ion 1)
Ln
[15], wepyridyl
through prepared
3+
N,
an ions in tricapped
analogous holmium trigonal
complex prismatic
Ho(qapl) geometries,
3 4, which which have been
provided observed previously
spectroscopic data that for other
was similar to
azo N and anionic phenanthrol O atoms [14]. Using a related ligand, qapl (Chart 1) [15], we prepared
tridentate
1–3,analogous NNO
including an ESI mass ligands, where each
spectrum papl
that 4,ligand
indicated is binding the lanthanide
m/z corresponding ion through
to [Ho(qapl) pyridyl N,
3H] . Single
+
an azo N and holmium complex
anionic phenanthrol Ho(qapl)
O atoms [14]. 3 Using which provided
a related ligand, spectroscopic
qapl (Chart 1)data [15], that was
we prepared similar
crystals
to 1–3, of 4
including were an obtained
ESI mass by slow
spectrum evaporation
that indicated of DCM/CH
m/z 3CN solutions of the precipitated
corresponding to [Ho(qapl) H] + . Single
an analogous holmium complex Ho(qapl)3 4, which provided spectroscopic data that was similar to 3
powder.ofThe
crystals molecular
4 were obtained structure
by slow ofevaporation
4 is shown in of Figure
DCM/CH 1 (crystallographic parameters can be found
1–3, including an ESI mass spectrum that indicated 3 CN solutionstoof[Ho(qapl)
m/z corresponding the precipitated
3H]+. Single powder.
in Table
The molecular
crystalsS1).ofstructure
There
4 wereisobtained
substantial
of 4 is shown
by slowdisorder
in Figure 1in(crystallographic
evaporation the ofstructure
DCM/CHthat was
parameters
3CN
modeled
solutions canof be using
thefound ingeometric
Table S1).
precipitated
constraints.
Therepowder. One of the
The molecular
is substantial ligands
disorder is
structure disordered
of 4 is shown
in the structure over
thatinwas the
Figure twofold crystallographic
1 (crystallographic
modeled using geometric parametersaxis and
can be essentially
constraints. is found
One of the
superimposed
ligands in isTable upon
S1).
disordered Thereitself.
over istheWhile
substantial
twofold R1 crystallographic
is a littleinhigh
disorder (0.1087),
the structure
axis and thatwe are
wasconfident
modeled
is essentially in thegeometric
using
superimposed overall
upon atomitself.
connectivity
constraints. and Onethe ofcoordinate
the ligands bond
is features
disordered over in the
the ordered
twofold parts of
crystallographic
While R1 is a little high (0.1087), we are confident in the overall atom connectivity and the coordinate the molecule.
axis and is The structural
essentially
data superimposed
bond confirms
features in the upon itself. While structure
thenine-coordinate
R1 is a little
ordered parts of the molecule. wehigh (0.1087), for
suggested
The structural
we Ln(papl)
are confident in the overall
3 complexes
data confirms and atom
given the
the nine-coordinate
connectivity
spectroscopic and the
similaritiesfor coordinate
between bond
complexesfeatures in the ordered parts of the molecule.
1–4 it is likely that the structures of complexes 1–3 areThe structural
structure we suggested Ln(papl) 3 complexes and given the spectroscopic similarities between
similar data to confirms
4. The the nine-coordinate
coordinate bonds in structure
4 are we suggested
shortest to the Ofor Ln(papl)
donor atoms3 complexes and given the
and longer to the Nazo and
complexes 1–4 it issimilarities
spectroscopic likely that the structures
between complexes of 1–4
complexes thatare
it is likely1–3 thesimilar to
structures of The
4. coordinate
complexes 1–3 arebonds
N quin donors (Figure 1). The bond distances in the ligand are similar to those in [Co(qapl)2]Cl reported
in 4 are shortest to the O donorbonds atoms
similar to 4. The coordinate in and
4 arelonger
shortest totothetheNOazo and atoms
donor Nquin and
donors
longer (Figure
to the 1).
NazoThe
andbond
earlier
distances and indicate a bound qapl phenolate anion [15].
Nquin in the ligand
donors (Figureare similar
1). The bond todistances
those inin [Co(qapl)
the ligand2 ]Cl are reported
similar to earlier
those inand indicate
[Co(qapl) 2]Cla bound qapl
reported
phenolate
earlieranion [15]. a bound qapl phenolate anion [15].
and indicate

Scheme 1. Preparation
Scheme
Scheme 1. of Ln(papl)
1. Preparation
Preparation of Ln(papl) 3 complexes.
of Ln(papl) 3 complexes. Ho(qapl) (4)was
Ho(qapl)3 3(4) wasprepared
prepared analogously
analogously using
using HoClHoCl
3 complexes. Ho(qapl)3 (4) was prepared analogously using HoCl3
3 3

hexahydrate
hexahydrate and and qapl
qapl (Chart
(Chart
hexahydrate and qapl (Chart 1). 1).
1).

Figure 1. Molecular structure of 4 (displacement ellipsoids at 30% probability). H atoms removed for
clarity. Complex 4 lies on a crystallographic twofold rotation axis and one of the qapl ligands is
Figure Molecular
1. Molecular
disordered aboutstructure
a twofoldof 4 (displacement
rotation ellipsoids
axis over two sites withatequal
30% occupancy.
probability).
probability). H atoms
In Figure one for
removed
1, only
clarity.
clarity. Complex
siteComplex lies
is shown4 for on on
the
4 lies a crystallographic
disordered twofold
ligand and
a crystallographic the rotation
atom
twofold axis
labels areand
rotation oneand
denoted
axis ofwith
the of ligands
qapl
suffix
one is disordered
“A”.qapl
the Unlabeled
ligands is
disordered about a twofold rotation axis over two sites with equal occupancy. In Figure 1, only one
site is shown for the disordered ligand and the atom labels are denoted with suffix “A”. Unlabeled
Inorganics 2018, 6, 56 4 of 13

about a twofold rotation axis over two sites with equal occupancy. In Figure 1, only one site is
shown for the disordered ligand and the atom labels are denoted with suffix “A”. Unlabeled atoms
in the figure and those in list below which are denoted by suffix “#” are related by the symmetry
operator (−x + 1, y, −z + 3/2). Relevant bond distances (Å) and angles (◦ ) [with standard uncertainties
(su) in brackets]: Ho(1)–O(1A), 2.122(11); Ho(1)–O(1)#1, 2.273(6); H(1)–O(1), 2.273(6); Ho(1)–N(2A),
2.555(10); Ho(1)–N(2)#1,
Inorganics 2018, 2.557(7); Ho(1)–N(2), 2.557(7); Ho(1)–N(3)#1, 2.596(8); Ho(1)–N(3),
6, x FOR PEER REVIEW 4 of 13
2.596(8); Ho(1)–N(3A), 2.737(12); N(1)–N(2), 1.308(8); C(1)–O(1), 1.283(10); N(1A)–N(2A), 1.303(11);
atoms in1.276(12).
C(1A)–O(1A), the figure and those in list below which
O(1A)–Ho(1)–O(1)#1, are denoted
84.3(4); by suffix “#” are related
O(1A)–Ho(1)–O(1), by O(1)#1–Ho(1)–O(1),
78.1(4); the symmetry
142.8(3);operator (−x + 1, y, −z + 3/2). Relevant bond distances (Å) and angles (°) [with standard uncertainties
O(1A)–Ho(1)–N(2A), 74.9(4); O(1)–Ho(1)–N(2A), 68.6(4); O(1A)–Ho(1)–N(2)#1, 143.5(4);
(su) in brackets]: Ho(1)–O(1A), 2.122(11); Ho(1)–O(1)#1, 2.273(6); H(1)–O(1), 2.273(6); Ho(1)–N(2A),
O(1)#1–Ho(1)–N(2)#1, 68.8(2); O(1)–Ho(1)–N(2)#1, 137.8(3); N(2A)–Ho(1)–N(2)#1, 121.2(4);
2.555(10); Ho(1)–N(2)#1, 2.557(7); Ho(1)–N(2), 2.557(7); Ho(1)–N(3)#1, 2.596(8); Ho(1)–N(3), 2.596(8);
O(1A)–Ho(1)–N(2),
Ho(1)–N(3A), 76.6(4);
2.737(12);O(1)#1–Ho(1)–N(2), 137.8(3); O(1)–Ho(1)–N(2),
N(1)–N(2), 1.308(8); C(1)–O(1), 1.283(10); N(1A)–N(2A), 68.8(2); N(2A)–Ho(1)–N(2),
1.303(11); C(1A)–
130.6(4);O(1A),
N(2)#1–Ho(1)–N(2), 106.9(4); O(1A)–Ho(1)–N(3)#1,
1.276(12). O(1A)–Ho(1)–O(1)#1, 84.3(4); O(1A)–Ho(1)–O(1),142.5(4); O(1)#1–Ho(1)–N(3)#1,
78.1(4); O(1)#1–Ho(1)–O(1),
131.2(2);142.8(3);
O(1)–Ho(1)–N(3)#1,
O(1A)–Ho(1)–N(2A), 77.3(3); N(2A)–Ho(1)–N(3)#1,
74.9(4); O(1)–Ho(1)–N(2A), 123.4; N(2)#1–Ho(1)–N(3)#1,
68.6(4); O(1A)–Ho(1)–N(2)#1, 143.5(4);
63.3(2); O(1)#1–Ho(1)–N(2)#1,
N(2)–Ho(1)–N(3)#1, 68.8(2); O(1)–Ho(1)–N(2)#1,
68.3(2); 137.8(3); N(2A)–Ho(1)–N(2)#1,
O(1A)–Ho(1)–N(3), 121.2(4); O(1A)– 77.3(3);
82.4(4); O(1)#1–Ho91)–N(3),
Ho(1)–N(2), 131.2(2);
O(1)–Ho(1)–N(3), 76.6(4); O(1)#1–Ho(1)–N(2),
N(2A)–Ho(1)–N(3), 137.8(3);
143.2(3);O(1)–Ho(1)–N(2),
N(2)#1–Ho(1)–N(3),68.8(2); 68.3(2);
N(2A)–Ho(1)–N(2),
N(2)–Ho(1)–N(3),
130.6(4); N(2)#1–Ho(1)–N(2), 106.9(4); O(1A)–Ho(1)–N(3)#1, 142.5(4); O(1)#1–Ho(1)–N(3)#1, 131.2(2);
63.2(2); N(3)#1–Ho(1)–N(3), 93.1(3); O(1A)–Ho(1)–N(3A), 131.6(4); O(1)#1–Ho(1)–N(3A),
O(1)–Ho(1)–N(3)#1, 77.3(3); N(2A)–Ho(1)–N(3)#1, 123.4; N(2)#1–Ho(1)–N(3)#1, 63.3(2); N(2)–Ho(1)–
89.8(5); N(3)#1,
O(1)–Ho(1)–N(3A), 78.4(4); N(2A)–Ho(1)–N(3A),
68.3(2); O(1A)–Ho(1)–N(3), 82.4(4); O(1)#1–Ho91)–N(3), 60.8(3);
77.3(3); N(2)#1–Ho(1)–N(3A),
O(1)–Ho(1)–N(3), 131.2(2); 74.3(4);
N(2)–Ho(1)–N(3A), 130.7(4); N(3)#1–Ho(1)–N(3A), 69.3(4); N(3)–Ho(1)–N(3A),
N(2A)–Ho(1)–N(3), 143.2(3); N(2)#1–Ho(1)–N(3), 68.3(2); N(2)–Ho(1)–N(3), 63.2(2); 142.6(4).
N(3)#1–Ho(1)–
N(3), 93.1(3); O(1A)–Ho(1)–N(3A), 131.6(4); O(1)#1–Ho(1)–N(3A), 89.8(5); O(1)–Ho(1)–N(3A), 78.4(4);
The electronic spectra of
N(2A)–Ho(1)–N(3A), the N(2)#1–Ho(1)–N(3A),
60.8(3); uncoordinated papl ligand
74.3(4); and complexes
N(2)–Ho(1)–N(3A), 130.7(4);1–3 are illustrated
N(3)#1–
in Ho(1)–N(3A), 69.3(4); N(3)–Ho(1)–N(3A), 142.6(4).
Figure 2. For the uncoordinated papl ligand, a keto-enol tautomerization exists (Scheme 2),
with the iminoquinone
The electronictautomer being
spectra of the the major component,
uncoordinated papl ligand and ascomplexes
found for1–3 related compounds
are illustrated in [16].
In its absorption spectrum,
Figure 2. For ligand centered
the uncoordinated π–π*
papl ligand, transitions
a keto-enol (225–350 nm)
tautomerization are(Scheme
exists observed, together
2), with the with
a broad iminoquinone
band (350–525 nm) with
tautomer beinga the
higher
majorenergy shoulder
component, (~400
as found fornm) in the
related visible region.
compounds [16]. In The
its latter
feature absorption
is assigned spectrum,
to the ligand centered π–π*
n-π* transitions oftransitions (225–350[11].
the azo moiety nm) are Theobserved, together with
three Ln(papl) 3
a
complexes
broad band (350–525 nm) with a higher energy shoulder (~400 nm) in the visible
present nearly identical UV-vis spectra, which feature ligand centered π–π* transitions (225–360 nm), region. The latter
feature is assigned to the n-π* transitions of the azo moiety [11]. The three Ln(papl)3 complexes
and two overlapping broad bands with a higher energy shoulder (375–600 nm) in the visible region,
present nearly identical UV-vis spectra, which feature ligand centered π–π* transitions (225–360 nm),
assigned andastwo
intraligand
overlappingcharge transfer
broad bands withtransitions (ILCT)
a higher energy [11,17].
shoulder (375–600Thenm) red shift
in the observed
visible region, for the
transitions in the
assigned as visible region
intraligand upon
charge the complexation
transfer transitions (ILCT)of[11,17].
the lanthanide
The red shift ions is in line
observed for with
the what
has been reported
transitions in for other region
the visible papl complexes with divalent
upon the complexation transitionions
of the lanthanide metalis inions [11],what
line with as well
has as for
beencomplexes
lanthanide reported for other
with papl complexes
similar with divalent
azo-type ligands transition
[18]. This effectmetal ions
arises upon[11],coordination,
as well as for as only
lanthanide complexes with similar azo-type ligands [18]. This effect arises upon coordination, as only
the enolate form of the ligand with the azo-type moiety exists with extended conjugation and a
the enolate form of the ligand with the azo-type moiety exists with extended conjugation and a
characteristic low lying azo-centered π*-orbital, which is also supported by the intense color of the
characteristic low lying azo-centered π*-orbital, which is also supported by the intense color of the
complexes [9,11,16,18].
complexes [9,11,16,18].

Figure 2. Electronic spectra of papl, Gd(papl)3 (1), Dy(papl)3 (2), Tb(papl)3 (3) in CH2Cl2 at room
Figure 2. Electronic spectra of papl, Gd(papl)3 (1), Dy(papl)3 (2), Tb(papl)3 (3) in CH2 Cl2 at
temperature.
room temperature.
 Inorganics 2018, 6, x FOR PEER REVIEW 5 of 13
Inorganics 2018,
Inorganics 2018, 6,
6, 56
x FOR PEER REVIEW 55of
of 13
13
Inorganics 2018, 6, x FOR PEER REVIEW 5 of 13

Scheme 2. Keto-enol tautomerization for the papl ligand showing intramolecular proton transfer.
2. Keto-enol tautomerization
Scheme 2.
Scheme tautomerization for the
the papl ligand showing
papl ligand showing intramolecular
intramolecular proton
proton transfer.
transfer.
Scheme 2.Keto-enol
Keto-enol tautomerization for
for the papl ligand showing intramolecular proton transfer.
2.2. Electrochemical and Variable Temperature Magnetic Susceptibility Data
2.2.
2.2. Electrochemical
2.2.Electrochemical
Electrochemical and
and Variable
and Variable
Variable Temperature
Temperature
Temperature Magnetic
Magnetic Susceptibility
Magnetic Susceptibility Data
Susceptibility Data
We have previously described the redox-activity of papl, inData the uncoordinated form and when
We
We have
have
coordinated previously
previously
We havetopreviously described
described
transitiondescribed the
the redox-activity
redox-activity
metal ions [11]. The anticipated of
of papl,
papl,
redox
papl, in
in the
in thethe uncoordinated
uncoordinated
behavior of papl is
uncoordinated form
form and when
andwhen
summarized
form and whenin
coordinated
coordinated
Scheme 3. The
coordinated to
to transition
to transition
electrochemical
transition metal
metal
metal ions ions [11].
properties
ions The
[11]. The anticipated
anticipated
of 1–3 redox behavior
redox behavior
were investigated
anticipated redox behaviorby CV of
ofand
of papl
paplDPV
papl is summarized
isissummarized
summarized
and the resultsinin
in
Scheme
Scheme
are shown
Scheme 3.3.The
3. The electrochemical
electrochemical
in Figures
The electrochemical properties
3–5 for 1properties
and all data
properties offor
of were
1–31–3
1–3 were investigatedby
investigated
is summarized
investigated byTable
by
in CVand
CV
CV and
and DPVand
DPV
1 (cyclic
DPV and
and
andthethe
the results
results
differential
results
are
are shown
shown
pulse
are in
in
voltammograms
shown Figures
inFigures
Figures 3–53–5
3–5 forfor
for
for and
2 111and
and all
aredata
and3 all data for 1–3
for
provided isFigures
1–3inis summarized
summarized
summarized S7–S12). inTable
in
in Table
Table
All three111(cyclic
(cyclic
(cyclic
complexesand differential
anddifferential
and differential
share very
pulse
pulse voltammograms
voltammograms
similar
pulse electrochemicalfor
voltammograms for 2 and
22 and
properties,
for 3
and 33 areare provided
provided
which in
resultin
fromFigures
Figures
Figures S7–S12).
S7–S12). All
ligand-centered
S7–S12). All three
Allredox complexes
threecomplexes
three complexesshare
processes. shareanodic
share
Over very
very
very
similar
similar
similar electrochemical
electrochemical
electrochemical
potentials, properties,
irreversible properties,
waves are which
properties, which result
found result
at highfrom
from ligand-centered
ligand-centered
ligand-centered
potentials (>+0.9 V,redox redox
redox processes.
processes.
processes.
vs. Ag/AgCl), Over anodic
Overresulting
Over
likely anodic
anodic
potentials,
potentials,
potentials, irreversible
from papl irreversible
irreversibleas
oxidation, waves
waves
waves
observed are
are found
are found
found at
in related high
at high potentials
potentials
potentials
M(papl) (>+0.9
(>+0.9
2 complexes V,
(>+0.9[11]. vs.
V, vs.
V, vs.TwoAg/AgCl),
Ag/AgCl),
Ag/AgCl), likely resulting
likelyresulting
likely
quasi-reversible resulting
cathodic
from
from
wavespaplareoxidation,
papl
papl observed as
oxidation, asobserved
at observed in
potentials in related
beyond M(papl)
related−1.0
M(papl)
V (vs.22 complexes
complexes
Ag/AgCl) for [11].
[11]. Two
Two
each quasi-reversible
ofquasi-reversible
the complexes, cathodic cathodic
which are
waves
waves are
are observed
observed
observed at
at
at potentials
potentials
potentials beyond
beyond
beyond − 1.0
−1.0 V (vs. Ag/AgCl)
Ag/AgCl)
Ag/AgCl)
assigned to ligand centered reduction processes. Complexes 1 and 3 exhibit a third irreversible for
for
for each
each
each ofof
of the
the
the complexes,
complexes,
complexes, which
which are
are
assigned
process to
assigned toligand
to
at ligand
ligand
very centered
centered
centered
negative reduction
reduction
reduction
potentials processes.
processes.
(>−1.8 Complexes
V) Complexes
Complexes
that 1 and
is only 3andexhibit
11 observed
and a in
33 exhibitthird
exhibit aairreversible
the third
third process
irreversible
irreversible
differential pulse
atprocess
very negative
process atat very
voltammogram. verypotentials
negative
negative
In M(papl) (> 2− 1.8 V) that
potentials
potentials
complexes (>−1.8is only
the observed
V) that
frontier is onlyin the
only
molecular differential
observed
observed
orbital in
in the
structure pulse
the voltammogram.
isdifferential
differential
nearly pulse
pulse
exclusively
In M(papl)
voltammogram.
voltammogram.
papl 2 complexes
in character, Inand
In the
M(papl)
M(papl)
similarfrontier
complexes
22 complexes molecular
behavior the orbitalmolecular
frontier
is anticipated structure
for 1–3. is
molecular nearly
orbital
orbital exclusively
structure
structure isisnearly
nearly in character,
papl exclusively
exclusively
and similar
paplin
papl behavior
incharacter,
character,and is anticipated
and similar
similar behavior for 1–3.
behavior is anticipated for 1–3. 1–3.

Scheme 3. Potential redox-activity anticipated for papl.

Scheme 3.
Scheme
Scheme 3. Potential
3. Potential redox-activity
Potential redox-activity
redox-activity anticipated
anticipatedfor
anticipated forpapl.
for papl.
papl.

Figure CV
3. 3.
Figure ofof
CV 1 in CH
1 in 2 Cl
CH 2 (containing
2Cl
ca. 0.5 M Bu4 NPF
2 (containing ca. 0.5 M Bu 6 ;6;scan
4NPF scanrate
rate200
200mV/s).
mV/s).
Figure 3. CV of 1 in CH2Cl2 (containing ca. 0.5 M Bu4NPF6; scan rate 200 mV/s).
Figure 3. CV of 1 in CH2Cl2 (containing ca. 0.5 M Bu4NPF6; scan rate 200 mV/s).
 Inorganics 2018, 6, x FOR PEER REVIEW 6 of 13

Inorganics 2018, 6, 56
x FOR PEER REVIEW 66 of
of 13

Figure 4. Anodic DPV of 1 in CH2Cl2 with a scan rate of 50 mV/s.

Figure 4. Anodic DPV of 1 in CH2 Cl2 with a scan rate of 50 mV/s.
Figure 4. Anodic DPV of 1 in CH2Cl2 with a scan rate of 50 mV/s.

Figure 5. Cathodic DPV of 1 in CH2 Cl2 with a scan rate of 50 mV/s.

Figure 5. Cathodic DPV of 1 in CH2Cl2 with a scan rate of 50 mV/s.

Figure 5. Cathodic DPV of 1 in CH2Cl2 with a scan rate of 50 mV/s.

Table1.1.Electrochemical
Table Electrochemicalproperties
propertiesofof1–3
1–3(vs.
(vs.Ag/AgCl).
Ag/AgCl).

Compound
CompoundTable 1. Electrochemical
E1/2E1/2 (Anodic)
(Anodic) properties of 1–3E1/2(vs. Ag/AgCl).
E1/2 (Cathodic)
(Cathodic)

Compound1 1 1.21.2 (irr),

E(irr), 0.9 (irr) −1.2 (qr),−1.2
0.9 (irr)
1/2 (Anodic)
−1.5(qr),
E(qr), −1.5
−1.8(qr),
(irr) −1.8 (irr)
1/2 (Cathodic)
2 2 1.21.2
(irr), 0.9 (irr)
(irr), 0.9 (irr) −1.2 (qr),−1.2
−1.4(qr),
(qr) −1.4 (qr)
1 1.21.2 (irr),
1.0 0.9 (irr) −1.2 (qr),
(qr),−1.5
−1.9(qr),
(irr)−1.8 (irr)
3 3 (irr),
1.2 (irr), 1.0 (irr) −1.2 (qr),−1.2
(irr) −1.5 (qr), −1.5 (qr), −1.9 (irr)
2 1.2 (irr), 0.9 (irr) −1.2 (qr), −1.4 (qr)
3
Variable temperature magnetic 1.2 (irr), 1.0 (irr) experiments
susceptibility −1.2 (qr), −1.5 (qr),
were −1.9 (irr)for all three
conducted
Variable temperature magnetic susceptibility experiments were conducted for all three complexes
complexes over a temperature range of 300-2 K at an external field of 2000 Oe on a Quantum Design
over Variable temperature
a temperature range ofmagnetic
300-2 K atsusceptibility
an external field experiments
of 2000 Oe were
on aconducted
Quantum Design for all PPMS
three
PPMS (vibrating sample magnetometer option) for 1 and on a Quantum Design MPMS squid
complexessample
(vibrating over a magnetometer
temperature range option)of 300-2
for 1 Kand at on
an aexternal
Quantum field of 2000
Design Oe onsquid
MPMS a Quantum Design
magnetometer
magnetometer for 2 and 3. The data obtained from samples of 1–3 (Figure 6) support the formulation
PPMS
for 2 and(vibrating sample
3. The data magnetometer
obtained from samples option)
of 1–3for 1 and6) on
(Figure a Quantum
support Design MPMS
the formulation squid
as Ln(papl) 3,
as Ln(papl)3, with free-ion type magnetism characteristic of the Gd(III), Dy(III), or Tb(III) 8 terms
6 (8S7/2 ,
magnetometer
with for 2magnetism
free-ion type and 3. The data obtained from
characteristic of thesamples
Gd(III),ofDy(III),
1–3 (Figure 6) support
or Tb(III) termsthe ( Sformulation
7/2 , H ,
6H15/2, or 7F6) exhibiting typical χmT values at 300 K of 7.6, 13.3, and 10.0 cm3 K mol −1 for 15/2
1–3,
as 7Ln(papl)
or 3, withtypical
F6 ) exhibiting free-ionχm type magnetism
T values at 300 characteristic
K of 7.6, 13.3, of andthe10.0 cm3 K
Gd(III), mol−1or
Dy(III), forTb(III) terms (8S7/2,
1–3, respectively.
respectively. At low temperatures, there are observed minor deviations
6H15/2, or 7F6) exhibiting typical χmT values at 300 K of 7.6, 13.3, and 10.0 cm3 K mol−1 for 1–3,
from the above χmT values,
At low temperatures, there are observed minor deviations from the above χm T values, primarily 2
primarily 2 and 3, indicating depopulation of Stark sublevels at these lower temperatures.
respectively.
and At low
3, indicating temperatures,
depopulation theresublevels
of Stark are observedat theseminor deviations
lower temperatures. from the above χmT values,
Magnetization versus
Magnetization versus field experiments (Figure 7) at low temperature (2K) were also performed on
primarily
field 2 and (Figure
experiments 3, indicating depopulation
7) at low temperatureof(2K) Stark
were sublevels at theseonlower
also performed temperatures.
all three complexes.
all three complexes. Preliminary AC SQUID experiments indicated no out-of-phase peaks at zero
Magnetization
Preliminary ACversus
SQUID field experiments
experiments (Figure 7)
indicated noatout-of-phase
low temperature peaks(2K) wereexternal
at zero also performed
field or onin
external field or in an external DC field; therefore, 1–3 do not exhibit slow relaxation of the
all external
an three complexes.
DC field; Preliminary
therefore, 1–3 ACdoSQUID experiments
not exhibit indicated
slow relaxation of no
theout-of-phase
magnetization, peaks at zero
which is a
magnetization, which is a characteristic feature of lanthanide single ion magnets (SIMs).
external fieldfeature
characteristic or in of anlanthanide
external DC single field;
ion therefore,
magnets (SIMs).1–3 do not exhibit slow relaxation of the
magnetization, which is a characteristic feature of lanthanide single ion magnets (SIMs).
 Inorganics2018,
Inorganics
Inorganics 2018, 6,xx56
2018,6,6, FOR
FORPEER
PEERREVIEW
REVIEW 7ofof13
77 of 13
13

15
15

mol-1-1
12.5
12.5

cm33KKmol
10

χχmmTT//cm
10

7.5
7.5

55
00 100
100 200
200 300
300
Temperature
Temperature//KK
Figure
Figure6.6.Variable
Figure Variabletemperature
Variable temperaturemagnetic
temperature magneticsusceptibility
magnetic susceptibilitydata
susceptibility data(ZFC/FC)
data (ZFC/FC)for
(ZFC/FC) for111(red),
for (red),222(green),
(red), (green),and
(green), and333
and
(blue)
(blue)(external
(blue) (external field
(external field 2000 Oe).
field 2000 Oe).

88
77
66
55
M/Nββ
M/N

44
33
22
11
00
00 20000
20000 40000
40000 60000
60000 80000
80000
HH//Oe
Oe
Figure7.7.
Figure
Figure Magnetizationversus
7.Magnetization
Magnetization versusfield
versus field(0–9000
field (0–9000Oe)
(0–9000 Oe)for
Oe) for111(red
for (redline),
(red line),222(green
line), (greenline)
(green line)and
line) and333(blue
and (blueline)
(blue line)atat
line) at222K.
K.
K.

2.3.
2.3.Emission
2.3. EmissionSpectroscopy
Emission Spectroscopyofof
Spectroscopy ofpapl
papland
papl and1–3
and 1–3
1–3
Figure
Figure888shows
Figure showsthe
shows theemission
the emission
emission profiles
profiles
profiles of the
ofofthe papl
the papl
papl ligand
ligand
ligand in CH
ininCH 2Cl
CH2Cl 2at
22Clat2room
at room
room temperature
temperature
temperature and atat77
andand at
77
K.77The
K. The emission
K. The emission
emission spectra
spectra of
spectraofthe
of papl
thethe papl
papl ligand obtained
ligand
ligand obtained
obtained while screening
while
while screening
screening different
different
different excitation
excitationwavelengths
excitation wavelengths
wavelengths
(λ(λ = 257
= 257to 600
to 600nm)nm) are presented
are presented in Figures
in Figures S13–S15.
S13–S15. Emission
Emission is
(λexc = 257 to 600 nm) are presented in Figures S13–S15. Emission is not observed upon excitation
exc
exc not
is observed
not observedupon uponexcitation
excitationof
of
the
of free
the papl
free paplligand
ligand in the
in thelowest
lowest energy
energy absorption
absorption band
band
the free papl ligand in the lowest energy absorption band (Figure S14). This observation was(Figure
(Figure S14).
S14). This
Thisobservation
observation was
was
previously
previouslyreported
previously reportedfor
reported forazo-type
for azo-typecompounds
azo-type compoundsand
compounds anditititwas
and wasexplained
was explainedby
explained bythe
by thegeneration
the generationof
generation ofaaavery
of verypolar
very polar
polar
excited
excited state
state relaxing
relaxing non-radiatively,
non-radiatively, associated
associated with
with photochemical
photochemical
excited state relaxing non-radiatively, associated with photochemical isomerization [19]. However, isomerization
isomerization [19].
[19].However,
However,
excitation
excitationatat
excitation athigher
higherenergy
higher energyleads
energy leadsto
leads todual
to dualemission
dual emissionatat
emission atroom
roomtemperature
room temperature(Figure
temperature (Figure888(orange
(Figure (orangeline)
(orange line)and
line) and
and
Figures
FiguresS13
Figures S13and
S13 andS14):
and S14):aaahigh
S14): highenergy
high energyband
energy band(325–425
band (325–425nm)
(325–425 nm)(with
nm) (withvibronic
(with vibronicstructure
vibronic structureof
structure ofsimilar
of similarenergy
similar energy
energy
(λ
(λ max===
(λmax
max 365,
365,384,
365, 384,419,
384, 419,and
419, and442
and 442nm),
442 nm),and
nm), andaaalower
and lowerenergy
lower energyband
energy band(425–600
band (425–600nm)
(425–600 nm)also
nm) alsofeaturing
also featuringvibronic
featuring vibronic
vibronic
structure
structure of
structure of similar
of similar energy
similar energy (λmax(λ = 490,
max ==490,
max 517,
490,517, and
517,and 560
and560 nm).
560 nm). At
nm). At low
Atlow temperature
low temperature
temperature (77 (77 K),
(77 K), the
K), the emission
the emission
emission
profile
profile of the papl ligand consists of a broad band (550 nm–750 nm) without vibronic structurewith
profile of
of the
the papl
papl ligand
ligand consists
consists of
of aabroad
broad band
band (550
(550 nm–750
nm–750 nm)
nm) without
without vibronic
vibronic structure
structure with
with
λλλmax = 645
= nm.
645 nm.This very
This interesting
very interestingand very
and complex
very complex emission profile
emission of
profile
max= 645 nm. This very interesting and very complex emission profile of the free ligand results from
max the free
of ligand
the free results
ligand from
results
aafrom
combination
a combination
combination of
of multiple
multiple functionalities
of multiple in
functionalities
functionalities in its
instructure
its its structure
structure (e.g., azoaryl,
(e.g.,
(e.g., azoaryl,
azoaryl, phenanthrol
phenanthroland
phenanthrol andpyridyl
and pyridyl
pyridyl
Inorganics 2018, 6, 56 8 of 13
Inorganics 2018, 6, x FOR PEER REVIEW 8 of 13
Inorganics 2018, 6, x FOR PEER REVIEW 8 of 13

moieties,
moieties, including
including keto-enol
keto-enol forms),
forms), each
each of of which
which maymay displaya specific
display a specificcharacteristic
characteristic behavior
behavior upon
uponmoieties, includingon
excitation. keto-enol systems
forms), each of which may display a specific
nm)characteristic behavior
excitation. Based onBased
related related
systems [19], the [19],high
the high energy
energy band
band (325–425
(325–425 nm) isisaalocally
locally excited
excited (LE)
upon excitation. Based on related systems [19], the high energy band (325–425 nm) is a locally excited
state(LE) state together
together
(LE) with
state
with radiative
radiative
together with
relaxation
relaxation
radiative from from
relaxation
a mixing
a from
mixing
a ofofhigher
mixing
higher SS and
of higherand
S
T.
T.The
and The
T.
emission
Theemission of complex
emission of
of complex
complex 1
1 confirms the triplet emission energy (see below). The lower energy band (425–600 nm) is assigned
confirms the triplet emission
1 confirms thechange energy
triplet emission (see below). The lower energy band (425–600 nm)
energy (see below). The lower energy band (425–600 nm) is assigned is assigned to
to intramolecular transfer states.
intramolecular change transfer
to intramolecular states. states.
change transfer

Figure 8. Emission
Figure 8. Emissionprofile of the
profile papl
of the paplligand
ligandin in
CH 2 Cl
CH 2 2atatroom
2Cl roomtemperature
temperature (orange
(orange line, max==365
λmax
line, λ 365 (sh),
419Figure
384, (sh), (sh), 8.
490 Emission
(sh), 517,profile
544, of
andthe
560 papl ligand
(sh) nm; in
sh CH
= 2Cl2 at room temperature (orange line, λmax = 365
shoulder) and at 77 K (red
384, 419 (sh), 490 (sh), 517, 544, and 560 (sh) nm; sh = shoulder) and at 77 K (red line, λmaxline, λ = 645
max = 645 nm)
(λexcnm) (sh),
= 257 nm;
(λexc 384, 419 (sh), 490 (sh),
concentration
= 257 nm; 1 ×517,
concentration 1−
10 ×544,
510M). M). 560 (sh) nm; sh = shoulder) and at 77 K (red line, λmax = 645
−5and

nm) (λexc = 257 nm; concentration 1 × 10−5 M).

Figure 9 displays the emission profiles of 1 in CH2Cl2 at room temperature and at 77 K. The
Figure 9 displays the emission profilesprofiles
of 1 in CH of 12 Cl at room
2Cl2 attemperature and at and 77 K. The emission
emissionFigurespectra9 of displays
1 obtained the while
emission screening different in2excitation
CH room temperature
wavelengths (λexc = 257 toat600 77nm)
K. The
spectra of 1
emission obtained
spectra while
of 1 screening
obtained while different
screening excitation
different
are presented in Figure S16. The emission profiles for 2 and 3 are shown in Figure wavelengths
excitation (λ
wavelengths exc = (λ257
10 and Figures are
exc = to
257 600
to 600nm)nm)
presentedare
S18–S26. presented
in Figure
In complexes in
S16. TheFigure S16.
emission
of Gd(III), The emission
the profiles
high energy profiles
for 2ofand for 2 and
3 are shown
the excited 3 are shown
level ofinGd(III) in
Figureion Figure
10(6and 10 andcm
Figures
P7/2, 32,200 Figures
S18–S26.
−1)
S18–S26.
In complexes
renders energy In complexes
of Gd(III),
transfer the of
high
from Gd(III),
theenergy the
ligand of high energy
the state
triplet excited of the
level
to the excited
metalof Gd(III)level of Gd(III)
6
ion ( P7/2
state impossible, ion (
, 32,200
while
6P7/2, 32,200
− 1
cm )ion
the heavy cm−1)
renders
energy renders
transfer
effect energy
promotes from thethetransfer from the
ligand triplet of
phosphorescence ligand
state triplet
the to state
the metal
ligand. to the
Therefore, metal
statethese state
impossible, impossible,
complexes while while
the heavy
are usually the heavy
used ion ion
to effect
effect
estimate promotes the phosphorescence of the ligand. Therefore, these complexes are usually used to
promotes thethe triplet energies ofof
phosphorescence ligands [20]. Thus,
the ligand. the lowest
Therefore, these triplet energy ofare
complexes theusually
papl ligand used(17,000
to estimate
estimate the triplet energies of ligands [20]. Thus, the lowest triplet energy of the papl ligand (17,000
cm−1 orenergies
the triplet 590 nm) of
cm−1 orof590
was
nm) was
determined
ligands determined
from the
[20]. Thus, from
short-wavelength
thethelowest triplet energy
short-wavelength
band edge of edge
bandpapl
theof papl
the phosphorescence
ligand
of theno
(17,000 cm−1
phosphorescence
spectrum
or 590 nm) complex
was determined 1 at 77
from K. As is the case for the uncoordinated ligand, emission is
spectrum
observed of complex
in complexes at 77the
1–31 when K. short-wavelength
As isinthe
excited the case
lowest
band
forenergy
the edge of thepapl
uncoordinated
absorption band
phosphorescence
ligand,S16,
(Figures no S18 spectrum
emission
and is
of complex
observed 1 at in77complexes
K. As is 1–3 thewhen
case excited
for theinuncoordinated
the1–3lowest papl ligand,band no emission is S18
observed
S19). When excited at higher energies, complexes showenergy absorption
only ligand-based (Figures
emission S16,
at both roomand
in complexes
S19). When when excited
1–3 excited at higher in the lowest
energies, complexesenergy 1–3 absorption
show only band (Figures
ligand-based S16, atS18
emission bothandroom S19).
temperature and 77 K (Figures 9 and 10 and Figures S16, S18 and S19). The characteristic narrow-line
When excited
temperature
emission at higher
from and
the excited77 energies,
K levels ofcomplexes
(Figures 9 and 10 and 1–3 show
Tb(III) and Dy(III)Figures ions only
S16, [21] isligand-based
S18 and S19). The
not observed. The emission
characteristic at both of room
narrow-line
triplet energy
the papl ligand (17,000 cm ) is lower than the excited levels of Tb(III) ( D4, 20,400 cm ) and Dy(III) of
emission
temperature and from
77 K the excited
(Figures −1 9levels
and of
10 Tb(III)
and and
Figures Dy(III)
S16, ions
S18 [21]
and is not
S19). 5 observed.
The The
characteristic
−1 triplet energy
narrow-line
(4F9/2the papltheligand (17,000 cm−1of
) is lower than
and the excited levels of
is Tb(III) by( D
5 4, 20,400 cm−1) and Dy(III)
emission from
, 20,600 cm excited
−1 ) [20], levels
therefore, Tb(III)
these lanthanide Dy(III)
ions ions
are not [21] not observed.
sensitized the paplThe triplet energy of
ligand.
( F9/2, 20,600 cm ) [20],
4 −1
−1therefore, these lanthanide ions are not sensitized 5 by the papl ligand. −1
the papl ligand (17,000 cm ) is lower than the excited levels of Tb(III) ( D4 , 20,400 cm ) and Dy(III)
(4 F9/2 , 20,600 cm−1 ) [20], therefore, these lanthanide ions are not sensitized by the papl ligand.

Figure 9. Emission profile of 1 in CH2 Cl2 at room temperature (blue line, λmax = 419 nm) and at 77 K
(red line, λmax = 652 nm) (λexc = 309 nm) (concentration 4 × 10−5 M).
Inorganics 2018, 6, x FOR PEER REVIEW 9 of 13

Figure 9. Emission profile of 1 in CH2Cl2 at room temperature (blue line, λmax = 419 nm) and at 77 K
(red2018,
Inorganics max = 652 nm) (λexc = 309 nm) (concentration 4 × 10−5 M).
line,6,λ56 9 of 13

Figure 10. Emission profile of 2 (yellow line) and 3 (green line) in CH2 Cl2 at RT; λexc = 309 nm. Dashed
Figure 10. Emission profile of 2 (yellow line) and 3 (green line) in CH2Cl2 at RT; λexc = 309 nm. Dashed
red line is CH2 Cl2 .
red line is CH2Cl2.

Complex
Complex 11in inCH CH22Cl Cl22 solution
solution at at room
room temperature
temperature (Figure (Figure 9, 9, blue
blueline)
line)exhibits
exhibitsligand-based
ligand-based
emission
emission at 419 419 nm nmwhen whenexcited
excitedat at higher
higher energies
energies (257(257nm nmto 394 to nm)—this
394 nm)—this state could
state could be a
be a higher
higher
triplet triplet
level oflevel of the ligand
the ligand or a mixing
or a mixing between between
a higher a higher
singlet singlet and a higher
and a higher triplet
triplet (in the (in
casetheof
case of incomplete intersystem crossing at room temperature)
incomplete intersystem crossing at room temperature) or another type of excited state (e.g., or another type of excited state
(e.g., intramolecular
intramolecular chargecharge transfer)transfer)
capable capable of relaxing
of relaxing radiatively.
radiatively. The energy Theofenergy of this
this level level is
is estimated
estimated at 24,200 cm −1 (Figure S17). An enhancement of the emission intensity of this band with
at 24,200 cm (Figure S17). An enhancement of the emission intensity of this band with respect to the
−1

respect
ligand is toalso
the observed
ligand is also observed3],
for [Gd(papl) foras[Gd(papl)
well as the 3 ],disappearance
as well as the of disappearance
the emission of bandtheatemission
425–600
band
nm. Theat 425–600
Tb(III) nm. The Tb(III)
and Dy(III) and Dy(III)
complexes exhibit complexes
very weak exhibit very weak
ligand-based ligand-based
emission: emission:
the high-energy
the
bandhigh-energy
decreases with bandrespect
decreasesto thewith respect
Gd(III) analog to the
andGd(III)
the papl analog and the
free ligand, papl
while thefree ligand, while
low-energy band
the low-energy
is the main feature bandofis theirthe main feature
emission of their
spectra. emissionthe
However, spectra.
emissionHowever, the emission
from this state(s) isfrom this
partially
state(s)
quenched is partially
in the Tb(III)quenched analog, in and
the Tb(III)
almostanalog, and almostintotally
totally quenched quenched
the Dy(III) analog, in the Dy(III)
vs. the paplanalog,
ligand
vs.
andtheitspapl ligand
Gd(III) and its As
complex. Gd(III) complex.
mentioned As mentioned
before, the energy before, the energy
gap between thegap between
lowest energy the excited
lowest
6 8
energy
(emissive)excitedstate(emissive)
of the metal state
ionofand
thethe metal ion and
ground statetheforground
Gd(III)stateions (for → 8S7/2ions
Gd(III)
6P7/2 ( P7/2
) equals 32 →
200 Scm7/2−1),
equals 32,200 cm − 1 , which is much higher than the energy of the excited state exhibiting emission at
which is much higher than the energy of the excited state exhibiting emission at room temperature
room temperature in 1 (24,200 −
cm the 1 ), thus explaining the absence
in 1 (24,200 cm ), thus
−1 explaining absence of the quenching of of
thethe quenching
emission of the
for this emission
state [20]. In
for
thethis
casestate [20]. In
of Dy(III) and the case of
Tb(III) Dy(III) and
complexes 2 andTb(III)
3, thecomplexes and 3, the quenching
quenching2 mechanism is not clear.mechanism
The presence is
not clear. The presence of Dy(III) or Tb(III) ions could contribute to
of Dy(III) or Tb(III) ions could contribute to the quenching of the ligand-based emission through the the quenching of the ligand-based
emission
enhancement through the enhancement
of inter-system crossing of (ISC)
inter-system
to the lowestcrossing (ISC)
triplet stateto of
thethelowest triplet state
papl ligand, of the
as expected
papl
based ligand,
on the as heavy
expected ionbased
effect.onThis
the heavy
latter ion
stateeffect. This latter
is thermally state is thermally
deactivated at roomdeactivated
temperature, at
room temperature, presumably by vibrational quenching, but it
presumably by vibrational quenching, but it is emissive at 77 K, as proven by the emission profile of is emissive at 77 K, as proven by
the
theemission
Gd(III) complexprofile of the Gd(III)
(Figure 9 andcomplex
Figure S26). (FigureThe9absence
and Figure of the S26).
same The absence
type of the same
of emission profiletype
for
of emission profile for Dy(III) and Tb(III) complexes at 77 K strongly
Dy(III) and Tb(III) complexes at 77 K strongly suggests that other quenching pathway(s) are also suggests that other quenching
pathway(s)
involved inare also 3involved
2 and (Figure in 2 and
S26). 3 (Figure S26).
Considering the Considering
excitation at the 309excitation
nm (32,360 at 309
cm−1nm, 4.0(32,360 cm−1 ,
eV), energy
4.0 eV), energy
transfer could take transfer placecould
fromtake place from
ligand-based ligand-based
higher higher
excited states excited
(e.g., states (e.g.,
the state(s) the state(s)
at 325–425 nm and at
325–425 nm and 425–600 nm) to suitably positioned higher excited
425–600 nm) to suitably positioned higher excited states of Ln(III) ions, followed exclusively by non- states of Ln(III) ions, followed
exclusively by non-radiative
radiative relaxation (throughrelaxation
the Ln(III)(through
ion manifold the Ln(III) ion manifoldtoorother
or (back-)transfer (back-)transfer
non-emissive to other
lower
non-emissive
energy ligand-centeredlower energy ligand-centered
excited states). Bearing excited
again states).
in mind Bearing again in at
the excitation mind309 the
nm,excitation
in case ofat 2,
309 nm, in
the possibilitycase of 2, the possibility of Dy(III/II) reduction by a ligand excited
Dy(III/II) reduction by a ligand excited state with generation of a non-radiatively state with generation of
adecaying
non-radiatively
LMCT state decaying couldLMCTalso be state could also
considered [20,be22].
considered
However, [20,22]. However,
even though very even though very
interesting from
interesting
the fundamental from thescience fundamental scienceidentifying
perspective, perspective,the identifying
exact nature the exact
of thenature of the ligand-based
ligand-based emission
emission
quenching quenching
pathwayspathways in 2 and 3in 2 and 3 (especially
(especially considering considering
that emission thatfrom
emission from the
the Dy(III) andDy(III)
Tb(III) and
ions
Tb(III)
was notions was not
identified belowidentified
800 nm) below
would 800require
nm) would require more
more in-depth in-depthstudies
spectroscopic spectroscopic
and it is studies
beyond
and it is beyond the scope of the present work. The effect of concentration of the sample on the
emission intensity was also tested for complexes 2 and 3 reported in this work. The increase in complex
concentration (10−6 to 10−4 M) results in the quenching of the emission at 425–600 nm in CH2 Cl2
Inorganics 2018, 6, 56 10 of 13

solution at both room temperature, and 77 K (Figures S24 and S25). In addition, no emission is detected
in the solid state at room temperature. For both 2 and 3, a large emission band centered at 600–650 nm
is observed, at high concentration, indicating that aggregation phenomena are (at least) partially
implicated in generating the respective emissive state.

3. Materials and Methods

3.1. General Procedures

All reagents were commercially available and used as received. Ligands papl and qapl were
prepared according to the literature procedures [10,11,15]. Anhydrous solvents were obtained from a
Puresolve MD-4 solvent purification system. The electronic spectra were recorded in CH2 Cl2 solutions
on a Cary UV–Vis–NIR spectrophotometer 6000i (Agilent Technologies, Santa Clara, CA, USA)
(concentration range of 10−4 –10−6 M). Luminescence spectra were obtained using a Perkin Elmer LS55
Luminescence Spectrometer (PerkinElmer, Waltham, MA, USA) equipped with a low temperature
accessory. The measurements were performed in CH2 Cl2 solutions (concentration range 10−4 –10−6 M),
at room temperature, and at liquid nitrogen temperature (77 K). Wavelength accuracy is ±1.0 nm. FT-IR
spectra were recorded on a Shimadzu IRAffinity spectrometer (Shimadzu America Inc., Columbia,
MD, USA) as KBr discs. ESI mass spectra were obtained on a Bruker HCT Plus Proteineer LC-MS
(Bruker Ltd., Milton, ON, Canada) with electrospray and a syringe pump was used for direct sample
infusion. Elemental analyses were carried out by Canadian Microanalytical Services, LTD., Delta,
BC, Canada.
CCDC 1844759 contains the supplementary crystallographic data for this paper. These data can
be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC,
12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033; E-mail: deposit@ccdc.cam.ac.uk)

3.2. Electrochemical Measurements

Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) experiments were performed
with a Bioanalytical Systems Inc. Epsilon electrochemical workstation. Compounds were dissolved in
anhydrous solvent (CH2 Cl2 ), and then deoxygenated by sparging with N2 gas for 20 min. Solution
concentrations were approximately 10−3 M in analyte containing 0.5 M supporting electrolyte
(Bu4 NPF6 ). A three-electrode set-up was used including a glassy carbon working electrode, Ag/AgCl
reference electrode, and a platinum wire auxiliary electrode. The scan rate for CV experiments was
200 mV/s. Parameters for the DPV experiments included a pulse amplitude of 50 mV, pulse width of
50 ms, and pulse period of 100 ms; scan rates were 40 mV/s.

3.3. DC Variable Temperature Magnetic Susceptibility Measurements

DC Magnetic susceptibility and magnetization measurements for complex 1 were made with a
9 T DynaCool Physical Property Measurement System (Quantum Design) using the vibrating sample
magnetometer option. The magnetic properties of complexes 2 and 3 were studied with a Quantum
Design Magnetic Property Measurement System using a Superconducting Quantum Interference
Device (SQUID). All samples were individually pelleted, weighed, tightly packed into plastic capsules
and loaded into brass holders. The signal from an empty capsule and the brass holder were measured
prior to filling and were found to be at least three orders of magnitude lower than the signal from
the samples.

3.4. Preparation of Complexes

Gd(papl)3 (1). 1-(2-pyridylazo)-2-phenanthrol (papl) (0.117 g, 0.391 mmol) was dissolved
in chloroform (5 mL) and 5 drops of triethylamine were added to the solution. A solution of
Gd(NO3 )3 ·6H2 O (0.061 g, 0.135 mmol) in methanol (5 mL) was added quickly drop-wise to the ligand
solution and then allowed to stir for 2 h. A purple precipitate was produced, which was collected by
Inorganics 2018, 6, 56 11 of 13

vacuum filtration, washed with water, methanol and dried. Yield (0.088 g, 64%). MS (ESI+): 1053.2
(MH+ ). Anal. Calc’d for (%) C57 H36 N9 O3 Gd (found%): C, 65.06 (65.34); H, 3.45 (3.39); N, 11.98 (11.87).
FT-IR (KBr, cm−1 ): 3063 (w), 1597 (m), 1584 (m), 1559 (m) 1510 (s) 1493 (s), 1437 (m), 1389 (w), 1319 (s),
1291 (m), 1275 (s), 1225 (s), 1208 (m), 1177 (m), 1161 (m), 1140 (s), 1101 (m), 1034 (m), 999 (m), 928 (w),
754 (m), 725 (m), 637 (w), 517 (w).
Dy(papl)3 (2). Papl (0.122 g, 0.407 mmol) was dissolved in chloroform (5 mL) and 5 drops
of triethylamine were added to the solution. A solution of Dy(NO3 )3 ·xH2 O (0.051 g) in methanol
(5 mL was added quickly drop-wise to the ligand solution and stirred for 2 h. A purple precipitate
was produced that was collected by vacuum filtration, washed with water, methanol and dried.
Yield (0.086 g, 59%). MS (ESI+): 1059.2 (MH+ ). Anal. Calc’d for (%) C57 H36 N9 O3 Dy (found%): C,
64.74 (65.19); H, 3.43 (3.25); N, 11.92 (12.00). FT-IR (KBr, cm−1 ): 3062 (w), 1597 (m), 1584 (m), 1559 (m),
1512 (s), 1493 (s), 1437 (m), 1389 (w), 1341 (m), 1319 (s), 1294 (m), 1277 (s), 1227 (s), 1207 (m), 1179 (s),
1161 (m), 1140 (s), 1126 (m), 1101 (m), 1034 (m) 999 (m), 928 (w), 872 (w), 754 (m), 725 (m), 654 (w).
Tb(papl)3 ·0.4CHCl3 (3). Papl (0.10 g, 0.33 mmol) was dissolved in chloroform (5 mL) and 5 drops
of triethylamine were added to the solution. A solution of Tb(NO3 )3 ·5H2 O (0.049 g, 0.113 mmol) in
methanol (5 mL) was added drop-wise to the ligand solution and allowed to stir for 2 h. A purple
precipitate was produced, which was collected by vacuum filtration, washed with water, methanol and
dried. Yield (0.074 g, 62%). MS (ESI+): 1054.2 (MH+ ). Anal. Calc’d for (%) C57 H36 N9 O3 Tb·0.4CHCl3
(found%): C, 62.58 (62.60); H, 3.33 (3.21); N, 11.44 (11.50). FT-IR (KBr, cm−1 ): 3065 (w), 1597 (m),
1584 (m), 1559 (m), 1510 (m), 1491 (m), 1437 (m), 1387 (w), 1341 (m), 1319 (s), 1292 (m), 1277 (s), 1227 (s),
1207 (m), 1179 (m), 1161 (m), 1140 (s), 1101 (m), 1034 (w), 999 (m), 871 (w), 756 (m), 725 (m).
Ho(qapl)3 ·1.1CH2 Cl2 (4). Qapl (0.075 g, 0.23 mmol) was dissolved in chloroform (15 mL) and
10 drops of triethylamine were added to the solution. A solution of HoCl3 ·6H2 O (0.029 g, 0.077 mmol)
in methanol (15 mL) was added drop-wise to the ligand solution and allowed to stir for 12 h at
approximately 35 ◦ C. A red-purple precipitate was produced, which was collected by vacuum filtration,
washed with water, methanol and dried. Yield (0.068 g, 75%). Single crystals of 4 were grown by
slow evaporation of DCM/CH3 CN solutions (approximately 2 mg in 11 mL DCM and 2 mL CH3 CN).
MS (ESI+): 1210.2 (MH+ ). Anal. Calc’d for (%) C69 H42 N9 O3 Ho·1.1CH2 Cl2 (found%): C, 64.59 (64.68);
H, 3.42 (3.59); N, 9.67 (9.49). FT-IR (KBr, cm−1 ): 3447 (m), 3061 (w), 3019 (w), 1605 (m), 1582 (m),
1558 (m), 1510 (m), 1487 (m), 1379 (m), 1341 (s), 1325 (s), 1300 (s), 1222 (s), 1204 (m), 1155 (w), 1105 (w),
1087 (w), 1051 (w), 1037 (w), 968 (w), 874 (w), 831 (w), 810 (w), 785 (w), 752 (m), 727 (m), 692 (w).
λmax (THF) = 506 nm.

4. Conclusions
Herein, we have reported the first lanthanide ion complexes 1–3 with the arylazo ligand papl.
In these complexes, three equivalents of the deprotonated ligand bind to the metal ion to produce nine
coordinate species with a likely tricapped trigonal prismatic geometry at the lanthanide ion, analogous
to the Ho(qapl)3 complex also reported in this work. As anticipated, complexes 1–3 exhibit similar
spectroscopic and electrochemical features to transition metal complexes containing papl, including
intense visible absorption bands and rich cathodic electrochemical behavior. Of note, we investigated
the luminescent properties of 1–3 and the uncoordinated papl ligand since there are very few reports
of the emission properties of lanthanide complexes coordinated to arylazo ligands. In all cases,
the typical sharp lanthanide ion centered luminescence is not observed and the emission profiles of
1–3 all resembled that obtained from the uncoordinated papl ligand. The emission intensities are
dependent on the ion with Gd the most intense and very weak emission observed from the Tb/Dy
complexes. While no slow relaxation of the magnetization was observed for the Tb or Dy complexes
described in this work, we are pursuing other heteroleptic lanthanide complexes containing papl using
[Ln(tta)3 ] (tta− = 2-thenoyltrifluoroacetonate) or [Ln(hfac)3 ] (hfac− = hexafluoroacethylacetonate)
salts, which have been shown to produce multifunctional luminescent SIMs with other redox active
ligand types [23].
Inorganics 2018, 6, 56 12 of 13

Supplementary Materials: Supplementary Materials can be found at http://www.mdpi.com/2304-6740/6/2/

56/s1. Figures S1–S26: ESI, CIF, electrochemical, variable temperature magnetic susceptibility and luminescence
data for 1–3. Table S1: Crystal data and structure refinement for 4, Cif and checkcif file of 4.
Author Contributions: M.T.L. conceived and designed the experiments; R.A.T. synthesized and characterized
the papl ligand and complexes 1–3; M.C. and J.Y. performed the photophysical experiments; N.M.B. prepared
qapl, complex 4 and grew single crystals; A.J.L. solved the crystal structure of 4; C.R.W., H.J.S. and C.M. designed
and completed the variable temperature magnetic susceptibility experiments; and M.T.L. wrote the paper with
contributions from all co-authors.
Acknowledgments: M.T.L. acknowledges funding from NSERC, CFI, Canada Research Chairs Program, Brandon
and Brock University and the University of Manitoba for providing an adjunct position. M.C. thanks NSERC and
the FRQNT and Université de Montréal for graduate fellowships. Y.J. thanks MITACS for a student fellowship.
C.R.W. acknowledges funding from NSERC, CFI, the Canada Research Chairs Program (Tier II), CIFAR, and the
University of Manitoba for providing an adjunct position.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Bottrill, M.; Kwok, L.; Long, N.J. Lanthanides in magnetic resonance imaging. Chem. Soc. Rev. 2006, 35,
557–571. [CrossRef] [PubMed]
2. Harvey, P.; Kuprov, I.; Parker, D. Lanthanide complexes as paramagnetic probes for 19F magnetic resonance.
Eur. J. Inorg. Chem. 2012, 2015–2022. [CrossRef]
3. Tsitovich, P.B.; Burns, P.J.; McKay, A.M.; Morrow, J.R. Redox-activated MRI contrast agents based on
lanthanide and transition metal ions. J. Inorg. Biochem. 2014, 133, 143–154. [CrossRef] [PubMed]
4. Zhang, M.; Qu, Z.B.; Han, C.M.; Lu, L.F.; Li, Y.Y.; Zhou, T.; Shi, G. Time-resolved probes and oxidase-based
biosensors using terbium(III)-guanosine monophosphate-mercury(II) coordination polymer nanoparticles.
Chem. Commun. 2014, 50, 12855–12858. [CrossRef] [PubMed]
5. Bünzli, J.-C.G. Lanthanide Luminescence for Biomedical Analyses and Imaging. Chem. Rev. 2010, 110,
2729–2755. [CrossRef] [PubMed]
6. Woodruff, D.N.; Winpenny, R.E.P.; Layfield, R.A. Lanthanide single-molecule magnets. Chem. Rev. 2013, 113,
5110–5148. [CrossRef] [PubMed]
7. Sorace, L.; Benelli, C.; Gatteschi, D. Lanthanides in molecular magnetism: Old tools in a new field.
Chem. Soc. Rev. 2011, 40, 3092–3104. [CrossRef] [PubMed]
8. Rinehart, J.; Long, J. Exploiting single-ion anisotropy in the design of f-element single-molecule magnets.
Chem. Sci. 2011, 2, 2078–2085. [CrossRef]
9. Samanta, S.; Ghosh, P.; Goswami, S. Recent advances on the chemistry of transition metal complexes of
2-(arylazo)pyridines and its arylamino derivatives. Dalton Trans. 2012, 41, 2213–2226. [CrossRef] [PubMed]
10. Chiswell, B.; Lions, F.; Tomlinson, M.L. Tridentate Chelate Compounds. IV. Metal Complexes from a-Diketone
Mono-a-pyridylhydrazone Type Ligands. Inorg. Chem. 1961, 611, 322–327. [CrossRef]
11. Van Damme, N.; Lough, A.J.; Gorelsky, S.I.; Lemaire, M.T. Molecular and electronic structures of complexes
containing 1-(2-pyridylazo)-2-phenanthrol (PAPL): Revisiting a redox-active ligand. Inorg. Chem. 2013, 52,
13021–13028. [CrossRef] [PubMed]
12. Taylor, R.A.; Lough, A.J.; Lemaire, M.T. Spin-crossover in a homoleptic cobalt(II) complex containing a
redox-active NNO ligand. J. Mater. Chem. C 2016, 4, 455–459. [CrossRef]
13. Takahashi, K.; Kawamukai, K.; Okai, M.; Mochida, T.; Sakurai, T.; Ohta, H.; Yamamoto, T.; Einaga, Y.;
Shiota, Y.; Yoshizawa, K. A New Family of Anionic FeIII Spin Crossover Complexes Featuring a Weak-Field
N2 O4 Coordination Octahedron. Chem. A Eur. J. 2016, 22, 1253–1257. [CrossRef] [PubMed]
14. Andreiadis, E.S.; Imbert, D.; Pécaut, J.; Demadrille, R.; Mazzanti, M. Self-assembly of highly luminescent
lanthanide complexes promoted by pyridine-tetrazolate ligands. Dalton Trans. 2012, 41, 1268. [CrossRef]
[PubMed]
15. Taylor, R.A.; Bonanno, N.M.; Mirza, D.; Lough, A.J.; Lemaire, M.T. A trivalent cobalt complex with the new
redox-active ligand 10-(8-quinolylazo)-9-phenanthrol (qapl). Polyhedron 2017, 131, 34–39. [CrossRef]
16. Bonanno, N.M.; van Damme, N.; Lough, A.J.; Lemaire, M.T. Transition metal complexes containing a ditopic
redox active ligand featuring very intense visible absorption bands. Dyes Pigment. 2015, 123, 212–217. [CrossRef]
Inorganics 2018, 6, 56 13 of 13

17. Zhou, J.L.; Xu, Y.H.; Jin, X.X.; Xiao, S.; Yi, H.B.; Yan, J. Synthesis and characterization of luminescent zinc
complexes containing redox-active 1-(2-pyridylazo)-2-acenaphthequinol ligands with nonlinear optical
property. Inorg. Chem. Commun. 2016, 64, 67–70. [CrossRef]
18. Wu, Y.; Wang, J.; Kong, X.; Sheng, C.; Wang, R.; Peyghambarian, N.; Norwood, R.A.; Zheng, Z. A dinuclear
europium(III) complex with thenoyltrifluoroacetonato and 1-(2-pyridylzao)-2-naphtholato ligands and its
optical properties. Inorg. Chim. Acta 2011, 370, 346–352. [CrossRef]
19. Santos, F.D.S.; Descalzo, R.R.; Gonçalves, P.F.B.; Benvenutti, E.V.; Rodembusch, F.S. Evidence for excited
state intramolecular charge transfer in benzazole-based pseudo-stilbenes. Phys. Chem. Chem. Phys. 2012, 14,
10994–11001. [CrossRef] [PubMed]
20. Shuvaev, S.; Utochnikova, V.; Marciniak, Ł.; Freidzon, A.; Sinev, I.; Van Deun, R.; Freire, R.O.; Zubavichus, Y.;
Grünert, W.; Kuzmina, N. Lanthanide complexes with aromatic o-phosphorylated ligands: Synthesis,
structure elucidation and photophysical properties. Dalton Trans. 2014, 43, 3121–3136. [CrossRef] [PubMed]
21. Bünzli, J.-C.G.; Piguet, C. Taking advantage of luminescent lanthanide ions. Chem. Soc. Rev. 2005, 34,
1048–1077. [CrossRef] [PubMed]
22. Meyer, A.U.; Slanina, T.; Heckel, A.; König, B. Lanthanide Ions Coupled with Photoinduced Electron Transfer
Generate Strong Reduction Potentials from Visible Light. Chem. Eur. J. 2017, 23, 7900–7904. [CrossRef]
[PubMed]
23. Pointillart, F.; le Guennic, B.; Cador, O.; Maury, O.; Ouahab, L. Lanthanide Ion and Tetrathiafulvalene-Based
Ligand as a “magic” Couple toward Luminescence, Single Molecule Magnets, and Magnetostructural
Correlations. Acc. Chem. Res. 2015, 48, 2834–2842. [CrossRef] [PubMed]

© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).