Threading Salen-type Cu- and Ni-Complexes into One-Dimensional Coordination Polymers: Solution versus Solid State and the Size Effect of the Alkali Metal Ion

Article abstract of DOI:10.1021/acs.cgd.7b01769

Compartmentalization of metal ions is crucial in biology as well as in materials science. For the synthesis of single source precursors, the preorganization of different metal ions is of particular interest for the low-temperature generation of mixed meta

Full text of DOI:10.1021/acs.cgd.7b01769

Subscriber access provided by READING UNIV
Article
Threading salen-type Cu- and Ni-complexes into one-
dimensional coordination polymers: Solution versus
solid state, and the size effect of the alkali metal ion
Alba Finelli, Nelly Hérault, Aurelien Crochet, and Katharina M. Fromm
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01769 • Publication Date (Web): 03 Jan 2018
Downloaded from http://pubs.acs.org on January 4, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Crystal Growth & Design is published by the American Chemical Society. 1155
Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Alba Finelli †, Nelly Hérault †, Aurélien Crochet ‡, Katharina M. Fromm *,†
† Department of Chemistry, University of Fribourg (UNIFR), Ch. du Musée 9, 1700 Fribourg, Switzerland
‡ FriMat, Department of Chemistry, University of Fribourg, Ch. du Musée 9, 1700 Fribourg, Switzerland.
Keywords: Mixed metal complexes, Schiff base, Metallohost-guest compounds, Alkali ions, Copper(II), Nickel(II).
ABSTRACT: Compartmentalization of metal ions is crucial in biology as well as in materials science. For the
synthesis of single source precursors, the preorganization of different metal ions is of particular interest for the
low-temperature generation of mixed metal oxides. Based on a potentially Ω-shaped salen-type ligand providing
an N2O2 as well as an O2O2 coordination site, mixed metal coordination compounds with Cu(II) or Ni(II) and
1
alkali metal ions have been studied for their structural and optical properties. UV-Vis and H-NMR titrations
show that the obtained compounds adopt partially different structures in solution compared to the solid state. In
the latter case, the coordination geometry is mainly governed by the size of the alkali metal ion as well as the
transition metal ion used.
INTRODUCTION
magnetic compounds25-30 and many other applica-
32
tions.31, Bermejo et al.33-37 have studied Mn-Schiff
The precise arrangement and compartmentalization
of metal ions are important both in biology as well as
in materials science.1-5 Siderophores such as iron
chelators produced by microbes are for example pro-
totypes for metal specific up-taking agents. These
could be used in industrial or environmental cleanup
processes to selectively extract metal ions.6 Artificial
systems such as salen (N,N′-disalicylidene-
ethylenediamine) and its derivatives are commonly
employed as versatile chelate ligands in coordination
chemistry and obtained by a straightforward conden-
sation reaction.7 Containing two Schiff base8 coordi-
nating moieties, this family of ligands is able to bind
to transition-metal ions in a tetradentate fashion
forming stable complexes through its N2O2 site. Fur-
thermore, they represent versatile ligands type thanks
to their tunable design9. Numerous mono-, di- or tri-
nuclear complexes have been synthetized with differ-
base complexes as possible catalysts for the dispro-
portionation of hydrogen peroxide38-41. Furthermore,
other interesting features such as metal-containing
gels and nanofibers made through supramolecular
assembly of Zn-salen based complexes have been
described by MacLachlan and co-workers42-44
.
Functional compartments can also be created by
substitution of the ligand, allowing the coordination
of two different metal ions22, 45-47 and originating mac-
rocycle-type compounds. The latter combination can
49
lead to new properties48,
coordination
in compounds such as
polymers,50-54
mono-
and
multimetallic55-63 complexes or oxide materials.64-67
Several structural studies were undertaken on bi- or
trinuclear mono or heterometallic Schiff base com-
plexes33-37. Interesting trinuclear structures of Zn-
salen based complexes were reported in Cai’s work,
by tuning the counter ions, the solvent or the reac-
tion conditions68. A structural description of a binu-
clear Zn complex able to undergo transmetalation as
well as polynuclear salen compounds were presented
by Kleij and co-workers69, 70. Based on salen-type
ent
transition
elements
exhibiting
diverse
properties10-17. The resulting compounds are em-
ployed e.g. as catalysts18,
for various organic
1918, 19
reactions18, 19, as supramolecular building blocks,20, 21
in nonlinear optical materials22-24 or as interesting
ACS Paragon Plus Environment
1

Crystal Growth & Design
Page 2 of 34
1
2
3
4
5
6
7
8
9
ligands, Nabeshima et al. have described multiple-
dination of the alkali metal compounds by the cop-
per, respectively the nickel salen complex, as well as
their possible structural isomers in solution and in
the solid state. Taken together, the structural studies
of the herein described alkali-bimetallic complexes in
the solid state and in solution represent an important
step towards the comprehension of the salen-based
complex chemistry.
metal containing host-guest complexes using
transmetalation reactions to incorporate the guest
ions.22, 71 These ligands can adopt, depending on the
ionic radius of the metal ions, a helical conformation
in solution.72, 73 They also reported the first efficient
and selective introduction of three different metal
ions into one ligand under thermodynamic control.4
While numerous transition metal ions were widely
employed along with the salen-derived ligands for
multiple purposes, the series with alkali metal ions
remain however not entirely investigated21, 74, 75. Pre-
vious tests to use alkali ions as guests in larger H2L
salen-type ligands using also transmetalation were
unsuccessful.72 While a recent publication by the
Nabeshima group deals with the formation of alkali
metal ion complexes with macrocyclic ligands in
solution, no solid state data could be obtained to gain
further proof and insight76.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
RESULTS AND DISCUSSION
The N2O2 imine-based chelating site of salen-based
compounds such as H2L has the property to perfectly
bind transition metal ions81, 82. After deprotonation
and complexation to divalent d-block transition met-
al ions such as Cu(II) and Ni(II) ions, neutral com-
pounds are obtained. Our symmetric ligand H2L
(Scheme 1) comprises two imines, two phenol and
two methoxy groups. The coordination of the N2O2
moiety to a transition metal ion preorganizes the
ligand in a Ω-shape, generating a second recognition
site, O2O2, able to accept further metal ions.
Here, we report on the study of a salen derivative,
H2L, synthesized from o-vanillin and ethylene dia-
mine.77 This ligand is composed by moieties which
potentially allow the coordination of two different
types of metal ions. The central coordination site is
an imine-based N2O2 entity which was used to coor-
dinate to copper(II) or nickel(II) under deprotona-
tion. This prearranges the ligand into a Ω-shape lead-
ing to a second recognition site, O2O2, composed by
two phenoxy and two methoxy functions. Due to the
high coordination aptitude of the negatively charged
phenolates formed upon deprotonation, the binding
of hard metal ions (alkali, alkaline earth, etc.) is more
favorable.78 Depending on the size of the metal ion to
be coordinated in the O2O2 site, the choice of the
counter ions and the solvent, different coordination
modes can be expected in solution and/or in the solid
state.74, 79 A total of eleven new compounds have been
obtained and characterized to provide more details
and information compared to previous works. Con-
taining two different Schiff base coordinating moie-
ties, our copper(II) or nickel(II) complexes are versa-
tile chelate ligands for the uptake80 of larger cations
such as rubidium or cesium. We also studied the
structural differences influenced by the uptake of
alkali metal ions between the nickel(II) and cop-
per(II) complexes. Indeed, the copper ion tends to
adopt a square pyramidal coordination sphere, while
the nickel ion is preferentially coordinated in a quasi-
perfect square planar way. We also studied the influ-
ence of the solvent and the counter ions upon coor-
The ligand H2L was synthetized following the liter-
ature
procedure77
from
the
2-hydroxy-3-
methoxybenzaldehyde (o-Vanillin) and ethane-1,2-
diamine by a nucleophilic addition forming an hemi-
aminal. The subsequent dehydration provides the
resulting imine in quantitative yield (Scheme 1).
Scheme 1: Synthetic route of H2L with two specific
coordination sites.
2
ACS Paragon Plus Environment

Page 3 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
1
Synthesis of the metallo-ligands. In the first
step, Ni(II) and Cu(II) have been used to bind to the
N2O2 cavity of L, yielding literature-known com-
pounds83-86 LNi and LCu, used further as ligands for
alkali metal ions (detailed data on all the individual
titrations can be found in the supplementary infor-
mation, Fig. S2-4). Solid state structures of the com-
pounds LCu and LNi obtained as single crystals con-
firm the binding of the metal ions in the N2O2 pocket
of the Ω-shaped ligand45, 87, 88 (Fig.S1). The difference
between the two complexes is that in LCu, a water
molecule coordinates the copper ion in order to yield
a square pyramidal environment, while the nickel ion
in LNi remains with a square planar coordination.
We used these compounds to study the influence of
alkali metal ion binding in the remaining O2O2 cavity.
Figure 2: H NMR titration binding isotherm of the
LNiNa complex formation focused on the imine proton
signal at 0°C, RT and 50°C and their corresponding fitted
curves.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Binding of Alkali metal ions to the O2O2 recog-
nition site – Solution studies. The second metal
ion insertion was investigated by mixing LCu or LNi
with the alkali metal salts. Stoichiometric amounts
were used in a solvent mixture of ACN/EtOH for 3h
Ni(II) complexes do not change color and are dia-
magnetic.
1
at RT. H-NMR and UV-Vis titrations have been per-
M2 coordination studies
formed for the LNi, respectively the LCu derived
compounds, to explore the formation of the different
heterometallic complexes in solution. Indeed, the
Cu(II) compounds are paramagnetic and change
color upon addition of the alkali metal ion, while the
1H NMR Study. Upon addition of aliquots of alkali
metal ion salt to the solution of LNi, peak shifts were
observed particularly for the imine and methyl sig-
nals. For the alkali metal ions Na(I) and K(I), high-
field shifts of the imine signals were observed while
for the two larger ones, Rb(I) and Cs(I), low-field
shifts signal a shielding effect, rendering the proton
less sensitive to the magnetic field. For the titration
of LNi with Li(I) ions, no apparent plateau is reached
as the shifts are too small to determine any tendency.
This might be explained by the fact that the addition
of lithium ions can apparently, due to its smaller size,
lead to the formation of many complex species in
solution.
1
Figure 1: (a) H NMR titration of LNi with NaNO3
1
forming the complex LNiNa. (b) H NMR titration bind-
ing isotherm of the LNiNa complex formation focused
on the imine proton signal and a Job plot performed
with constant total concentration of [0.04 M].
The binding isotherm for Na(I) shows a plateau at
0.5 equiv. of metal ion, corresponding to 0.66 on the
Job plot and hence confirming the presence of a 2:1
(LM1:M2 ratio) species in solution (Fig. 1). The titra-
tion curve for the potassium ion is not well defined.
The Job plot reveals a plateau at around 0.4 equiv. of
metal indicating the presence of different oligomers
in solution, probably stemming from a coordination
polymer. For the larger Rb(I) ion, the proton signal
becomes more and more shielded upon addition of
the Rb(I) ion until almost 0.5 equiv. of metal. Upon
further addition, the signal is shifting back to down-
field again. This indicates the formation of a 2:1 spe-
cies at around 0.5 equiv., before the adoption of a 1:1
binding mode. Although similar, a less pronounced
pattern is observed for the Cs ion, indicating a weaker
binding according to its softer character (detailed
3
ACS Paragon Plus Environment

Crystal Growth & Design
Page 4 of 34
1
2
3
4
5
6
7
8
Scheme 2: Existing equilibrium between the 1:1 and
the 2:1 species in solution.
Figure 3: UV-Vis titration of the LCu with NaNO3
complex. Diminution of the absorbance of the two first
bands along the titration and appearance of the two
isobestic points. Binding isotherm of LCuNa focused on
the first band and a Job plot performed with constant
total concentration of [0.0001 M].
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Vis spectral changes of each titration reach a plateau
at around 0.5 equiv. of added alkali metal ions (Fig.3)
indicative of the formation of a 2:1 complex (detailed
data on all the individual titrations can be found in
the supplementary information, Fig. S5 – S9). No
correlation can be drawn for the d-d transition band
during the titration, indicating different coordination
possibilities for the transition metal ion, e.g. with
solvent molecules or counter ions, as confirmed later
by the solid-state structures.
data on all the individual titrations can be found in
the supplementary information, Fig. S11 – S16).
1H NMR titrations at room temperature, 0°C and
50°C (Fig. 2) have been undertaken in a mixture of
deuterated acetonitrile and methanol in order to
confirm the equilibrium between the 1:1 and 2:1 com-
plexes in solution (Scheme 2), which becomes more
apparent at 0°C, indicating also a fast exchange on
the NMR time scale.
In completion of the solution studies, the ESI mass
spectra of the mother liquors in MeOH of the LNi
and LCu alkali complexes also indicate in all cases
the presence of two main peaks for the 1:1 and 2:1
compositions (Scheme 2). The compounds corre-
sponding to the 1:1 ratio might also indicate the pres-
ence of oligomers stemming from of a coordination
polymer (see Fig. S28).
UV-Vis Measurement. The corresponding LCu
complexes were analyzed by UV-Vis during addition
of aliquots of the alkali metal ion solutions. For the
UV-titrations, the measurements were performed in a
mixture of acetonitrile and DMSO due to solubility
reasons. Ni(II) and Cu(II) complexes with σ-donor/π-
acceptor salen ligands present similar UV-Vis spectra
and show two characteristic high intensity bands
located below λ= 450 nm and one broad band in the
visible region89. The typical main band is assigned to
the π→π* transition stemming from the extended
delocalized π-systems of the azomethine group in-
volving the molecular π-orbitals localized on the C=N
group and the aromatic ring appearing at around 280
nm. The band at 380 nm is associated to the metal-
to-ligand charge transfer (MLCT) transition. Both
bands are related to the non-resolved d-d transitions
Crystallography
In order to gain further insight into the way that
LCu and LNi bind to the different alkali metal ions,
single crystal X-ray analysis was performed on all
compounds, except “LCuK” (3), for which no single
crystals could be obtained. [{LCuLi(µ-NO3)(µ-
H2O)}2]n will be abbreviated as “LCuLi” (1), [LCu-
Na(NO3)]n as “LCuNa” (2), [LCuRb(µ-NO3)]n and
[LCuCs(µ-NO3)]n as “LCuRb” (4) and “LCuCs” (5),
respectively. For the nickel containing compounds,
the nomenclature “LNiLi” for [(LNiLi(NO3))2(µ-H2O)]
(6), “LNiNa” for [LNiNa(NO3)] (7), “LNiK” for
[(LNiK(µ-NO3)]n (8), “LNiRb” for [(LNiRb(NO3)]n (9)
and “(LNi)2Cs” for [{(LNi)2Cs(NO3)}(HCCl3)]n (10) is
employed. Furthermore, the structure of a copper
analogue to 6, [(LCuLi(NO3))2(µ-H2O)] (1’) will be
presented as well as an unusual alternative to 2, a
compound with three “LCuNa” entities in the asym-
metric unit, namely [{LCuNa(NO3)}3]n (2’). The use of
methanol during the reaction produce yielded the
complex [LNiNa(MeOH)] (7’), a solvate analogue to
7. A detailed description of all single crystal struc-
tures and their corresponding figures can be found in
the supplementary information, Fig. S29 – S37, Table
S1).
from the four low-lying d-orbitals (dxz, dyz, dz ,dx -y2)
2
2
to the empty (Ni), or half-filled (Cu) dxy orbital89, 90
.
Concerning the copper complexes, the color of the
LCu solution in ACN/DMSO immediately changed
from pale green to pale purple upon the addition of
the alkali metal nitrate solution while for those con-
taining nickel, the solutions maintain their initial
orange tint. During the formation of new species in
solution upon titration, the two intense absorption
bands decrease and are slightly hypsochromically
shifted revealing two isosbestic points, indicating the
transformation of one species into another. The UV-
4
ACS Paragon Plus Environment

Page 5 of 34
Crystal Growth & Design
1
2
3
4
Table 1 : Crystallographic data for 1-10, 1’, 2’ and 7’.
1
C36H40Cu2Li2N6O16
953.72
2
4
C18H18CuN3O7Rb
537.37
5
C18H18CsCuN3O7
584.81
6
7
8
9
10
C37H38Cl3CNNi2O11
1084.36
5
6
7
8
Formula
Mw
C18H18CuN3NaO7
474.89
C36H38Li2N6Ni2O15 C18H18N3NaNiO7 C18H18N3KNiO7 C18H18NNiO7Rb
525.98
200
470.03
200
486.14
200
537.37
200
T [K]
Lattice
200
200
200
200
200
9
Triclinic
Orthorhombic
Monoclinic
Monoclinic
Orthorhombic
Monoclinic
Monoclinic
Monoclinic
Monoclinic
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
Space
group
P-1
P212121
P21/n
P21/n
Pbca
P21/n
P21/c
P21/a
P21/c
a [Å]
b [Å]
c [Å]
α [°]
β [°]
γ [°]
V [Å3]
Z
6.8904(3)
14.0730(6)
20.1289(9)
91.332(3)
91.223(3)
95.912(3)
1940.41(15)
2
6.7926(2)
12.5138(6)
7.0649(2)
22.879(11)
90
12.1968(7)
7.3733(3)
23.0872(14)
90
21.1167(11)
6.0152(6)
14.6893(16)
21.613(2)
90
11.8080(7)
22.9185(11)
7.1057(4)
90
7.8817(89
22.9008(19)
11.9317(14)
90
12.6803(4)
23.7600(9)
14.1706(5)
90
16.2300(6)
16.8677(9)
17.3134(8)
21.7489(11)
90
90
90
99.936
90
97.221
90
90
93.470(8)
90
94.986(5)
90
95.440
99.271(3)
90
90
1908.7(13)
4
90
77465.74(7)
8
90
1975.67(15)
4
2059.78(19)
4
1906.2(3)
4
1915.68(18)
4
1975.67(15)
4
4213.6(3)
4
dcalc
1.632
1.653
1.807
1.886
1.588
1.638
1.686
1.801
1.709
[g cm-3]
R1/ wR2
[I>2sigma(I)]
0.0305/0.0673
0.0383/0.0879
0.0274/0.0690
0.0355/0.0925
0.0387/0.1134
0.0442/0.0994
0.0362/0.0670
0.0394/0.0934
0.0253/0.0616
1'
2’
C54H54Cu3N9Na3O21
1424.65
7’
C19H22N3NaNiO8
502.09
Formula
C36H38Cu2Li2N6O15
Mw
935.68
250
T [K]
Lattice
250
250
Orthorhombic
Monoclinic
Triclinic
Space group
Pbca
P21
P-1
a [Å]
21.3235(16)
16.6448(8)
21.9257(18)
11.5629(5)
7.1551(5)
b [Å]
c [Å]
α [°]
β [°]
γ [°]
V [Å3]
Z
16.0104(5)
16.0578(7)
90
11.0125(7)
13.5223(9)
95.481(5)
99.145(5)
98.594(5)
90
90
90
106.675(4)
90
7782.0(9)
1
1.597
2847.7(2)
2
1.661
1032.35(12)
2
dcalc[g cm-3]
1.615
R1/ wR2
[I>2sigma(I)]
0.0914/ 0.1490
0.0929/0.1970
0.0337/0.0668
5
ACS Paragon Plus Environment

Crystal Growth & Design
Page 6 of 34
1
2
3
4
5
6
7
8
9
Figure 5: Crystal structure of LCuNa complex 2 (#1(-1+x,
y, z), #2(1+x, y, z), #3( ½ -x, 1-y, ½+z) ,#4( /2 -x, 1-y, - ½
+z)), its Na(I) π-system packing and Cu(II)-C4 interaction
(dash bonds). All H-atoms are omitted for clarity.
All the complexes were crystallized from the moth-
er liquor of the reaction after reacting H2L first with
Cu(OAc)2 or Ni(OAc)2 respectively, and second, with
the corresponding alkali salts. In the following com-
pounds, copper(II) and nickel(II) are coordinated in a
quasi-perfect square planar way by the N2O2 chelat-
ing moiety of the ligand formed by the phenolate
moieties and imine groups with (for copper) or with-
out (for nickel) additional axial oxygen donor atoms,
as considered by the bond valence sums91. The angle
sum around the metal ions within the chelating moi-
ety is always approximately 360°, indicating the pla-
narity of this coordination.
3
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Concerning the occupation of the O2O2 site, the
mono coordinated ligand will adopt different con-
formations depending on the size of the alkali metal
ions as well as on their non-covalent bonds, forming
Figure 4: Crystal structure of LCuLi complex 1 (#1 (1+x, y,
z)) bridged by one molecule of water and two nitrate ions
and its corresponding 1D coordination polymer formation.
H-atoms except for water are omitted for clarity.
simple monomer complexes, or coordination poly-
mers.
Copper(II) (LCu) complexes
The two independent lithium ions of LCuLi, 1, are
each bound by only one side of the O2O2 cavity of a
ligand molecule, namely via one phenolate and the
corresponding methoxy group. A “dimer” structure is
formed in which a single water molecule O15 acts as
bridging ligand between the two alkali metal ions,
connecting two independent LCuLi-complexes. The
latter are packed in an antipararallel fashion. While
the oxygen atoms of water molecule act as bridging
atom between the lithium ions of neighbor complex-
es, the nitrate anions act also as bridging ligands
towards the copper as well as the lithium ions. An
overall one-dimensional (1D) coordination polymer is
then obtained, in which the ligand molecules are
6
ACS Paragon Plus Environment

Page 7 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Figure 6: Crystal structure of the 1D coordination of
arranged anti, hence alternatingly head to tail along
the crystallographic c-axis (Fig. 4).
LCuRb complex 4 (above, #3( ½ -x, ½+y, ½-z), #4(x, 1+y, z),
#5( ½ -x, 3/2 +y, ½-z)) and, LCuCs complex 5 showing a tail
to face packing (#1( ½ -x, ½+y, ½-z), #4( ½ -x, - ½ +y, ½-z),
#7(x, 1+y, z)). All H-atoms are omitted for clarity.
In contrast to 1, the sodium ion in 2 is coordinated by
all four oxygen atoms of the O2O2 compartment of
the ligand. Its hexacoordinated ligand sphere is com-
pleted by the two O-atoms of a nitrate ion. Five out of
these six oxygen atoms coordinate in an almost per-
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
93
fect plane, similar to a crown ether complex,92,
while the sixth oxygen atom, stemming from the
bidentate nitrate anion, is out of plane. While a
Na(I)-π contact allows an expansion of the structure
into the direction of the a-axis, a growth along the c-
axis is revealed by the short contact of Cu2 in the
N2O2 site with the O-atom of the nitrate ion of a
neighbor unit (Fig. 5).
Compounds LCuRb, 4, and LCuCs, 5, adopt similar
structural motifs. The alkali metal ion is in both cases
too large to fit into the O2O2 compartment of the
ligand. Instead, two antiparallel neighbor ligands
form a head to tail sandwich complex using all O-
atoms of both ligand molecules to coordinate to one
alkali metal cation. In addition, one nitrate anion
coordinates with two of its O-atoms to each alkali
metal ion. These oxygen atoms also act as bridging
ligands to two copper ions of two second neighbor
parallel ligands, while one of the oxygen atoms also
connects to a next neighbor alkali metal ion (Fig. 6).
Both compounds form a one-dimensional (1D) coor-
dination polymer with antiparallel arrangement of
the ligands. However, the distance of the cesium ion
to the mean plane of oxygen atoms of each of its
ligands is more asymmetric than for the rubidium
ion. This is explained by the softer character of ce-
sium with respect to rubidium.
Nickel(II) (LNi) complexes
Compared to 1 (LCuLi), the corresponding “LNiLi”
compound 6 has a similar L:M1:M2 ratio, but only one
water molecule. This, together with the terminal
monodentate nitrate anions linked to the lithium
ions (see Fig. S30), prevents the formation of a one-
dimensional Li-H2O-chain as in 1. A finite “dimer”
structure is formed in which the single water mole-
cule acts as bridging ligand between the two alkali
metal ions of two almost parallel LNiLi-entities. In
contrast to 1, the anions in 6 act as terminal ligands
on the lithium ions, form a hydrogen bond to the
bridging water molecule and are not coordinated to
the transition metal ion (Fig. 7).
7
ACS Paragon Plus Environment

Crystal Growth & Design
Page 8 of 34
1
2
3
4
5
6
7
8
9
the c-axis, with the ligands arranged on one side with
Figure 7: Crystal structure of the “dimer” LNiLi com-
plex 6 (#1 (½ +x, y, ½-z)) bridged by one molecule of
water with forming two H bonds. The packing reveals C‒
H…π interactions along the a-axis (dash bonds). All H-
atoms are omitted for clarity. Blue dashes correspond to
H-bonds.
offsets of ca. 40°. The structure of LNiRb (9) is very
similar to 8 (Fig. 8), except that the rubidium ion is
coordinated in a more symmetric way between the
two mean planes of five-rings of O-atoms. For 8, the
potassium ions form a zigzag chain with angles of
174°, while the rubidium ions in compound 9 form
angles of 177°. The LNiRb compound 9 is “more re-
laxed” than the LCuRb compound 4, which is due to
the lack of Ni‒O(nitrate) interactions. While com-
pound 4 features Cu‒O(nitrate) bonds, which force
the ligands to be alternating antiparallel to each oth-
er, the ligands in 9 can all pack on one side of the
chain.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The nickel analogue to compound 5 (LCuCs), ce-
sium analogue to 9 (LNiRb), could not be obtained,
Figure 8: Crystal structure of the 1D coordination of
LNiK complex 8 (#1(x, - ½ -y, - ½ +z), #2(x, - ½ -y, ½+z),
#3(x, y, 1+z)) and, LNiRb complex 9 (#1( ½ +x, ½-y, z),
#2(- ½ +x, ½-y, z)) showing face to face packing. All H-
atoms are omitted for clarity.
The Ni-analogue to 2 (LCuNa), compound 7, has a
similar five-fold coordination of Na1 as 2, and the
packing, occurring in an offset parallel fashion, is
governed by Na(I)‒π interactions (see Fig. S32).
While the LCuK compound 3 could not be isolated
as single crystals, the LNiK compound 8 was ob-
tained in single crystalline form. In contrast to com-
pounds 2 (LCuNa) and 7 (LNiNa), and similar to
compounds 4 (LCuRb) and 5 (LCuCs), the potassium
ion in 8 is too large to be accommodated in the O2O2
compartment. Nevertheless, similar as in 2 and 7, the
four O-atoms of the O2O2 compartment form, to-
gether with one O-atom of a nitrate anion, a crown
ether type cavity made of five O-atoms within a
plane. The five-rings of O-atoms in 8 are parallel to
each other, while the potassium ion is ca. 1.72 Å out
of plane with respect to one ligand, and 1.83 Å out of
plane with respect to the other. An overall one-
dimensional coordination polymer is obtained along
8
ACS Paragon Plus Environment

Page 9 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Figure 10: Color change of the alkali complexes 1-5 de-
pending on the M2 metal ion size used compared to LCu
(left).
instead, this is the only case for which a 2:1 com-
pound LNi:Cs was found in the solid state. Two LNi
complexes use all eight of their O-atoms to coordi-
nate the cesium ion in a sandwich fashion while the
nitrate anion uses two of its O-atoms to complete the
tenfold coordination of the alkali metal ion. These
“sandwich” complexes are stacking parallel to each
other via short π-π interactions. Co-crystallizing chlo-
roform molecules are found in the channels between
the chains and promote non-polar interactions. This
compound remained the only one for which the 2:1
complex could be verified in the solid-state structure
(Fig. 9).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
compound. This is due to the fact that in the nickel
compound, the O2O2 cavity is smaller, underlined by
the higher bond valence sum for the nickel than for
the copper ion. Having an average bond valence
sum91 of 1.94 provided by the N2O2 cavity of the lig-
and, the Cu(II) completes its coordination sphere
using the O-donors of the anions, leading to alternat-
ing arrangements of the ligands in an antiparallel
fashion along the polymer propagation direction,
featuring a Jahn-Teller effect94. These interactions
might also explain the “head to tail” arrangements of
the complexes in all LCu-based structures and may
induce the color change of the copper complexes
from green to various pink hues (Fig. 10). On the
other hand, the Ni(II) ion does not require this inter-
action, owing to an average bond valence of 2.35 pro-
vided by the N2O2 cavity, leading thus to parallel
arrangements of the ligand moieties with slight off-
sets. For the sodium compounds, the donor atoms
from the O2O2 cavity are typically completed with a
fifth O-atom from a counter ion, yielding crown ether
like environment for the alkali metal ion. All larger
alkali metal ions cannot be accommodated in the
mean plane of the O2O2 cavity, but they are coordi-
nated by two such entities in a sandwich type fashion.
This then leads to a coordination polymeric structure
as proposed by Nabeshima et al.76 for their closed
crown ether type ligands. While they had no solid-
state evidence for this proposed conformation, we
have shown this effect here.
In comparison, there is a clear trend to form the 1:1
compounds between LM1 and M2, independently of
the alkali metal ion M2, in the solid state, while this is
not the case in solution. The solvents used, e.g. ace-
tonitrile and ethanol, are coordinating solvents able
to interact strongly with the (hard) alkali metal ions.
When single crystals of the 1:1 stoichiometry are re-
dissolved in a donor solvent, the structure falls apart
in solution, leading to 1:1 and 2:1 complexes with LM1
and M2 respectively, as seen in ESI-MS (see Fig. S28).
The alkali metal ions M2 are then also solvated by the
solvent which acts as a concurrent donor with respect
to the LM1 complexes.
The solid-state structures predominantly form one-
dimensional coordination polymers, either by bridg-
ing water molecules, nitrate anions or the alkali metal
ions themselves. The lithium ion is too small to fill
the O2O2 cavity in the copper compound, while it is
well coordinated by all four O-atoms in the nickel
Figure 9: Crystal structure of the sandwich confor-
mation of (LNi)2Cs complex 10 (#1(x, ½-y, ½+z)) with a
Ni(II)-Ni(II) inteaction (dashed bond). All H-atoms are
omitted for clarity.
So far, only one 2:1 compound “(LNi)2Cs” (10) has
been isolated in the solid state, probably a result of
the use of a bulky, non-polar solvent. Although we
tried to use this or similar solvents to produce other
2:1 complexes as single crystals, compound 10 re-
mains the only such example to date.
CONCLUSION
The synthesis of heterometallic complexes upon
reaction of a salen-type ligand with M1 = Cu(II) or
Ni(II), and different alkali nitrate salts has been in-
vestigated. We showed that the coordination of the
transition metal ion is crucial for the preorganization
of the ligand to bind the alkali metal ion M2. Hence,
the coordination of the N2O2 chelating site of the
ligand to M1 produces an Ω-shaped O2O2 recognition
9
ACS Paragon Plus Environment

Crystal Growth & Design
Page 10 of 34
1
2
3
4
5
6
7
8
9
site which can easily host alkali metal ions M2 similar
IPDS-II or IPDS-II T diffractometers equipped with
Oxford Cryosystem open-flow cryostats.95 Single
crystals were picked under the microscope, and
placed in inert oil. All crystals were mounted on loops
and all geometric and intensity data were taken from
one single crystal. The absorption corrections were
partially integrated in the data reduction procedure.96
The structures were solved and refined using full-
matrix least-squares on F2 with the SHELX-2014
package97, 98. All atoms (except hydrogen atoms) were
refined anisotropically. Hydrogen atoms were refined
where possible, and otherwise added using the riding
model position parameters. Crystallographic data can
be found in the Supporting Information (see Table
S1). CIF files can be obtained from the Cambridge
Crystallographic Data Centre, CCDC-1497630 (1),
CCDC-1518363 (1’), CCDC-1497673 (2), CCDC-1518361
(2’), CCDC-1497674 (4), and CCDC-1497675 (5),
CCDC-1497676 (6), CCDC-1497677 (7), CCDC-
1518362 (7’), CCDC-1497678 (8), CCDC-1497679 (9),
CCDC- 1497680 (10). Copies of these data can be
obtained free of charge from the Cambridge Crystal-
lographic Data Centre via www.ccdc.cam.ac.uk or e-
mail, deposit@ccdc.cam.ac.uk. Powder X-ray spectra
were collected on a Stoe STADIP using Cu-Kα1 radia-
tion (1.5406 Å) using a Mythen detector.
to crown ethers. The M2 recognition was investigated
1
in solution by UV-Vis and H-NMR titration at differ-
ent temperatures and clearly showed the presence of
the 2:1 LM1:M2 compounds next to 1:1 complexes upon
addition of the alkali salt. The presence of two species
(2:1 and 1:1) in solution was also demonstrated by ESI
mass spectrometry where both masses can be ob-
served, even when the 1:1 solid state compounds are
redissolved in solution. The compound correspond-
ing to the 1:1 ratio is also indicative of the presence of
oligomers stemming from a coordination polymer.
Furthermore, the use of different solvents, equiva-
lents of alkali salt with respect to LM1, as well as
counter-ions lead in almost all cases to the 1:1 coordi-
nation compounds. An equilibrium involving mixed
metal complexes with different stoichiometries in
solution was thus demonstrated, while in most cases,
one single stoichiometry was preferred in the solid
state. The X-ray crystallographic analysis of the dif-
ferent alkali complexes shows a size-dependent coor-
dination of the alkali metal ions by the O2O2 cavity.
While Li(I) and Na(I) ions fit into this compartment,
the coordination of the K(I), Rb(I) or Cs(I) ions oc-
curs by two different ligands, leading to a bridging via
the alkali metal ions into 1D coordination polymers.
Such heteromultimetallic salen-based complexes
juxtaposing two metals ions within one ligand entity
are of crucial significance in diverse research areas. In
particular, the development of oxide material precur-
sors and optical chemosensors from these com-
pounds is currently ongoing in our group.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Synthesis
Synthesis of Lithium Complex [{LCuLi(µ-NO3)(µ-
H2O)}2]n “LCuLi” (1). A solution of LiNO3 (18 mg,
0.256 mmol) was added to a solution of LCu (100 mg,
0.256 mmol), previously dissolved in a mixture of
acetonitrile/ethanol (7:3, 30 ml). The reaction mix-
ture turned dark purple immediately. After stirring
for 2h at room temperature, the solvent of the result-
ing solution was removed under reduced pressure to
produce a powder of the complex (1) (110 mg, 90%).
X-ray-suitable single crystals were obtained by dis-
solving (1) in a mixture of acetonitrile/ethanol (7:3, 30
ml), which was allowed to evaporate at room temper-
ature for one week; purple, needle-like single crystals
resulted. ESI-MS (m/z): 396.1 [M+H]+. Anal. Calcd for
C22H27CuLiN3O5 (1): C, 55.65; H, 5.63; N, 8.80%.
Found: C, 54.6; H, 5.61; N, 8.68%.
EXPERIMENTAL SECTION
All experiments were performed in air and at RT.
Ligand H2L was prepared according to the procedure
reported by Avecilla et al.77 “LCu” and LNi were syn-
thesized as described in the literature.83 84 All chemi-
cals were commercial products of reagent grade and
1
were used without further purification. H and 13C
measurements were carried out for the Ni-
compounds with a Bruker 400 MHz spectrometer at
ambient temperature, and chemical shifts are given
in ppm with respect to the residual solvent peak.
Mass spectra (ESI-TOF, positive mode) were recorded
with a Bruker esquire HCT spectrometer with a
DMF/ACN mixture as solvent. The UV/Vis spectra
were recorded with a Perkin–Elmer Lambda 40 spec-
trometer. The elemental analysis relative to the nickel
compounds are not shown in the presented work due
to the possible interferences with the metal during
the mineralization. The crystallographic data of sin-
gle crystals were collected with Mo-Kα radiation (λ =
0.71073 Å). All measurements were performed at 200
K, or 250 K for the compounds 1’, 2’ and 7’, with Stoe
Synthesis of Lithium Complex [(LCuLi(NO3))2(µ-
H2O)] “LCuLi’” (1’). A solution of LiNO3 (18 mg, 0.256
mmol) was added to a solution of LCu (100 mg, 0.256
mmol), previously dissolved in a mixture of acetoni-
trile/ethanol (7:3, 30 ml). The reaction mixture
turned dark purple immediately. After stirring for 2h
at room temperature, the resulting solution was par-
tially evaporated and the product precipitated with
diethyl ether. The precipitate was collected by filtra-
tion and dried under vacuum to produce the complex
(1’) (105 mg, 86%). The filtrate was allowed to stand at
room temperature for one week after partial evapora-
10
ACS Paragon Plus Environment

Page 11 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
tion of the solvent; dark green, needle-like single
]+. Anal. Calcd for C24H30CuN4O5Rb (4): C, 47.76; H,
5.01; N, 9.28%. Found: C, 48.01; H, 5.19; N, 9.07%.
crystals suitable for X-ray crystallographic analysis
were obtained. ESI-MS (m/z): 396.1 [M+H]+.
Synthesis of Sodium Complex [LCuNa(NO3)]n
“LCuNa” (2). A solution of NaNO3 (22 mg, 0.256
mmol) was added to a solution of LCu (100 mg, 0.256
mmol) in a mixture of acetonitrile/ethanol (7:3, 30
ml). The mixture turned red immediately and the
reaction was stirring for 2h at room temperature. Red
rhombohedral-like single crystals were obtained by
vapor phase diffusion of diethyl ether into the mother
liquor of the reaction in a long tube. ESI-MS (m/z):
412.0 [M+H]+. Anal. Calcd for C19H19.5CuNaN2.5O4 (2):
C, 52.65; H, 4.24; N, 8.08%. Found: C, 54.97; H, 4.43;
N, 7.74%.
Synthesis of Cesium Complex [LCuCs(µ-NO3)]n
“LCuCs” (5). A solution of CsNO3 (50 mg, 0.256
mmol) in water (10 ml) was added to a solution of
LCu (100 mg, 0.256 mmol) in a mixture of acetoni-
trile/ethanol (7:3, 30 ml). The mixture turned purple
immediately. After the mixture was stirred for 2h at
room temperature, the metallic purple precipitate
was collected and dried under vacuum to produce the
complex (5) (159 mg, 96%). The filtrate was allowed
to stand at room temperature for four weeks. The
solvent was partially evaporated and purple needle-
like single crystals suitable for X-ray crystallographic
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
analysis were obtained. H NMR (400 MHz, DMSO-
d6): δ(ppm) 3.41 (s, 4H), 3.69 (s, 6H), 6.44-6.45 (t, J=
7.8 Hz, 2H), 6.76-7.78 (dd, J=7.6, 1.5 Hz, 2H), 6.85-
6.88 (dd, J=8, 1.6 Hz, 2H), 7.87 (s, 2H). ESI-MS (m/z):
407.1 [M+H]+. ]+. Anal. Calcd for C24H30CsCuN4O5 (5):
C, 44.28; H, 4.65; N, 8.61%. Found: C, 44.73; H, 4.55;
N, 8.52%.
Synthesis of Sodium Complex [{LCuNa(NO3)}3]n
“LCuNa’” (2’). A solution of NaNO3 (22 mg, 0.256
mmol) was added to a solution of LCu (100 mg, 0.256
mmol) in a mixture of acetonitrile/ethanol (7:3, 30
ml). The mixture turned red immediately and after
stirring for 2h at room temperature, the resulting
solution was partially evaporated and the product
precipitated with diethyl ether. The precipitate was
collected and dried under vacuum to afford the com-
plex (2’) (112 mg, 92%). After a few days, red needle-
like single crystals suitable for X-ray crystallographic
analysis were obtained by vapor phase diffusion of
diethyl ether into the mother liquor of the reaction in
a long tube. ESI-MS (m/z): 412.0 [M+H]+.
Synthesis of [(LNiLi(NO3))2(µ-H2O)] “LNiLi” (6),
[(LNiNa(NO3)] “LNiNa” (7), [(LNiK(µ-NO3)]n
“LNiK”
(8),
[(LNiRb(NO3)]n
“LNiRb”
(9),
[{(LNi)2Cs(NO3)}(HCCl3)]n “(LNi)2Cs” (10). These
compounds were prepared by the same method as
described above, by reacting LNi instead of LCu in an
acetonitrile/ethanol (7:3) solution with one equiva-
lent of the appropriate alkali metal salt. The metal
salts used were as follows: LiNO3 for 6, NaNO3 for 7,
KNO3 for 8, RbNO3 for 9 and CsNO3 for 10.
Synthesis of Potassium Complex “LCuK” (3). A
solution of KNO3 (26 mg, 0.256 mmol) was added to a
solution of LCu (100 mg, 0.256 mmol) in a mixture of
acetonitrile/ethanol (7:3, 30 ml). The mixture turned
purple immediately. After the mixture was stirred for
2h at room temperature, the precipitate was collected
and dried under vacuum to produce complex (3) (116
mg, 92%). ESI-MS (m/z): 428.0 [M+H]+. Anal. Calcd
for C26H36CuKN4O6 (3): C, 51.77; H, 6.02; N, 9.29%.
Found: C, 53.16; H, 6.62; N, 9.22%.
1
Data for 6. Yield: 91%. H NMR (400 MHz, DMSO-
d6): δ(ppm) 3.41 (s, 4H), 3.70 (s, 6H), 6.41-6.46 (t, J=
7.8 Hz, 2H), 6.76-7.79 (dd, J=7.6, 1.5 Hz, 2H), 6.86-
6.89 (dd, J=8, 1.6 Hz, 2H), 7.88 (s, 2H). ESI-MS (m/z):
391.1 [M+H]+. ]+.
1
Data for 7. Yield: 92%. H NMR (400 MHz, DMSO-
d6): δ(ppm) 3.41 (s, 4H), 3.69 (s, 6H), 6.44-6.45 (t, J=
7.8 Hz, 2H), 6.76-7.78 (dd, J=7.6, 1.5 Hz, 2H), 6.85-
6.88 (dd, J=8, 1.6 Hz, 2H), 7.87 (s, 2H). ESI-MS (m/z):
407.1 [M+H]+.
Synthesis of Rubidium Complex [LCuRb(µ-NO3)]n
“LCuRb” (4). A solution of RbNO3 (38 mg, 0.256
mmol) in water (10ml) was added to a solution of LCu
(100 mg, 0.256 mmol) in a mixture of acetoni-
trile/ethanol (7:3, 30 ml). The mixture turned purple
immediately. After the mixture was stirred for 2h at
room temperature, the metallic purple precipitate
was collected and dried under vacuum to produce
complex (4) (146 mg, 95%). The filtrate was allowed
to stand at room temperature for four weeks. The
solvent was partially evaporated and purple needle-
like single crystals suitable for X-ray crystallographic
analysis were obtained. ESI-MS (m/z): 473.9 [M+H]+.
1
Data for 8. Yield: 87%. H NMR (400 MHz, DMSO-
d6): δ(ppm) 3.42 (s, 4H), 3.72 (s, 6H), 6.50-6.55 (t, J=
7.8 Hz, 2H), 6.82-6.85(dd, J=7.6, 1.5 Hz, 2H), 6.90-6.93
(dd, J=8, 1.6 Hz, 2H), 7.92 (s, 2H). ESI-MS (m/z): 423.1
[M+H]+.
1
Data for 9. Yield: 89%. H NMR (400 MHz, DMSO-
d6): δ(ppm) 3.31 (s, 4H), 3.63 (s, 6H), 6.42-6.47 (t, J=
7.8 Hz, 2H), 6.70-7.72 (dd, J=7.6, 1.5 Hz, 2H), 6.83-
6.86 (dd, J=8, 1.6 Hz, 2H), 7.80 (s, 2H). ESI-MS (m/z):
469.0 [M+H]+.
11
ACS Paragon Plus Environment

Crystal Growth & Design
Page 12 of 34
1
2
3
4
5
6
7
1
Data for 10. Yield: 95%. H NMR (400 MHz, DMSO-
d6): δ(ppm) 3.33 (s, 4H), 3.63 (s, 6H), 6.40-6.46 (t, J=
7.8 Hz, 2H), 6.67-7.70 (dd, J=7.6, 1.5 Hz, 2H), 6.83-
6.86 (dd, J=8, 1.6 Hz, 2H), 7.81 (s, 2H). ESI-MS (m/z):
517.0 [M+H]+.
1.
2.
J.-M. Lehn, Toward self-organization
and complex matter, Science, 2002,
295, 2400-2403.
S. S. Sharma, K. J. Dietz and T.
Mimura, Vacuolar
8
9
Synthesis of Sodium Complex [LNiNa(MeOH)]
“LNiNa(MeOH)” (7’). A solution of NaNO3 (4 equiv.,
44.2 mg, 0.520 mmol) was added to a solution of LNi
(50 mg, 0.1530 mmol) in MeOH (10 ml) or a mixture
of DCM and MeOH (1:1, 10 ml). The mixture turned
red immediately and after stirring for 2h at room
temperature, the precipitate was collected and dried
under vacuum to produce the complex (7’) (119 mg,
97%). After a few days, red needle-like single crystals
suitable for X-ray crystallographic analysis were ob-
tained by slow evaporation of the mother liquor of
compartmentalization as indispensable
component of heavy metal
detoxification in plants, Plant, cell &
environment, 2016.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3.
4.
I. Pinchuk and D. Lichtenberg, The
effect of compartmentalization on the
kinetics of transition metal ions-
induced lipoprotein peroxidation,
Chemistry and physics of lipids, 2016,
195, 39-46.
S. Akine, T. Matsumoto and T.
Nabeshima, Overcoming Statistical
Complexity: Selective Coordination
of Three Different Metal Ions to a
Ligand with Three Different
Coordination Sites, Angewandte
Chemie International Edition, 2016,
55, 960-964.
T. Nakamura, H. Kimura, T. Okuhara,
M. Yamamura and T. Nabeshima, A
Hierarchical Self-Assembly System
Built Up from Preorganized Tripodal
Helical Metal Complexes, Journal of
the American Chemical Society, 2016,
138, 794-797.
E. M. Tristani, J. I. Wirgau, G. R.
Dubay, J. W. Sibert and A. L.
Crumbliss, Siderophore-redox active
ionophore host-guest assemblies: A
prototype for selective metal ion
compartmentalization, Inorganica
Chimica Acta, 2010, 363, 3611-3615.
A. Biswas, S. Mondal and S.
Mohanta, Syntheses,
1
the reaction. H NMR (400 MHz, DMSO-d6): δ(ppm)
3.41 (s, 4H), 3.69 (s, 6H), 6.44-6.45 (t, J= 7.8 Hz, 2H),
6.76-7.78 (dd, J=7.6, 1.5 Hz, 2H), 6.85-6.88 (dd, J=8,
1.6 Hz, 2H), 7.87 (s, 2H). ESI-MS (m/z): 407.1 [M+H]+.
1H-NMR Spectroscopy Titration. Samples of LNi
were prepared in deuterated DMSO varying the
M(NO3) concentration from 0 to 3 equiv. (M= Li, Na,
K, Rb, Cs) with a volume of 0.5 mL in the NMR tube.
Spectra of the nickel complexes were recorded at
ambient temperature in a 400 MHz. A Job plot was
performed under the conditions where the sum of the
concentration of the host and the guest is constant,
namely [0.04 M] in DMSO. Due to the para-
5.
6.
7.
1
magnetism of the Cu(II) compounds, no H NMR
measurement has been performed on these complex-
es.
UV-Vis Titration. Samples containing 0.1 mM of LCu
in acetonitrile were prepared (3 mL in the cuvette).
Additions from 0 to 3 equiv. of alkali metal salts were
performed using 0.03 M solutions of M(NO3) (M= Li,
Na, K, Rb, Cs) in DMSO (addition of 2 µL), respec-
tively. Spectra were recorded at ambient temperature
in a 1-mm-path-length quartz cell on a Perkin–Elmer
Lambda 40 spectrometer. A Job plot was performed
under the conditions where the sum of the concen-
tration of the host and the guest is constant, namely
[0.0001 M] in a mixture of DMSO and acetonitrile.
ACKNOWLEDGEMENTS
characterizations, and crystal
structures of 3d–s/d10 metal
complexes derived from two
compartmental Schiff base ligands,
Journal of Coordination Chemistry,
2013, 66, 152-170.
A.F. is grateful to Emmanuel Kottelat for fruitful
discussions. This work was supported by the Swiss
National Science Foundation (grant number
200020_152777), by Frimat and the University of Fri-
bourg.
REFERENCES
12
ACS Paragon Plus Environment

Page 13 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
8.
S. Akine, A. Akimoto, T. Shiga, H.
15.
16.
L. Canali and D. C. Sherrington,
Utilisation of homogeneous and
supported chiral metal (salen)
complexes in asymmetric catalysis,
Chemical Society Reviews, 1999, 28,
85-93.
C. Baleizão, B. Gigante, M. J.
Sabater, H. Garcia and A. Corma, On
the activity of chiral chromium salen
complexes covalently bound to solid
silicates for the enantioselective
epoxide ring opening, Applied
Catalysis A: General, 2002, 228, 279-
288.
M. Andruh, R. Clerac, D. Visinescu,
M.-G. Alexandru, A. M Madalan, C.
Mathonier and I.-R. Jeon, A new
family of [CuIILnIIIMV]
heterotrimetallic complexes (Ln = La,
Gd, Tb; M = Mo, W): Model systems
to probe exchange interactions and
Single-Molecule Magnet properties,
2016.
Oshio and T. Nabeshima, Synthesis,
stability, and complexation behavior
of isolable salen-type N2S2 and
N2SO ligands based on thiol and
oxime functionalities, Inorganic
chemistry, 2008, 47, 875-885.
A. W. Kleij, Zinc-centred salen
complexes: versatile and accessible
supramolecular building motifs,
Dalton Transactions, 2009, 4635-
4639.
N. S. Venkataramanan, G. Kuppuraj
and S. Rajagopal, Metal–salen
complexes as efficient catalysts for
the oxygenation of heteroatom
containing organic compounds—
synthetic and mechanistic aspects,
Coordination chemistry reviews,
2005, 249, 1249-1268.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
9.
10.
17.
11.
12.
13.
14.
M. Mechler, W. Frey and R. Peters,
Macrocyclic salen–bis-NHC hybrid
ligands and their application to the
synthesis of enantiopure bi-and
trimetallic complexes,
18.
19.
K. Gupta and A. K. Sutar, Catalytic
activities of Schiff base transition
metal complexes, Coordination
Chemistry Reviews, 2008, 252, 1420-
1450.
Organometallics, 2014, 33, 5492-
5508.
E. Gallo, E. Solari, C. Floriani, A.
Chiesi-Villa and C. Rizzoli, Use of
Manganese (II)− Schiff Base
Complexes for Carrying Polar
Organometallics and Inorganic Ion
Pairs, Inorganic chemistry, 1997, 36,
2178-2186.
W. Zhang, J. L. Loebach, S. R.
Wilson and E. N. Jacobsen,
Enantioselective epoxidation of
unfunctionalized olefins catalyzed by
salen manganese complexes, Journal
of the American Chemical Society,
1990, 112, 2801-2803.
S. Akine, T. Taniguchi and T.
Nabeshima, Acyclic bis (N2O2
chelate) ligand for trinuclear d-block
homo-and heterometal complexes,
Inorganic chemistry, 2008, 47, 3255-
3264.
M. Mousavi, V. Béreau, J.-P. Costes,
C. Duhayon and J.-P. Sutter,
Oligomeric and polymeric
organizations of potassium salts with
compartmental Schiff-base complexes
Y. Hai, J.-J. Chen, P. Zhao, H. Lv, Y.
Yu, P. Xu and J.-L. Zhang,
20.
21.
Luminescent zinc salen complexes as
single and two-photon fluorescence
subcellular imaging probes, Chemical
Communications, 2011, 47, 2435-
2437.
P. G. Cozzi, Metal–Salen Schiff base
complexes in catalysis: practical
aspects, Chemical Society Reviews,
2004, 33, 410-421.
13
ACS Paragon Plus Environment

Crystal Growth & Design
Page 14 of 34
1
2
3
4
5
6
7
8
9
as ligands, CrystEngComm, 2011, 13,
5908-5914.
Physical, Theoretical, 1968, 1699-
1703.
S. Karasawa, K. Nakano, D.
Yoshihara, N. Yamamoto, J.-i.
Tanokashira, T. Yoshizaki, Y. Inagaki
and N. Koga, Magnetic Properties of
1: 2 Mixed Cobalt (II)
22.
23.
X. Lü, W. Y. Wong and W. K. Wong,
Self‐Assembly of Luminescent
Platinum‐Salen Schiff‐Base
Complexes, European Journal of
Inorganic Chemistry, 2008, 2008,
523-528.
J. Cheng, X. Ma, Y. Zhang, J. Liu, X.
Zhou and H. Xiang, Optical
chemosensors based on
29.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Salicylaldehyde Schiff-Base
Complexes with Pyridine Ligands
Carrying High-Spin Carbenes (S car=
2/2, 4/2, 6/2, and 8/2) in Dilute Frozen
Solutions: Role of Organic Spin in
Heterospin Single-Molecule Magnets,
Inorganic chemistry, 2014, 53, 5447-
5457.
R. E. Winpenny, The structures and
magnetic properties of complexes
containing 3d-and 4f-metals,
Chemical Society Reviews, 1998, 27,
447-452.
A. W. Jeevadason, K. K. Murugavel
and M. Neelakantan, Review on
Schiff bases and their metal
complexes as organic photovoltaic
materials, Renewable and Sustainable
Energy Reviews, 2014, 36, 220-227.
A. Kajal, S. Bala, S. Kamboj, N.
Sharma and V. Saini, Schiff bases: a
versatile pharmacophore, Journal of
Catalysts, 2013, 2013.
J.-P. Sutter, S. Dhers, R. Rajamani, S.
Ramasesha, J.-P. Costes, C. Duhayon
and L. Vendier, Hetero-Metallic {3d-
4f-5d} Complexes: Preparation and
Magnetic Behavior of Trinuclear
[(LMe2Ni− Ln){W (CN) 8}]
Compounds (Ln= Gd, Tb, Dy, Ho, Er,
Y; LMe2= Schiff base) and Variable
SMM Characteristics for the Tb
Derivative, Inorganic chemistry,
2009, 48, 5820-5828.
transmetalation of salen-based Schiff
base complexes, Inorganic chemistry,
2014, 53, 3210-3219.
24.
25.
S. K. Shoora, A. K. Jain and V. K.
Gupta, A simple Schiff base based
novel optical probe for aluminium
(III) ions, Sensors and Actuators B:
Chemical, 2015, 216, 86-104.
P. L. Then, C. Takehara, Y. Kataoka,
M. Nakano, T. Yamamura and T.
Kajiwara, Structural switching from
paramagnetic to single-molecule
magnet behaviour of LnZn 2
30.
31.
trinuclear complexes, Dalton
Transactions, 2015, 44, 18038-18048.
C. Takehara, P. L. Then, Y. Kataoka,
M. Nakano, T. Yamamura and T.
Kajiwara, Slow magnetic relaxation of
light lanthanide-based linear LnZn 2
trinuclear complexes, Dalton
Transactions, 2015, 44, 18276-18283.
M. Gerloch, J. Lewis, F. Mabbs and
A. Richards, The preparation and
magnetic properties of some Schiff
base–iron (III) halide complexes,
Journal of the Chemical Society A:
Inorganic, Physical, Theoretical,
1968, 112-116.
J. Lewis, F. Mabbs and H. Weigold,
The magnetic properties of some
manganese (II) Schiff-base complexes
and the oxidation products of NN′-
ethylenebis (salicylaldiminato)
manganese (II), Journal of the
Chemical Society A: Inorganic,
32.
33.
26.
27.
28.
34.
S. Zhao, X. Lü, A. Hou, W.-Y. Wong,
W.-K. Wong, X. Yang and R. A.
Jones, Heteronuclear trimetallic and
1D polymeric 3d–4f Schiff base
complexes with OCN− and SCN−
14
ACS Paragon Plus Environment

Page 15 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
ligands, Dalton Transactions, 2009,
9595-9602.
salen type ligand, Polyhedron, 2004,
23, 963-967.
35.
K.-Q. Hu, S.-Q. Wu, G.-Y. An, A.-L.
Cui and H.-Z. Kou, Syntheses,
structure, and magnetic properties of
heteronuclear Cu (ii) 4 Fe (iii) 4
cluster and Cu (ii) 8 bimetallacycles,
Dalton Transactions, 2013, 42, 1102-
1108.
41.
M. Maneiro, M. R. Bermejo, M. I.
Fernandez, E. Gómez-Fórneas, A. M.
González-Noya and A. M. Tyryshkin,
A new type of manganese-Schiff base
complex, catalysts for the
disproportionation of hydrogen
peroxide as peroxidase mimics, New
Journal of Chemistry, 2003, 27, 727-
733.
A. K. Crane and M. J. MacLachlan,
Portraits of Porosity: Porous
Structures Based on Metal Salen
Complexes, European Journal of
Inorganic Chemistry, 2012, 2012, 17-
30.
A. C. Leung and M. J. MacLachlan,
Schiff base complexes in
macromolecules, Journal of Inorganic
and Organometallic Polymers and
Materials, 2007, 17, 57-89.
J. K. H. Hui, Z. Yu and M. J.
MacLachlan, Supramolecular
Assembly of Zinc Salphen
Complexes: Access to Metal‐
Containing Gels and Nanofibers,
Angewandte Chemie International
Edition, 2007, 46, 7980-7983.
H. Zhou, C. Chen, Y. Liu and X.
Shen, Construction of copper (II)–
dysprosium (III)–iron (III) trinuclear
cluster based on Schiff base ligand:
Synthesis, structure and magnetism,
Inorganica Chimica Acta, 2015, 437,
188-194.
M. Sarwar, A. M. Madalan, C.
Tiseanu, G. Novitchi, C. Maxim, G.
Marinescu, D. Luneau and M.
Andruh, A new synthetic route
towards binuclear 3d–4f complexes,
using non-compartmental ligands
derived from o-vanillin. Syntheses,
crystal structures, magnetic and
luminescent properties, New Journal
of Chemistry, 2013, 37, 2280-2292.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
36.
37.
X. Gong, Y.-Y. Ge, M. Fang, Z.-G.
Gu, S.-R. Zheng, W.-S. Li, S.-J. Hu,
S.-B. Li and Y.-P. Cai, Construction
of four 3d-4d/4d complexes based on
salen-type schiff base ligands,
CrystEngComm, 2011, 13, 6911-6915.
P. Seth, S. Ghosh, A. Figuerola and A.
Ghosh, Trinuclear heterometallic Cu
II–Mn II complexes of a salen type
Schiff base ligand: anion dependent
variation of phenoxido bridging
angles and magnetic coupling, Dalton
Transactions, 2014, 43, 990-998.
M. R. Bermejo, R. Carballido, M. I.
Fernández-García, A. M. González-
Noya, G. González-Riopedre, M.
Maneiro and L. Rodríguez-Silva,
Synthesis, Characterization, and
Catalytic Studies of Mn (III)-Schiff
Base-Dicyanamide Complexes:
Checking the Rhombicity Effect in
Peroxidase Studies, Journal of
Chemistry, 2017, 2017.
42.
43.
44.
38.
45.
46.
39.
40.
M. R. Bermejo, M. I. Fernández, A.
M. González-Noya, M. Maneiro, R.
Pedrido, M. J. Rodríguez, J. C.
García-Monteagudo and B.
Donnadieu, Novel peroxidase mimics:
μ-Aqua manganese–Schiff base
dimers, Journal of inorganic
biochemistry, 2006, 100, 1470-1478.
J. Sanmartın, A. M. Garcıa-Deibe, M.
́
́
Fondo, D. Navarro and M. R.
Bermejo, Synthesis and crystal
structure of a mononuclear iron (III)(η
2-acetato) complex of a β-cis folded
15
ACS Paragon Plus Environment

Crystal Growth & Design
Page 16 of 34
1
2
3
4
5
6
7
8
9
47.
R. Modak, Y. Sikdar, G. Cosquer, S.
Dalton Transactions, 2014, 43, 5558-
5563.
A. Crochet, J.-P. Brog and K. M.
Fromm, Mixed Metal Multinuclear Cr
(III) Cage Compounds and
Coordination Polymers Based on
Unsubstituted Phenolate: Design,
Synthesis, Mechanism, and Properties,
Crystal Growth & Design, 2015, 16,
189-199.
K. M. Fromm, A. Crochet, Y.
Cheremond, F. Gschwind and W.
Maudez, 2013.
F. Gschwind, A. Crochet, W. Maudez
and K. M. Fromm, From Alkaline
Earth Ion Aggregates via Transition
Metal Coordination Polymer
Networks towards Heterometallic
Single Source Precursors for Oxidic
Materials, CHIMIA International
Journal for Chemistry, 2010, 64, 299-
302.
H. Xu, R. Chen, Q. Sun, W. Lai, Q.
Su, W. Huang and X. Liu, Recent
progress in metal–organic complexes
for optoelectronic applications,
Chemical Society Reviews, 2014, 43,
3259-3302.
T. K. Ronson, S. Zarra, S. P. Black
and J. R. Nitschke, Metal–organic
container molecules through
subcomponent self-assembly,
Chemical Communications, 2013, 49,
2476-2490.
P. D. Frischmann and M. J.
MacLachlan, Metallocavitands: An
emerging class of functional
multimetallic host molecules,
Chemical Society Reviews, 2013, 42,
871-890.
Chatterjee, M. Yamashita and S.
Goswami, Heterometallic CuII–DyIII
Clusters of Different Nuclearities with
Slow Magnetic Relaxation, Inorganic
chemistry, 2015, 55, 691-699.
S. J. Wezenberg and A. W. Kleij,
Material applications for salen
frameworks, Angewandte Chemie
International Edition, 2008, 47, 2354-
2364.
S. Matsunaga and M. Shibasaki,
Recent advances in cooperative
bimetallic asymmetric catalysis:
dinuclear Schiff base complexes,
Chemical Communications, 2014, 50,
1044-1057.
K. M. Fromm, J. L. Sagué and A. Y.
Robin, Silver coordination polymers
with isonicotinic acid derived short
polyethylene glycol–Synthesis,
structures, anion effect and solution
behavior, Inorganica Chimica Acta,
2013, 403, 2-8.
A. J. Heeger, Semiconducting and
metallic polymers: the fourth
generation of polymeric materials
(Nobel lecture), Angewandte Chemie
International Edition, 2001, 40, 2591-
2611.
55.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
48.
49.
56.
57.
50.
51.
58.
59.
60.
61.
52.
53.
Z. Wang, W. Ye, X. Luo and Z.
Wang, Fabrication of
Superhydrophobic and Luminescent
Rare Earth/Polymer complex Films,
Scientific reports, 2016, 6, 24682.
M. Y. Masoomi and A. Morsali,
Applications of metal–organic
coordination polymers as precursors
for preparation of nano-materials,
Coordination Chemistry Reviews,
2012, 256, 2921-2943.
A. Datta, K. Das, C. Massera, J. K.
Clegg, C. Sinha, J.-H. Huang and E.
Garribba, A mixed valent
heterometallic Cu II/Na I coordination
polymer with sodium–phenyl bonds,
A. M. Abu-Dief and I. M. Mohamed,
A review on versatile applications of
transition metal complexes
incorporating Schiff bases, Beni-suef
university journal of basic and
applied sciences, 2015, 4, 119-133.
54.
16
ACS Paragon Plus Environment

Page 17 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
62.
S. Y. Ebrahimipour, I. Sheikhshoaie,
tetradentate symmetrical Schiff base
ligand, Crystal Growth & Design,
2010, 10, 4014-4022.
G. Salassa, A. M. Castilla and A. W.
Kleij, Cooperative self-assembly of a
macrocyclic Schiff base complex,
Dalton Transactions, 2011, 40, 5236-
5243.
L. San Felices, E. C. Escudero-Adꢀn,
J. Benet-Buchholz and A. W. Kleij,
Isolation and structural
characterization of a binuclear
intermediate species pertinent to
transmetalation of Zn (salphen)
complexes and the formation of
polynuclear Salen structures,
Inorganic chemistry, 2008, 48, 846-
853.
A. Crochet, M. Khaleghi and K. M.
Fromm, A new mixed-ligand copper
(II) complex of (E)-N′-(2-
hydroxybenzylidene) acetohydrazide:
Synthesis, characterization, NLO
behavior, DFT calculation and
biological activities, Journal of
Molecular Structure, 2014, 1072, 267-
276.
T. D. Pasatoiu, C. Tiseanu, A. M.
Madalan, B. Jurca, C. Duhayon, J. P.
Sutter and M. Andruh, Study of the
luminescent and magnetic properties
of a series of heterodinuclear
[ZnIILnIII] complexes, Inorganic
chemistry, 2011, 50, 5879-5889.
A. Knizhnik, G. Shter, G. Grader, G.
Reisner and Y. Eckstein, Interrelation
of preparation conditions,
morphology, chemical reactivity and
homogeneity of ceramic YBCO,
Physica C: Superconductivity, 2003,
400, 25-35.
Z. Quan, E. Ni, S. Hayashi and N.
Sonoyama, Structure and
electrochemical properties of multiple
metal oxide nanoparticles as cathodes
of lithium batteries, Journal of
Materials Chemistry A, 2013, 1, 8848-
8856.
H. Ge, B. Zhang, X. Gu, H. Liang, H.
Yang, Z. Gao, J. Wang and Y. Qin, A
Tandem Catalyst with Multiple Metal
Oxide Interfaces Produced by Atomic
Layer Deposition, Angewandte
Chemie, 2016, 128, 7197-7201.
J. Brog, A. Crochet and K. Fromm,
Lithium metal aryloxide clusters as
starting products for oxide materials,
WO/2012/000123, 05-Jan-2012.
X.-X. Zhou, H.-C. Fang, Y.-Y. Ge, Z.-
Y. Zhou, Z.-G. Gu, X. Gong, G. Zhao,
Q.-G. Zhan, R.-H. Zeng and Y.-P.
Cai, Assembly of a series of trinuclear
zinc (II) compounds with N2O2 donor
69.
70.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
63.
64.
65.
66.
71.
S. Akine, T. Taniguchi and T.
Nabeshima, Helical metallohost-guest
complexes via site-selective
transmetalation of homotrinuclear
complexes, Journal of the American
Chemical Society, 2006, 128, 15765-
15774.
72.
73.
S. Akine, S. Hotate and T.
Nabeshima, A molecular leverage for
helicity control and helix inversion,
Journal of the American Chemical
Society, 2011, 133, 13868-13871.
S. Akine, S. Sairenji, T. Taniguchi
and T. Nabeshima, Stepwise helicity
inversions by multisequential metal
exchange, Journal of the American
Chemical Society, 2013, 135, 12948-
12951.
P. Bhowmik, S. Chatterjee and S.
Chattopadhyay, Heterometallic
inorganic–organic frameworks of
sodium–nickel (vanen): Cation–π
interaction, trigonal dodecahedral Na+
and unprecedented heptadentate
coordination mode of vanen 2−,
Polyhedron, 2013, 63, 214-221.
N. Mahlooji, M. Behzad, H. A.
Rudbari, G. Bruno and B. Ghanbari,
74.
75.
67.
68.
17
ACS Paragon Plus Environment

Crystal Growth & Design
Page 18 of 34
1
2
3
4
5
6
7
8
9
Unique examples of copper
81.
E. N. Jacobsen, W. Zhang, A. R.
Muci, J. R. Ecker and L. Deng, Highly
enantioselective epoxidation catalysts
derived from 1, 2-
diaminocyclohexane, Journal of the
American Chemical Society, 1991,
113, 7063-7064.
F. J. Uribe-Romo, J. R. Hunt, H.
Furukawa, C. Klꢁck, M. O’Keeffe and
O. M. Yaghi, A crystalline imine-
linked 3-D porous covalent organic
framework, Journal of the American
Chemical Society, 2009, 131, 4570-
4571.
S. Majumder, R. Koner, P. Lemoine,
M. Nayak, M. Ghosh, S. Hazra, C. R.
Lucas and S. Mohanta, Role of
Coordinated Water and Hydrogen‐
Bonding Interactions in Stabilizing
Monophenoxido‐Bridged Triangular
CuIIMIICuII Compounds (M= Cu,
Co, Ni, or Fe) Derived from N, N′‐
Ethylenebis (3‐
methoxysalicylaldimine): Syntheses,
Structures, and Magnetic Properties,
European Journal of Inorganic
Chemistry, 2009, 2009, 3447-3457.
S. Sarkar, M. Nayak, M. Fleck, S.
Dutta, U. Flörke, R. Koner and S.
Mohanta, Syntheses, Crystal
Structures and Mass Spectrometry of
Mononuclear NiII Inclusion Product
and Self‐Assembled [2× 1+ 1× 2]
NiII3MII (M= Cu, Ni, Co, Fe or Mn)
Cocrystals Derived from N, N′‐
Ethylenebis (3‐
ethoxysalicylaldimine), European
Journal of Inorganic Chemistry, 2010,
2010, 735-743.
A. Jana, S. Majumder, L. Carrella, M.
Nayak, T. Weyhermueller, S. Dutta,
D. Schollmeyer, E. Rentschler, R.
Koner and S. Mohanta, Syntheses,
Structures, and Magnetic Properties of
Diphenoxo-Bridged CuIILnIII and
NiII (Low-Spin) LnIII Compounds
(II)/sodium (I) and nickel (II)/sodium
(I) Schiff base complexes with
bridging bis-bidentate Salen type
ligand: Synthesis, crystal structures
and antibacterial studies, Inorganica
Chimica Acta, 2016, 445, 124-128.
S. Akine, F. Utsuno, S. Piao, H. Orita,
S. Tsuzuki and T. Nabeshima,
Synthesis, Ion Recognition Ability,
and Metal-Assisted Aggregation
Behavior of Dinuclear Metallohosts
Having a Bis (Saloph) Macrocyclic
Ligand, Inorganic chemistry, 2016,
55, 810-821.
I. Correia, J. C. Pessoa, M. T. Duarte,
M. da Piedade, T. Jackush, T. Kiss,
M. Castro, C. F. Geraldes and F.
Avecilla, Vanadium (IV and V)
Complexes of Schiff Bases and
Reduced Schiff Bases Derived from
the Reaction of Aromatic o‐
Hydroxyaldehydes and Diamines:
Synthesis, Characterisation and
Solution Studies, European journal of
inorganic chemistry, 2005, 2005, 732-
744.
T. Nabeshima, Regulation of ion
recognition by utilizing information at
the molecular level, Coordination
chemistry reviews, 1996, 148, 151-
169.
S. Hazra, P. Chakraborty and S.
Mohanta, Heterometallic Copper (II)–
Tin (II/IV) Salts, Cocrystals and Salt
Cocrystals: Selectivity and Structural
Diversity Depending on Ligand
Substitution and Metal Oxidation
State, Crystal Growth & Design,
2016.
S. N. Spisak, Z. Wei, A. Y. Rogachev,
T. Amaya, T. Hirao and M. A.
Petrukhina, Double Concave Cesium
Encapsulation by Two Charged
Sumanenyl Bowls, Angewandte
Chemie, 2017, 129, 2626-2631.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
76.
77.
82.
83.
78.
79.
84.
85.
80.
18
ACS Paragon Plus Environment

Page 19 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Derived from a Compartmental
Synthesis and Structures, European
Journal of Inorganic Chemistry, 2004,
2004, 1115-1124.
M. L. Cole, C. Jones and P. C. Junk,
Ether and crown ether adduct
Ligand (Ln= Ce− Yb), Inorganic
chemistry, 2010, 49, 9012-9025.
A. Bhunia, P. W. Roesky, Y. Lan, G.
E. Kostakis and A. K. Powell, Salen-
based infinite coordination polymers
of nickel and copper, Inorganic
chemistry, 2009, 48, 10483-10485.
M. Odabaşoğlu, F. Arslan, H. Ölmez
and O. Büyükgüngör, Synthesis,
crystal structures and spectral
characterization of trans-bisaquabis
(o-vanillinato) copper (II), cis-aquabis
(o-vanillinato) copper (II) and aqua
[bis (o-vanillinato)-1, 2-
86.
87.
93.
complexes of sodium and potassium
cyclopentadienide and
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
methylcyclopentadienide—molecular
structures of [Na (dme) Cp]∞,[K
(dme) 0.5 Cp]∞,[Na (15-crown-5)
Cp],[Na (18-crown-6) Cp Me] and the
“naked Cp−” complex [K (15-crown-
5) 2][Cp], Journal of the Chemical
Society, Dalton Transactions, 2002,
896-905.
M. Veidis, G. Schreiber, T. Gough
and G. J. Palenik, Jahn-Teller
distortions in octahedral copper (II)
complexes, Journal of the American
Chemical Society, 1969, 91, 1859-
1860.
J. t. Cosier and A. Glazer, A nitrogen-
gas-stream cryostat for general X-ray
diffraction studies, Journal of Applied
Crystallography, 1986, 19, 105-107.
E. Blanc, D. Schwarzenbach and H.
Flack, The evaluation of transmission
factors and their first derivatives with
respect to crystal shape parameters,
Journal of applied crystallography,
1991, 24, 1035-1041.
ethylenediimin] copper (II), Dyes and
pigments, 2007, 75, 507-515.
94.
88.
89.
P. K. Saha, B. Dutta, S. Jana, R. Bera,
S. Saha, K.-i. Okamoto and S. Koner,
Immobilization of a copper-Schiff
base complex in a Y-zeolite matrix:
preparation, chromogenic behavior
and catalytic oxidation, Polyhedron,
2007, 26, 563-571.
J. Tedim, S. Patrício, R. Bessada, R.
Morais, C. Sousa, M. B. Marques and
C. Freire, Third‐Order Nonlinear
Optical Properties of DA‐salen‐Type
Nickel (II) and Copper (II)
Complexes, European journal of
inorganic chemistry, 2006, 2006,
3425-3433.
A. B. P. Lever, Inorganic electronic
spectroscopy, 1968.
W. Liu and H. H. Thorp, Bond
valence sum analysis of metal-ligand
bond lengths in metalloenzymes and
model complexes. 2. Refined
distances and other enzymes,
Inorganic Chemistry, 1993, 32, 4102-
4105.
95.
96.
97.
98.
G. M. Sheldrick, SHELX-97, program
for the solution and refinement of
crystal structures, University of
Göttingen, Germany, 1997.
G. M. Sheldrick, Crystal structure
refinement with SHELXL, Acta
Crystallographica Section C:
90.
91.
Structural Chemistry, 2015, 71, 3-8.
92.
H. Nöth and M. Warchhold, Sodium
Hydro (isothiocyanato) borates:
19
ACS Paragon Plus Environment

Crystal Growth & Design
Page 20 of 34
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Based on a Ω-shaped salen-type ligand affording an N2O2 as well as an O2O2 coordination site,
mixed metal coordination compounds with Cu(II) or Ni(II) and alkali metal ions have been syn-
thetized adopting different structures. In the latter case, the coordination geometry is mainly
governed by the size of the alkali metal ion as well as the transition metal ion used.
20
ACS Paragon Plus Environment

Page 21 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(a) 1H NMR titration of LNi with NaNO3 forming the complex LNiNa. (b) 1H NMR titration binding isotherm of
the LNiNa complex formation focused on the imine proton signal and a Job plot performed with constant
total concentration of [0.04 M].
247x255mm (96 x 96 DPI)
ACS Paragon Plus Environment

Crystal Growth & Design
Page 22 of 34
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1H NMR titration binding isotherm of the LNiNa complex formation focused on the imine proton signal at
0°C, RT and 50°C and their corresponding fitted curves.
163x124mm (96 x 96 DPI)
ACS Paragon Plus Environment

Page 23 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
UV-Vis titration of the LCu with NaNO3 complex. Diminution of the absorbance of the two first bands along
the titration and appearance of the two isobestic points. Binding isotherm of LCuNa focused on the first
band and a Job plot performed with constant total concentration of [0.0001 M].
251x101mm (96 x 96 DPI)
ACS Paragon Plus Environment

Crystal Growth & Design
Page 24 of 34
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Crystal structure of LCuLi complex 1 (#1 (1+x, y, z)) bridged by one molecule of water and two nitrate ions
and its corresponding 1D coordination polymer formation. H-atoms except for water are omitted for clarity.
110x176mm (96 x 96 DPI)
ACS Paragon Plus Environment

Page 25 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Crystal structure of LCuNa complex 2 (#1(ꢀ1+x, y, z), #2(1+x, y, z), #3( ½ ꢀx, 1ꢀy, ½+z) ,#4( 3/2 ꢀx, 1ꢀ
y, ꢀ ½ +z)), its Na(I) ̶ πꢀsystem packing and Cu(II) ̶ꢀC4 interaction (dash bonds). All Hꢀatoms are omitted
for clarity.
118x209mm (96 x 96 DPI)
ACS Paragon Plus Environment

Crystal Growth & Design
Page 26 of 34
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Crystal structure of the 1D coordination of LCuRb complex 4 (above, #3( ½ -x, ½+y, ½-z), #4(x, 1+y, z),
#5( ½ -x, 3/2 +y, ½-z)) and, LCuCs complex 5 showing a tail to face packing (#1( ½ -x, ½+y, ½-z), #4(
½ -x, - ½ +y, ½-z), #7(x, 1+y, z)). All H-atoms are omitted for clarity.
114x213mm (96 x 96 DPI)
ACS Paragon Plus Environment

Page 27 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Crystal structure of the “dimer” LNiLi complex 6 (#1 (½ +x, y, ½ꢀz)) bridged by one molecule of water with
forming two H
̶
bonds. The packing reveals C‒H…π interactions along the aꢀaxis (dash bonds). All Hꢀatoms
are omitted for clarity. Blue dashes correspond to Hꢀbonds.
145x215mm (96 x 96 DPI)
ACS Paragon Plus Environment

Crystal Growth & Design
Page 28 of 34
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Crystal structure of the 1D coordination of LNiK complex 8 (#1(x, - ½ -y, - ½ +z), #2(x, - ½ -y, ½+z),
#3(x, y, 1+z)) and, LNiRb complex 9 (#1( ½ +x, ½-y, z), #2(- ½ +x, ½-y, z)) showing face to face
packing. All H-atoms are omitted for clarity.
116x200mm (96 x 96 DPI)
ACS Paragon Plus Environment

Page 29 of 34
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Crystal structure of the sandwich conformation of (LNi)2Cs complex 10 (#1(x, ½-y, ½+z)) with a Ni(II)-
Ni(II) inteaction (dashed bond). All H-atoms are omitted for clarity.
142x128mm (96 x 96 DPI)
ACS Paragon Plus Environment