F,f Homodinuclear and d,f or f,f′ heterodinuclear complexes with a [2+2] macrocyclic compartmental schiff base

Article abstract of DOI:10.1002/ejic.200901165

The [2+2] compartimentai macrocyclic complexes [Ln(H₂-L)(NO ₃)], where H₂-L is the cyclic Schiff base, derived from the condensation of 2,6-diformyl-4-chlorophenol (H-L^A) or 2,6diformyl-4-methylphenol (H-L^B) and N,N-bis(2-aminoethyl)2- hydroxybenzylamlne-3HCl (HA′-3HCl), contains a free N₃O ₃ coordination chamber and. can act as a ligand toward an identical or a different lanthanide(III) ion and a d transi-tion metal(II) ion to give the related f ,f homodinuclear [Ln₂(L)(X)₂f,f,′P heterodinuclear [LnLn′(L)(X)₂] or d,f heterodi-nuclear [LnM(L)(X)] complexes. They have been charac-terized by ESEM-EDS, ESI-MS, and IR and ¹H and ¹³C NMR spectroscopy. The X-ray single-crystal analysis of the [2+1] acyclic complex [Lu₂(L′ )₂], derived, from, partial hydrolysis of the related [2+2] homodinuclear complex [Lu₂(L)(Cl)₂I, followed by the loss of one lutetium(III) ion with the free formyl groups turning into diacetal ones, is also reported.

Full text of DOI:10.1002/ejic.200901165

FULL PAPER
DOI: 10.1002/ejic.200901165
f,f Homodinuclear and d,f or f,fЈ Heterodinuclear Complexes with a [2+2]
Macrocyclic Compartmental Schiff Base
[a]
[a]
[a]
[a]
Sergio Tamburini,* Valentina Peruzzo, Franco Benetollo, and P. Alessandro Vigato
Keywords: Lanthanides / Schiff bases / Macrocycles / Heteronuclear complexes
The [2+2] compartmental macrocyclic complexes [Ln(H
2
-L)-
(X)
2 2
] and f,fЈ heterodinuclear [LnLnЈ(L)(X) ] or d,f heterodi-
(
NO )], where H -L is the cyclic Schiff base, derived from the
3
2
nuclear [LnM(L)(X)] complexes. They have been charac-
terized by ESEM-EDS, ESI-MS, and IR and H and C NMR
spectroscopy. The X-ray single-crystal analysis of the [2+1]
A
1
13
condensation of 2,6-diformyl-4-chlorophenol (H-L ) or 2,6-
diformyl-4-methylphenol (H-L ) and N,N-bis(2-aminoethyl)-
B
2
N
-hydroxybenzylamine·3HCl (HAЈ·3HCl), contains a free
coordination chamber and can act as a ligand toward
an identical or a different lanthanide(III) ion and a d transi-
acyclic complex [Lu
the related [2+2] homodinuclear complex [Lu
lowed by the loss of one lutetium(III) ion with the free formyl
groups turning into diacetal ones, is also reported.
2
(LЈ)
2
], derived from partial hydrolysis of
(L)(Cl) ], fol-
3
O
3
2
2
2
tion metal(II) ion to give the related f,f homodinuclear [Ln (L)-
Introduction
atoms. Each six-coordinate metal(II) ion resides in a N O
3 3
unit composed of two imino nitrogen atoms, one tertiary
nitrogen atom, two phenolic oxygen atoms, as well as one
oxygen atom from one of the pending phenolic groups. The
phenolic oxygen atom of each pendant arm is bound to the
adjacent manganese ion and two pendant groups are on the
The synthesis of macrocyclic Schiff base dinuclear com-
plexes derived from the [2+2] template condensation of 2,6-
diformyl-4-substituted phenol and a variety of primary di-
amines has successfully been experienced for more than
[
1–5]
three decades.
This synthetic pathway gives rise to sym-
[
8]
same side of the macrocycle.
metric systems containing two identical adjacent coordina-
tion chambers capable of securing two metal ions in close
proximity. The shape of these coordination moieties mainly
depends on the employed amine.[
In these studies the coordinating cavity of the two adja-
cent coordination chambers was progressively enlarged to
allow the encapsulation of two larger metal ions [i.e., lan-
thanide(III) metal ions]. This was achieved by using pri-
mary amines of the type H N(CH ) X(CH ) NH (X =
These macrocycles are not stable in the presence of spe-
cific metal ions and can lose the -CH C H OH lateral arms,
2
6
4
as observed when the above-condensation reaction is car-
ried out in the presence of Fe(ClO ) . This reaction affords
6,7]
4
2
[
[
Fe(H -LЈ)(Cl)](ClO ) , where H -LЈ is the 21-membered
2+2] asymmetric compartmental Schiff base macrocycle
2 4 2 2
derived from the release of a lateral arm of H -L and the
2
subsequent ring contraction of the free chamber by ring
closure. In consequence of these reactions, the resulting
complex is a mononuclear species with a six-coordinate dis-
torted octahedral iron(III) ion, equatorially surrounded by
two phenoxy oxygen atoms, one imine nitrogen atom, and
the adjacent secondary amine nitrogen atom and axially
bound by the other imine nitrogen and a chloride anion.
The free chamber, owing to the presence of a NH group,
undergoes ring contraction with the formation of an ad-
2
2 n
2 n
2
NH, NCH , O, S) with longer aliphatic or aromatic chains
3
bearing additional donor atoms.[
6,7]
Furthermore, these
amines were further functionalized by the insertion, espe-
cially at the secondary amine group, of appropriate coordi-
nating groups (i.e., phenol, pyridine, carboxylic acid, etc.)
to modify the recognition ability of the resulting coordinat-
ing chambers towards specific metal ions. Thus, the reaction
of sodium 2,6-diformyl-4-X-phenolate (X = -CH , -Cl) with
N,N-bis(2-aminoethyl)-2-hydroxybenzylamine, followed by
in situ transmetalation with Cd(ClO ) or Mn(ClO ) re-
sulted in the formation of [Cd (H -L)](ClO ) and [Mn -
3
[8]
ditional five-membered ring.
In this paper, 2,6-diformyl-4-X-phenol (X = -CH , -Cl)
3
4
2
4 2
and
were successfully employed in the synthesis of the related
2+2] macrocyclic derivatives, capable of forming, thanks to
N,N-bis(2-aminoethyl)-2-hydroxybenzylamine·3HCl
2
2
4 2
2
(
H-L)](ClO ), respectively, whose structures contain two oc-
4
[
tahedral metal(II) ions bridged by two µ -phenoxy oxygen
2
the coordinating ability of the phenol group appended to
the central nitrogen atom of the diamine precursor, stable
mononuclear lanthanide(III) complexes that can evolve into
f,f homodinuclear and f,fЈ or d,f heterodinuclear species
whose physicochemical properties were examined by envi-
[
a] Istituto di Chimica Inorganica e delle Superfici – C.N.R.,
Corso Stati Uniti 4, 35127 Padova, Italy
E-mail: sergio.tamburini@icis.cnr.it
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.200901165.
Eur. J. Inorg. Chem. 2010, 1853–1864
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1853

S. Tamburini, V. Peruzzo, F. Benetollo, P. A. Vigato
FULL PAPER
ronmental scanning electron microscope energy-dispersive
The reaction between the preformed acyclic ligand and
1
13
X-ray spectroscopy (ESEM-EDS), IR, H, and C NMR one equivalent of the desired lanthanide(III) salt in the
spectroscopy, and ESI-MS data. In the past, the use of sim- presence of base in methanolic solution results in the for-
ilar ligands, without these lateral coordinating functionali- mation of a mixture of products. The IR spectrum of the
ties, often resulted in mixtures of complexes in consequence yttrium(III) complex is characterized by a broad band in
of transmetalation, site migration, and demetalation reac- the range 1670–1600 cm–1 probably due to the sum of the
[
9]
tions.
ν(C=O) and ν(C=N) strong absorption bands arising from
Furthermore, the X-ray diffraction structure of the [2+1] different species (i.e., carbonyls or acetals), as proved by the
acyclic complex [Y (LЈ) ], resulting from recrystallization of occurrence of very complex NMR spectra.
2
2
B
the related [2+2] macrocyclic complex [Y (L)(Cl) ]·3.5H O,
The template reaction of H-L , HAЈ·3HCl, Ln(X) ·n-
2
2
2
3
is also reported. During the crystallization procedure, par- H O, and NaOH in a 2:1:1:6 molar ratio in methanol af-
2
tial hydrolysis at the imine groups occurred with the forma- fords, according to elemental analyses, the [2+1] mononu-
3
–
tion of the [2+1] acyclic Schiff base [LЈ] , whose formyl clear acyclic diacetal complex [Ln(LЈ)]. In the IR spectrum
–1
groups turned into the related diacetal derivatives.
there is only a ν(C=N) band at 1630 cm , which is typical
These data revealed the need to pay attention to the syn- of the coordinated iminic group. IR and NMR spec-
thesis and properties of [2+1] acyclic ligands and related troscopy revealed the absence of the C=O groups, which
complexes, and the results of our efforts are briefly re- turned in the less reactive acetal groups.
ported.
To avoid the formation of acetals and/or a mixture of
products, template reactions were carried out in CHCl3/
CH OH (95:5). However, the addition of a methanol solu-
3
tion of HAЈ·3HCl, NaOH, and YCl to a warm CHCl3
solution of 2,6-diformyl-4-methylphenol again gives rise to
3
Results and Discussion
an unidentified mixture of products.
Attention was primarily focused on the synthesis of the
[
2+1] acyclic ligand and related complexes, as they can rep-
In conclusion, attempts to isolate pure [2+1] lantha-
resent useful intermediates in the preparation of homo- and nide(III) acyclic complexes failed; in any case, a mixture of
heterodinuclear complexes and, hence, in setting up a step- diformyl and/or diacetal derivatives, not useful for further
by-step pathway. In this synthetic route, the obtainment of condensation reaction, occurs.
well-characterized acyclic complexes with the metal ion in
a defined site occupancy is of great relevance in the subse-
quent condensation reaction with a second amine precursor
and a second metal ion.
Appropriate knowledge of compounds arising from dif-
ferent steps allows the generation of metal complexes with
the metal ion in a previously designed site and, in turn, to
verify the occurrence of site migration, transmetalation, or
Synthesis and Characterization of the [2+2] Macrocyclic
Complexes
In light of the above-reported results, the [2+2] macro-
cyclic f,f homodinuclear and f,fЈ or d,f heterodinuclear com-
plexes have been prepared, according to Scheme 2, through
a template or step-by-step procedure by following the dif-
ferent synthetic pathways A–E.
Also, 2,6-diformyl-4-methylphenol was employed as a di-
formyl precursor in the analogous synthetic procedures re-
ported in Scheme 2. The obtained complexes, thanks to
their favorable solubility in organic solvents, revealed to be
useful in confirming the results obtained for the compounds
derived from the chlorophenol precursor.
demetalation processes.
The acyclic ligand H -acy obtained by condensation of
3
B
H-L with HAЈ·3HCl under high dilution conditions in
CHCl is sparingly soluble in CHCl and CH CN, thus pre-
3
3
3
venting further condensation and complexation reactions in
these solvents. This ligand is soluble in alcohol where, how-
ever, acetal or diacetal formation at both carbonyl groups
can take place, giving rise to the H -LЈ derivative
3
(Scheme 1).
The synthesis of the macrocyclic ligand H -L (Scheme 3)
4
by addition of HAЈ·3HCl (previously neutralized with
B
NaOH) to a solution of H-L under high dilution condi-
tions in CHCl was not successful. The obtained product
3
was an oil containing several compounds that were difficult
to be separated. This is not unexpected, as it was already
reported that similar self-condensations give rise to dif-
[
7,10]
ferently shaped macrocycles or oligomers.
Conse-
quently, the template procedures, following routes A, B, C,
D or E depicted in Scheme 2, were successfull in the synthe-
sis of mononuclear and f,fЈ LnLnЈ or d,f LnM heterodinu-
Scheme 1.
854
clear or f,f Ln homodinuclear complexes.
2
1
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Eur. J. Inorg. Chem. 2010, 1853–1864

Dinuclear Ln Complexes
Scheme 2.
were used instead of the chloride salts to avoid the presence
–
of Cl as a counteranion in the final complex and to facili-
tate the ESEM-EDS evaluation of the Ln/Cl ratio and
2–
hence of the Ln/[H -L] ratio. The formulation of the lan-
2
thanum(III) complex as [La(H -L)(NO )]·0.5CH Cl , pro-
2
3
2
2
posed on the basis of elemental analysis, was supported also
by ESEM-EDS measurements, which indicate a La/Cl ratio
1
of 1:3, and was confirmed by H and 2D NMR spectro-
scopic experiments, which show two iminic protons at 8.40
(13-H, 13Ј-H) and 8.14 ppm (3-H, 3Ј-H) and the aromatic
protons of the diformyl precursors as one broad singlet at
7
7
.62 ppm (2-H, 2Ј-H), scalar coupled with a doublet at
.48 ppm (1-H, 1Ј-H), indicating that one of the two coordi-
nating sites is not involved in coordination.
Scheme 3.
The yttrium(III) complex [Y(H -L)(NO )]·3H O shows a
2
3
2
quite simple 1H NMR spectrum in CD OD with some
3
Mononuclear Complexes
small signal shifts from those of the lanthanum(III) ana-
To avoid acetal formation, experienced in the preparation logue. The four iminic protons generate one broad singlet
of the [2+1] acyclic complexes, procedure A (Scheme 2) was at 8.60 ppm (13-H, 13Ј-H) and one sharp singlet at
successfully tested to obtain the designed macrocyclic spe- 8.32 ppm (3-H, 3Ј-H). The signals of the aromatic protons
cies. In particular, the addition of a methanolic solution of of the formyl precursor are characterized by a doublet at
–
HAЈ·3HCl, LnX ·nH O (Ln = La, Lu, Y, Gd; X = NO , 7.76 ppm (2-H, 2Ј-H) and by a broad singlet at 7.55 ppm
3
2
3
–
CH COO ), and NaOH (stoichiometrically added to neu- (1-H, 1Ј-H). The peaks of the pendant arms are partially
tralize the amine precursor) to a warm CHCl solution of overlapped, but the H– H COSY experiment clarified the
H-L , followed by the addition of two equivalents of NaOH spectrum. The aliphatic region presents a series of mul-
3
1
1
3
B
to favor the deprotonation of two phenolic groups, affords tiplets attributable to geminal couplings due to the asym-
the related mononuclear complexes [Ln(H -L)(X)]·nS, as metry of the system. Elemental analysis is consistent with
2
indicated by elemental analysis, ESEM-EDS, and IR spec- the proposed formulation, and the ESEM-EDS analyses
troscopy. The large excess of chloroform with respect to indicate a Y/Cl ratio of 1:2. The IR spectra is characterized
–1
methanol (95:5) favors the solubility of all the reagents and by one ν(C=N) band at 1658 cm (noncoordinated) and
depresses the formation of acetal groups. The 1:2 H -L/ one ν(C=N) band at 1638 cm–1 (coordinated); the presence
4
NaOH molar ratio in these complexation reactions causes of the coordinated nitrate group is confirmed by the bands
–1
partial deprotonation of the ligand, which according to the at 1442 and 1343 cm . This mononuclear complex was in-
experimental data, coordinates the lanthanide(III) ion as vestigated also by ESI-MS spectrometry in methanol: the
2
–
+
the partially deprotonated form [H -L] and not in the en- parent peak at m/z = 800.83 belongs to the ion [Y(H -L)]
2
2
4
–
tirely deprotonated one [L] . The nitrate and acetate salts species.
Eur. J. Inorg. Chem. 2010, 1853–1864
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1855

S. Tamburini, V. Peruzzo, F. Benetollo, P. A. Vigato
FULL PAPER
The same reaction using 2,6-diformyl-4-methylphenol as mal analysis (Figure 1) shows that the YMn complex un-
the diformyl precursor resulted in the analogous complex dergoes weight loss in line with the proposed formulation,
[
Y(H -LЈЈ)(NO )] as testified by elemental analyses, ESI giving rise to the mixed oxide YMnO whose Y/Mn = 1:1
2
3
3
mass spectrometry, ESEM-EDS, and NMR and IR spec- ratio was determined by ESEM-EDS analyses. The final
1
troscopy. In the H NMR spectrum in CD OD the signals weight loss at about 1000 °C (79.93%) agrees well with the
3
in the aliphatic region and the signals due to the two pen- calculated value (80.10%) for the formation YMnO as the
3
dant arms are superimposable with those of the analogous final product.
complex [Y(H -L)(NO )], whereas the signals of the imine
2
3
protons and the protons of the diformyl precursor are
shifted upfield. The methyl groups of the aromatic rings
generate a singlet at 2.28 ppm. In the ESI mass spectrum
the parent peak is at m/z = 761, which corresponds to the
+
[
[
Y(H -LЈЈ)] fragment, but a small percentage of the species
2
+
Y(H -LЈЈ)(NO )] + H at m/z = 823.92 is present.
2
3
[
Y(H -L)(NO )]·3H O, [Lu(H -L)(NO )]·2H O, and [La-
2 3 2 2 3 2
(
H -L)(NO )]·0.5CH Cl revealed to be suitable starting
2 3 2 2
products for obtaining d,f or f,fЈ heterodinuclear complexes
through synthetic pathways B and E (Scheme 2).
d,f Heterodinuclear LnM Complexes
3 2
Figure 1. TG-DTA thermogram of [MnY(L)(CH COO)]·3H O.
The d,f heterodinuclear complexes were obtained by fol-
lowing synthetic routes B and C of Scheme 2. Step-by-step
procedure B consists in the reaction of equivalent amounts
SEM-EDS analyses of [LuZn(L)(CH COO)]·3.5H O,
3
2
of the mononuclear lanthanide(III) complex [Ln(H2- synthesized from [Lu(H -L)(NO )]·2H O and Zn(CH -
2
3
2
3
L)(NO )]·mH O (Ln = Y, m = 3; Ln = Lu, m = 2) with COO) ·2H O, show a Lu/Zn/Cl ratio of 1:1:2, which is con-
3
2
2
2
Zn(CH COO) ·2H O, Cd(NO ) ·4H O, Mn(CH COO) · sistent with the proposed formulation. In the IR spectrum
3
2
2
3 2
2
3
2
4
H O, or Ni(CH COO) ·4H O in methanol to afford the the nitrate bands, present in the lutetium(III) starting com-
2
3
2
2
d,f
heterodinuclear
complexes
[LnM(L)(X)]·xH O· plex, are missing in the LuZn complex, and the ν(C=O)
2
–
–
–1
yC H OH (X = CH COO , NO ; x = 2–5; y = 1), whose acetate band at 1655 cm has been detected. Moreover, the
counteranion is always derived from the incoming metal(II) ν(C=N) band of the uncoordinated imine at 1658 cm in
2
5
3
3
–1
salt, this indicating a metathesis of the starting complex. In the mononuclear precursor appears as a strong band at
–
1
this way, [ZnY(L)(CH COO)]·2H O, [CdY(L)(NO )]·5H O, 1648 cm , whereas the absorption of the coordinated imine
3
2
3
2
[
MnY(L)(CH COO)]·3H O, [NiY(L)(NO )]·H O·C H OH, at ca. 1636 cm–1 of the mononuclear precursor does not
3 2 3 2 2 5
[
5
ZnLu(L)(CH COO)]·3.5H O, and [LuNi(L)(CH COO)]· change upon coordination of the transition-metal ion. The
3
2
3
+
H O were synthesized.
peak at m/z = 951.50 corresponding to the [LuZn(L)] spe-
2
In [MnY(L)(CH COO)]·3H O, resulting from the reac- cies in the ESI mass spectrum confirms the stability of the
3
2
tion of [Y(H -L)(NO )]·3H O and Mn(CH COO) ·4H O in heterodinuclear core.
2
3
2
3
2
2
the presence of two equivalents of NaOH, the coordinated
nitrate group of the starting complex was substituted by an plate condensation of H-L in CHCl with HAЈ·3HCl in
According to synthetic pathway C (Scheme 2), the tem-
B
3
acetate of the manganese(II) salt; this was confirmed by the the presence of Y(NO ) ·6H O or Lu(NO ) ·6H O and
3
3
2
3 3
2
lack of bands of the coordinated nitrate at 1442 and NaOH in CH OH followed by the addition of
3
–
1
1
343 cm occurring in the mononuclear yttrium(II) com- Zn(CH COO) ·2H O and NaOH to deprotonate the -OH
3 2 2
–1
plex and the appearance of a ν(C=O) band at 1653 cm
phenolic groups forms [YZn(L)(NO )]·2CH COONa and
3 3
assigned to the acetate group, possibly acting as a mono- [LuZn(L)](CH COO)·NaCl according to SEM-EDS, which
3
–
1
dentate ligand. One ν(C=N) band at 1648 cm is shifted ascertains the presence of Na in the correct ratio and ele-
with respect to the ν(C=N) bands of the starting mononu- mental analyses. The counteranion of the final complex, de-
–
1
clear yttrium(III) complex (1658 to 1636 cm ). ESEM- rived from synthetic pathway C, is not always that of the
EDS analyses indicate a Y/Mn/Cl ratio of 1:1:2, in agree- incoming transition-metal(II) ion, as the formation of
ment with the proposed formulation. The ESI mass spec- [YZn(L)(NO )] shows.
3
trum in methanol shows the molecular peak at m/z =
Surprisingly, the success of this synthetic way underlines
+
854.17, corresponding to the [YMn(L)] species derived the stability of the mononuclear lanthanide(III) macrocyclic
from the loss of the acetate counteranion. This indicates a intermediate that originates from the addition of one equiv-
considerable stability of the heterodinuclear core. The sub- alent of metal salt and of the equivalents of base necessary
+
sequent fragmentation of the [YMn(L)] species gives rise for the neutralization of the amine and the deprotonation
to two peaks at m/z = 765.78 and m/z = 779.77, assigned to of two OH phenolic groups. Experimental data, especially
+
the {YMn[(L)-CH C H OH](OH)} and {YMn[(L)-CH2- the similarity between the LnM complexes obtained by the
2
6
4
+
C H OH + CH ](OH)} species, respectively. Finally, ther- template and step-by-step procedures, suggest that both
6
4
3
1856
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Eur. J. Inorg. Chem. 2010, 1853–1864

Dinuclear Ln Complexes
synthetic pathways form the mononuclear lanthanide(III) lar, the ESI mass spectrum of [LuZn(L)](CH COO)·NaCl
3
intermediate thanks to the migration of the two remaining is characterized by a peak at m/z = 951.50 corresponding
2
–
+
protons of the [H -L] macrocycle from the phenolic oxy- to the [LuZn(L)] species, whereas [YZn(L)(NO )]·2CH -
2
3
3
gen toward the imine nitrogen atoms, thus preventing the COONa is characterized by a peak at m/z = 865.50 corre-
+
formation of homodinuclear Ln species. The further ad- sponding to the [YZn(L)] species (Figure 2).
dition of the transition-metal(II) ion and NaOH, which
2
1
Although difficult to interpret, the H NMR spectra in
cause the deprotonation of the other two protons making CD OD of the YZn and LuZn complexes derived from syn-
3
the phenolic groups prone to act as donor groups for the thetic route C, parallel each other and parallel the ones of
incoming d metal ion, makes the formation of the heterobi- the complexes generated by route B (Scheme 2).
metallic species possible, avoiding the production of a mix-
ture of complexes.
The final products of the thermal decomposition of these
complexes, except for the YMn and YNi ones already dis-
The IR spectra of the LuZn and YZn complexes, ob- cussed, contain variable amounts of transition-metal oxides,
tained by the two different procedures, are superimposable; which under the thermogravimetric conditions are found to
the only difference is the nitrate stretching bands at 1421 be volatile enough to escape from the reaction vessel. The
–
1
and 1370 cm present in the YZn complex obtained with [LuZn(L)](CH COO)·NaCl final oxide is composed of, as
3
procedure C. In particular, the IR spectra show two strong verified by ESEM-EDS analysis, 80% Lu O3 and 20%
2
–
1
ν(C=N) bands at ca. 1648 and 1636 cm , which corrobo- ZnO; the weight loss at 1200 °C (81%) agrees with the cal-
rate the asymmetry of the obtained d,f complexes. NMR culated value (83.6%) for the final product.
solution studies of d,f complexes obtained by both pro-
cedures were not successful because of the high degree of
asymmetry arising from complexation. Mass spectrometry
was useful in the characterization of the complexes with the
identification of the pattern associated with the presence of
two different metal ions and two chlorine atoms. In particu-
f,f Homodinuclear and f,fЈ Heterodinuclear Lanthanide(III)
Complexes
The f,fЈ LnLnЈ heterodinuclear and the f,f Ln homodi-
2
nuclear complexes were prepared by template procedure D
or step-by-step procedure E (Scheme 2).
Template procedure D parallels procedure C employed in
the synthesis of the d,f heterodinuclear complexes, except
for the use of a lanthanide(III) salt instead of a transition-
metal(II) one. By this procedure, [YLu(L)(NO ) ]·
3
2
5
CH OH, [Lu (L)(Cl) ]·3.5H O, and [Y (L)(Cl) ]·2CH Cl
3 2 2 2 2 2 2 2
were obtained. For the synthesis of the homodinuclear
complexes equivalent amounts of LnCl ·nH O, HAЈ·3HCl,
3
2
B
and NaOH in CH OH were added to H-L in CHCl3.
3
SEM-EDS analyses of the diyttrium(III) complex reveal a
Y/Cl ratio of 2:8 in agreement with the presence of two
methylene dichloride solvent molecules. Similarly, in the di-
lutetium(III) complex, the Lu/Cl ratio of 2:4, found by
SEM-EDS analyses, supports the above formulation (Fig-
ure 3).
3 2
Figure 2. ESI mass spectra of [LuZn(L)(CH COO)]·3.5H O (top+)
with the detailed pattern and MS simulation of the {LuZn(L)}
species (bottom).
Figure 3. SEM and EDX analyses of the complex [Lu
2 2
(L)(Cl) ]·
3.5H O.
2
Eur. J. Inorg. Chem. 2010, 1853–1864
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1857

S. Tamburini, V. Peruzzo, F. Benetollo, P. A. Vigato
FULL PAPER
Comparison of the IR spectra of the dinuclear complexes with 4Ј-H protons in the range 4.30–3.99 and 3.77–
with those of the related mononuclear complexes does not 3.52 ppm, respectively (Figures 4 and 5, top).
show any drastic variations; the ν(C=N) bands at 1657 and
–
1
–1
1
640 cm for the Lu complex and at 1658 and 1639 cm
2
for the Y complex are almost similar to those of the mono-
2
–
1
nuclear ones (1658 and 1636 cm for the Lu complex and
1
658 and 1636 cm–1 for the Y one). The very small shifts
suggest coordination of the second lanthanide(III) ion re-
markably far from the mean plane of the N O2 donor
3
chamber. Furthermore, the presence of two ν(C=N) bands
suggests external coordination and the occurrence of an en-
hanced asymmetry in the homodinuclear complexation.
1
This asymmetry is corroborated also by the H NMR spec-
tra of [Y (L)(Cl) ]·2CH Cl in CD OD, where the signals
2
2
2
2
3
of the iminic protons at 8.69 and 8.37 ppm (3-H, 13-H, 3Ј-
A –
H, 13Ј-H) and of the protons of [L ] , represented by two
doublets centered at 7.80 and 7.63 ppm (1-H, 2-H, 1Ј-H, 2Ј-
H), have been detected.
Further evidence of the proposed coordination of the
second lanthanide(III) ion comes from the ESI mass spec-
trum of complex Y , which shows one peak at m/z = 800.92
2
+
corresponding to the mononuclear species [Y(H-L) + H] .
The ESI mass spectrum of the Lu complex shows one peak
2
at m/z = 887.25 corresponding to the mononuclear ion
+
[
Lu(H-L) + H] .
Although far from the imine groups of [L]4– the lantha-
nide(III) ion is firmly coordinated, as verified by NMR
spectra, probably because of the presence of the pendant
arm, which under the ESI-MS conditions easily undergoes
protonation and hence releases the metal(III) ion.
1
The H NMR spectra in CD OD of the homodinuclear
3
Y and Lu complexes parallel each other; there are only
2
2
small shifts and broadening of some signals. The attri-
bution of the signals to the corresponding proton of the
Figure 4. [Lu
2
(L)(Cl)
2 2 3
]·3.5H O in CD OD at 298 K: (top) 2D
1
H NMR spectra of [Lu (L)(Cl) ]·3.5H O is quite difficult
1
1
13
2
2
2
COSY H NMR spectrum; (bottom) 2D HETCORR H– C
1
in spite of a very simple H NMR spectrum, this de- HMQC. Geminal correlations in the aliphatic region.
pending on the degree of overlap between the aliphatic sig-
nals and the geminal couplings of the protons of the iminic
1
1
1
13
1
1
chain. The 2D H– H COSY, H– C HMQC, and H– H
NOESY experiments, quite useful in the interpretation of
1
the H NMR spectrum, show that the imine protons gen-
erate broad and sharp singlets at 8.78 and 8.42 ppm (13-
H and 13Ј-H, 3-H and 3Ј-H). Furthermore, one doublet at
7
.83 ppm and one broad singlet at 7.68 ppm are assigned
to the aromatic 2-H, 2Ј-H and 1-H, 1Ј-H protons, respec-
tively, according to the coupling between these two signals.
The pendant arms with the related aliphatic methylenic 6-
H and 6Ј-H protons are represented by two different sets
of peaks properly correlated. The aliphatic region is char-
1
acterized by two multiplets centered at 3.33 and 3.06 ppm Figure 5. H NMR spectra in CD OD at 298 K of (top)
3
belonging to the geminal 5a–11a-H and 5b–11b-H pro- [Lu
tons, respectively, whereas the 4-H, 12-H, and 11Ј-H pro-
tons generate one multiplet in the range 4.30–3.99 ppm.
2 2 2 3 2 3
(L)(Cl) ]·3.5H O and (bottom) [YLu(L)(NO ) ]·5CH OH.
Attempts to recrystallize [Lu (L)(Cl) ]·3.5H O from
2
2
2
The signals of the other protons are split into two mul- CH OH resulted in separate crystals whose structure corre-
3
tiplets: one in the range 3.18–2.94 ppm and the other hid- sponds to a dimer of mononuclear [Lu(LЈ)]2 complexes
den by the strong signal of the methanol present in composed of two [2+1] acyclic [LЈ]3– ligands derived from
CD OD. Finally, the 12Ј-H and 5Ј-H protons in the range the hydrolysis of the [2+2] cyclic ligand. This indicates that,
3
3
.18–2.94 ppm are coupled with the above cited 11Ј-H and on standing in alcoholic solution, the dilutetium(III) com-
1858
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Eur. J. Inorg. Chem. 2010, 1853–1864

Dinuclear Ln Complexes
plex undergoes partial hydrolysis of the imine groups with (L)(NO ) ]·CH OH, [LuEr(L)(NO3)2], [YEr(L)(NO3)2]·
3
2
3
consequent loss of one lanthanide(III) ion, followed by di- 3H O, or [YLu(L)(NO ) ]·H O, whose formulations have
2
3 2
2
acetal formation of the resulting formyl groups and dimer- primarily been inferred by ESEM-EDS and elemental
ization of the complex to form [Lu(LЈ)] (following dis- analyses.
2
cussion later).
The IR spectra of [LuY(L)(NO ) ]·NaNO ·CHCl and
3 2 3 3
The heterodinuclear complex [YLu(L)(NO ) ]·5CH OH [YLu(L)(NO ) ]·H O obtained from the mononuclear lute-
3
2
3
3 2
2
was synthesized according to procedure D (Scheme 2) by tium(III) and yttrium(III) complex, respectively, are almost
the addition of a methanolic solution of N,N-bis(2-amino- identical with the same ν(C=N) bands at 1648 and
ethyl)-2-hydroxybenzylamine·3HCl, Y(NO ) ·nH O, and 1640 cm–1 and the ν(NO ) bands at ca. 1440 and 1345 cm ;
–1
3
3
2
B
3
NaOH (8 equiv.) to a hot CHCl solution of H-L followed they reveal interesting shifts with respect to the related mo-
3
by the addition of LuCl ·nH O and NaOH (2 equiv.). Anal- nonuclear complexes with two ν(C=N) bands at 1658 and
3
2
–1
ogously to procedure C, the first step in procedure D is also 1636 cm . The marked differences as regards the YLu and
represented by the formation of a mononuclear lantha- LuY heterodinuclear species derived from template pro-
nide(III) complex that consequently evolves into a heterodi- cedure D suggest a stronger contribution of the imine
nuclear complex as a consequence of the addition of the groups in the coordination.
1
second metal and the remaining amount of base.
The H NMR spectra in CD OD of the two YLu com-
3
SEM-EDS measurements, showing a Y/Lu/Cl ratio of plexes are superimposable with that of the complex deriving
:1:2, and elemental analyses agree with the above formula- from procedure D. All these data indicate the equivalence
1
tion of the heterodinuclear compound obtained by pro- of the two procedures in the formation of heterodinuclear
cedure D. Furthermore, its IR spectrum is quite superim- species.
posable on the Y2 and Lu2 homodinuclear ones with
ν(C=N) bands at 1660 and 1642 cm ; the only difference from the mononuclear yttrium(III) complex show two pre-
The ESI mass spectra of [YLu(L)(NO ) ]·H O derived
3 2 2
–
1
is the presence of the two ν(NO ) bands at 1421 and dominant peaks at m/z = 949.92 and m/z = 863.92 assigned
3
–
1
+
1
350 cm .
to the {[Lu(H -L)(NO )] + H } and {[Y(H -L)(NO )] +
2 3 2 3
+
Also, the ESI mass spectra corroborate the formation of H } species, respectively, which belong to the mononuclear
a true heterodinuclear complex that is not contaminated by yttrium(III) and lutetium(III) complexes with nitrate as
2
the related homodinuclear analogues owing to the presence counteranion. The MS fragmentation of the {[Lu(H -L +
2
+
of a peak at m/z = 1035.92 attributable to the [YLu- H)(NO )] + H } species at m/z = 949.92 gives rise to one
L)(NO3)] ion. Mass fragmentation generates a peak at fragment at m/z = 843.83, corresponding to the mononu-
3
+
(
m/z = 929.83, which corresponds to the loss of one pendant clear lutetium(III) complex {[Lu(L-CH C H OH
+
2
6
4
+
arm, as was also verified for other compounds.
H)(NO )] + H } where a pendant arm is substituted by
3
1
2
The H NMR spectra of [YLu(L)(NO ) ]·5CH OH in a hydrogen atom. The MS fragmentation of the{[Y(H -
3
2
3
2
+
CD OD (Figure 5B) reveal an asymmetry of the two pen- L)(NO )] + H } species at m/z = 863.92 gives rise to one
3
3
dant arms, which generates quite a complicated system of fragment at m/z = 757.92, corresponding to the mononu-
signals resolved with 2D experiments: one pendant group clear yttrium(III) complex {[Y(L-CH C H OH + H)(NO )]
2
6
4
3
+
is characterized by two doublets at 6.91 (7Ј-H) and + H } where a pendant arm is substituted by a hydrogen
6
6
.56 ppm (10Ј-H) and one multiplet in the range 6.51– atom.
.29 ppm (8Ј-H + 9Ј-H). The other pendant arm shows one The ESI mass spectra of [LuY(L)(NO ) ]·NaNO ·CHCl
3
3
2
3
doublet at 7.15 ppm (7-H), one triplet at 7.05 ppm (9-H) derived from the mononuclear and lutetium(III) complex
and one multiplet in the range 6.72–6.58 ppm (8-H + 10- show one peak at m/z = 1036.08 corresponding to the
+
2
H). The iminic protons generate one broad singlet at {LuY(L)(NO )} species. The MS fragmentation generates
3
8
.63 ppm (13-H, 13Ј-H) and one sharp singlet at 8.34 ppm one peak at m/z = 929.83 attributed to the {LuY(L-
+
(3-H, 3Ј-H), whereas the aromatic 2-H, 2Ј-H and 1-H, 1Ј- CH C H OH + H)(NO )} species where a pendant arm is
2 6 4 3
H protons generate two doublets at 7.76 and 7.56 ppm, substituted by a hydrogen atom.
1
13
respectively. The aliphatic region was resolved with H– C
Unlike the NMR and IR spectroscopic investigations
HMQC, which clarified the presence of only one geminal that show that the spectra of the same complexes, prepared
coupling with two multiplets centered at 3.22 and 2.99 ppm, by the different routes of Scheme 2, are mainly superimpos-
belonging to the 5a,5b-H and 11a,11b-H protons, coupled able, the ESI mass spectra reveal that, under similar experi-
with the multiplet of the 4-H and 12-H protons (4.22– mental conditions, only [LuY(L)(NO ) ]·NaNO ·CHCl
3
3
2
3
+
3.96 ppm). The methylenic 6-H and 6Ј-H protons generate shows the molecular peak of the [LuY(L)(NO3)] species.
two singlets at 3.94 and 3.61 ppm, respectively. The other This might be due to the different ionic radii of the two
aliphatic chain is characterized by two multiplets at 3.79– lanthanide ions and to the conformation of the macrocycle
3
.54 and 3.13–2.99 ppm (11Ј-H, 5Ј-H and 4Ј-H, 12Ј-H).
Procedure E (Scheme 2) parallels step-by-step pro- this last fact determining the entire coordination process. In
cedure B: the addition of one equivalent of Ln(NO ) ·6H O the mononuclear lutetium(III) complex precursor, due to
in consequence of the coordination of the first metal ion,
3
3
2
and two equivalents of NaOH to [Y(H -L)(NO )]·3H O, the small radius of the metal ion, the free compartmental
2
3
2
[
Lu(H -L)(NO )]·2H O, or [La(H -L)(NO )]·0.5CH Cl in chamber is able to better accommodate the larger yt-
2 3 2 2 3 2 2
CH OH affords [LuY(L)(NO ) ]·NaNO ·CHCl , [YLa- trium(III) ion; on the contrary, in the mononuclear yt-
3
3 2
3
3
Eur. J. Inorg. Chem. 2010, 1853–1864
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1859

S. Tamburini, V. Peruzzo, F. Benetollo, P. A. Vigato
FULL PAPER
trium(III) complex precursor the free compartmental cham- in maintaining the heterodinuclear moiety. Unfortunately,
ber shows greater difficulty in coordinating the incoming attempts to grow suitable crystals to corroborate this pro-
lutetium(III) ion. This makes the heterodinuclear complex posal structurally failed so far; consequently, we can put
less stable, at least under the ESI+ MS conditions. Further- forward reasonable proposals that need further X-ray struc-
2
more, the observation that the MS fragmentation of the tural confirmation.
+
[
LuY(L)(NO )] species causes the loss of the pendant arm,
3
while the heterodinuclear core still exists, is additional proof
that the two metal ions in the LuY complex are strongly X-ray Structure of the [Lu
linked to the N O sites.
(LЈ) ] Complex
2
2
3
2
Crystals of [Lu (LЈ) ] were grown from a methanol solu-
2
2
By thermal degradation of the YLu complex, the related
tion of the crude product. The solid-state structure consists
of discrete centrosymmetric dinuclear [Lu (LЈ) ] complexes
as shown in Figure 6 (top) with the labeling scheme used.
mixed oxide YLuO oxide is obtained, its Y/Lu = 1:1 ratio
3
2
2
being inferred by SEM-EDS measurements. The final
weight loss at 1100 °C (75.02%) is consistent with the pro-
posed formulation (72.1%). XRD data also agree with
those already obtained for mixed oxides derived from ther-
[11]
mal degradation of heterodinuclear complexes.
The two yttrium(III) and lutetium(III) mononuclear
complexes, when treated with the paramagnetic erbium(III)
nitrate salt afford [LnEr(L)(NO ) ]·nH O, according to
3
2
2
SEM-EDS analyses, which show a Y/Lu/Er/Cl ration of
:1:2 and elemental analyses. In the IR spectra of
YEr(L)(NO ) ]·3H O the ν(C=N) bands shifted from the
1
[
3
2
2
values of the mononuclear yttrium(III) complex to 1648
–
1
and 1639 cm as happens with [YLu(L)(NO ) ]·H O ob-
3
2
2
tained from the same starting product. The ν(NO ) bands
3
–
1
are at 1418 and 1365 cm . The presence of the erbium(III)
ion in these complexes does not allow a detailed NMR in-
vestigation, aimed at verifying the influence of the para-
1
magnetic center in the proton signals. Thus, the H NMR
spectrum in CD OD of the YEr complex shows many
3
hardly attributable peaks in the range from +60 to –40 ppm.
The IR spectra of [LuEr(L)(NO ) ] shows two ν(C=N)
3
2
–
1
bands at 1649 and 1638 cm analogously to the YEr com-
plex reported above. The H NMR spectrum in [D ]DMSO
1
6
of the LuEr complex show 26 signals in the range from 90
to –80 ppm.
Comparison between the ESI mass spectra of the YEr
and LuEr complexes reveals an interesting similar behavior
with the YLu and LuY complexes obtained from the same
starting mononuclear complex. The ESI mass spectra of the
YEr complex, as that of the YLu complex, are charac-
terized by the presence of signals with the correct pattern
+
Figure 6. (Top) ORTEP representation of the molecular structure
of [Lu (LЈ) ]; (bottom) dinuclear Lu coordination environment
2 2
comprised of N and O Schiff base donor atoms.
of two mononuclear complexes: [Y(H-L) + H] at m/z =
3
+
+
8
00.92, with the corresponding Na derivative [Y(H-L) +
+
+
Na] at m/z = 822.92 and [Er(H-L) + H] at m/z = 879.83
with the corresponding Na derivative [Er(H-L) + Na ] at
+
+
The hexadentate ligand [LЈ]3– coordinates to the lute-
m/z = 901.92. The ESI mass spectra of the LuEr complex, tium(III) ion through the two imine and one amine nitrogen
as that of the LuY complex, is characterized by signals of atoms (N1, N2, N3), by the two phenoxy oxygen atoms (O2
+
the dinuclear core [LuEr(L)(NO )] at m/z = 1114.92 whose and O3) and by the bridging O1 oxygen atom of the Schiff
3
2
MS mass fragmentation generates a peak at m/z = 1008.83 base pendant arm. The lutetium(III) ion reaches the sev-
corresponding to the loss of one pendant arm –CH2- enth coordination by the centrosymmetrically related O1Ј
C H OH.
atom. The whole system is a centrosymmetric binuclear
6
4
This behavior agrees with the proposal that the ionic ra- complex with a Lu O2 rhombic core; the O1···O1Ј and
2
dius strongly influences the conformation and hence the Lu···LuЈ contacts are 2.549(4) and 3.700(1) Å, respectively
stability of the heterodinuclear complex. Again, the loss of (Figure 6, bottom). The coordination polyhedron around
2
the pendant arm, in consequence of the MS fragmentation the lutetium(III) ion could be described as a distorted pen-
+
of the [LuEr(L)(NO )] ion, clearly shows that the phenol tagonal bipyramid with N1 and O1Ј as apexes (the angle
3
moiety of the pendant arm is not the determining factor N1–Lu–O1Ј is 172.9°). and the base formed by O1, O2, O3,
1860
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Eur. J. Inorg. Chem. 2010, 1853–1864

Dinuclear Ln Complexes
N2, and N3. The distances within the metal ion coordina- complexation; thus, these systems can act as molecular
tion sphere are: Lu–O1 2.251(3), Lu–N1 2.383(4), Lu–N2 probes or devices and is currently under investigations.
2.660(4), Lu–N3 2.400(4), Lu–O2, 2.167(3), Lu–O3
The stability of the mononuclear complexes, as starting
2.1667(3), and Lu–O1Ј 2.242(3) (Table 1), which are com- or intermediate ligands in the step-by-step and template re-
parable to those observed in the dinuclear Schiff base (SB) actions, makes the synthesis of pure heterodinuclear LnLnЈ
complex of the general formula Ln (O N C H ) (Ln = or LnM complexes successful, avoiding transmetalation re-
2
2
2 13 20 3
[
12]
Nd, Sm, Er)
exhibiting seven coordination around the actions encountered with other dinucleating systems. The
metal ion and in other analogous Ln(SB) complexes.
[
13,14]
d,f complexes resulting from the template or step-by-step
reaction revealed to be stable under ESI-MS conditions
without fragmentation of the dinuclear core. Furthermore,
the formation of acyclic diformyl complexes is under scru-
tiny to set up a convenient synthetic route for the synthesis
of asymmetric macrocyclic complexes.
3
2 2
Table 1. Selected bond lengths and angles for [Lu LЈ ].
Bond lengths [Å]
Lu–N1
Lu–N3
Lu–O1Ј
Lu–O3
2.383(4)
2.400(4)
2.242(3)
2.167(3)
Lu–N2
Lu–O1
Lu–O2
2.661(4)
2.251(3)
2.167(3)
Bond angles [°]
Experimental Section
O3–Lu–O2
O2–Lu–O1
O1–Lu–O1Ј
O2–Lu–N1
N3–Lu–O1Ј
O1–Lu–N2
N3–Lu–N2
O3–Lu–O1
O1–Lu–N1Ј
O1–Lu–N3
O2–Lu–N2
82.4(1)
83.7(1)
69.1(1)
76.2(1)
84.4(1)
76.4(1)
67.4(1)
149.6(1)
172.9(1)
122.2(1)
124.7(1)
O3–Lu–O1Ј
89.8(1)
83.7(1)
85.2(1)
74.8(1)
89.4(2)
68.8(1)
108.2(1)
117.4(1)
154.0(1)
133.2(1)
Materials: All the salts and solvents were commercial products
O2–Lu–O1Ј
O3–Lu–N1
O3–Lu–N3
N1–Lu–N3
N1–Lu–N2
O2–Lu–O1Ј
O1–Lu–N1
O2–Lu–N3
O3–Lu–N2
used without further purification. The diformyl precursor 2,6-di-
B
formyl-4-chlorophenol (H-L ) was prepared according to litera-
ture[ by MnO
15]
oxidation of the related 2,6-dimethyl-4-chlorophe-
and purified by chromatography on silica gel (CHCl
OH, 95:5). The diformyl precursor 2,6-diformyl-4-methylphe-
2
nol in CHCl
CH
3
3
/
3
B
nol (H-L ) was purchased and used without any further purifica-
tion. Also, the amine precursor N,N-bis(2-aminoethyl)-2-
hydroxybenzylamine·3HCl (HAЈ·3HCl) was prepared according to
the literature by heating a mixture of diethylenetriamine (1.03 g,
10 mmol) and salicylaldehyde (2.44 g, 20 mmol) in EtOH (200 mL)
The Lu–O bond lengths of the bridging phenolate at reflux for 30 min. After the resulting solution was cooled to
room temperature, 2-bromomethylphenyl acetate (2.28 g, 10 mmol)
[
2.251(3) Å] are larger than those of the other coordinated
and Na
was heated at reflux for 36 h. Upon cooling to room temperature,
the excess amount of solid Na CO was filtered off and the filtrate
2 3
CO (1.06 g, 10 mmol) were added, and then the solution
oxygen atoms [2.167(3) Å]. The Lu–Nimino distances
[
distances [2.660(4) Å] and indicate a weak interaction for
this latter, related to the requirement of the central atom
coordination saturation and to the twisting of the bridging
phenolate moieties.
2.383(4) and 2.400(4) Å] are shorter than the Lu–N2tertiary
2
3
was concentrated under reduced pressure. Yellow deposits were col-
lected and recrystallized from ethanol. The purity and the proposed
formulation of both the precursors were checked by elemental
analysis, ESI-MS, and IR and NMR spectroscopic measurements.
The five membered –Lu–N–C–C–N–diamine chelate ring
of the Schiff base adopts the familiar twisted conformation
with the torsion angles N1–C11–C12–N2 and N2–C14–
C15–N3 of 63.1(5) and 55.2(5)°, respectively.
Physicochemical Measurements: Elemental analyses were carried
out by using a Fison 1108 analyzer. IR spectra were recorded as
KBr pellets with a Mattson FTIR spectrometer and as powders
with a Nicolet Magna-560 equipped with a Continuum Spectra-
Tech microscope. NMR spectra ( H, C) were recorded with a
Bruker AMX300 spectrometer equipped with direct and inverse
broad-band multinuclear probes. The T1 longitudinal relaxation
times and the mixing times of NOESY experiments were measured
1
13
Conclusions
The symmetric [2+2] macrocycle H -L, derived from the by using the standard inversion recovery pulse sequence. All ESI
4
condensation of 2,6-diformyl-4-chlorophenol and HAЈ· mass spectrometric measurements were performed by using an ESI-
3
HCl, was used as a suitable ligand for the preparation of MS spectrometer (ThermoFisher LCQ-Fleet) and methanolic solu-
–5 –6
tions of the samples (10 to 10 ). Thermogravimetric (TG) and
differential thermoanalyses (DTA) curves were obtained by using
a Netzsch STA449 thermoanalyzer equipped with Saft Proteous
Netzsch software. The measurements were carried out in the range
f,f homodinuclear and d,f or f,fЈ heterodinuclear complexes.
The pendant arm of the amine precursor is the turning
point in the possibility to coordinate two large metal ions
i.e., two lanthanide(III) ions] in a relatively small coordi-
nating cavity hosting the second metal ion in a stable, some-
times far from the mean N O plane. Different synthetic
[
3
–1
3
5–1200 °C in alumina crucibles in air (flux rate 50 cm min ) and
–1
a heating rate of 5 °Cmin , using neutral alumina as reference
material.
3
3
strategies have successfully been tested. The resulting com-
plexes revealed to be quite useful in the study of the proper-
ties arising from metal–metal interactions and in mixed ox-
ide formation. Furthermore, the obtainment of stable mo-
nonuclear lanthanide(III) complexes opens new interesting
X-ray Measurements and Structure Determination for Lu
intensity data were collected at room temperature by using a Philips
PW1100 diffractometer by using graphite monochromated Mo-K
radiation (0.71073 Å), following the standard procedures at room
temperature. There were no significant fluctuations in the inten-
2 2
(L) : The
α
possibilities for specific recognition processes at the free sities other than those expected from Poisson statistics. All inten-
[
16]
N O chamber, which can be engaged in subsequent metal sities were corrected for Lorentz polarization and absorption.
3
3
Eur. J. Inorg. Chem. 2010, 1853–1864
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1861

S. Tamburini, V. Peruzzo, F. Benetollo, P. A. Vigato
FULL PAPER
The structures were solved by standard direct methods.[17] Refine-
1 H, 9Ј-H), 6.47 (t, 1 H, 8-H), 6.28 (d, 1 H, 10-H), 3.99–3.85 (m,
2 H, 4Јa-H, 12Јa-H), 3.80–3.61 (m, 4 H, 4-H, 12-H), 3.80 (s, 2 H,
6-H), 3.77 (s, 2 H, 6Ј-H), 3.61–3.47 (m, 2 H, 4Јb-H, 12Јb-H), 3.21–
2.69 (m, 8 H, 5-H, 11-H, 5Јa-H, 5Јb-H, 11Јa-H, 11Јb-H) ppm.
ment was carried out by full-matrix least-squares procedures (based
2
on F
0
) by using anisotropic temperature factors for all non-hydro-
gen atoms. Hydrogen atoms were placed in calculated positions
with fixed, isotropic thermal parameters (1.2 Uequiv of the parent
carbon atom). The calculations were performed with the SHELXL-
[
(
Y(H
2
-L)(NO
3 2
)]·3H O: IR: ν˜ = 1658 (νC=N uncoordinated), 1636
–1
νC=N coordinated), 1442–1343 (νNO
3
) cm . ESI-MS: m/z =
2 2 7
L)] . C38H44Cl N O10Y (918.58): calcd. C 49.69, H
[
18]
[19]
97
program implemented in the WinGX package.
Crystallo-
+
8
4
(
00.83 [Y(H
.83, N 10.67; found C 49.60, H 5.11, N 10.33. H NMR
OD): δ = 8.60 (br. s, 2 H, 13-H, 13Ј-H), 8.32 (s, 2
H, 3-H, 3Ј-H), 7.76 (s, 2 H, 2-H, 2Ј-H), 7.55 (s, 2 H, 1-H, 1Ј-H),
.16 (d, 1 H, 7-H), 7.03 (t, 1 H, 9-H), 6.91 (d, 1 H, 7Ј-H), 6.60 (t,
3 H, 8-H, 10-H, 10Ј-H), 6.41 (t, 1 H, 9Ј-H), 6.34 (t, 1 H, 8Ј-H),
.21–3.82 (m, 8 H, 4-H, 12-H, 6-H, 11Ј-H), 3.79–3.44 (m, 4 H, 6Ј-
graphic and experimental details for the structure are summarized
in Table 2.
1
300 MHz, CD
3
2 2
Table 2. Crystal and refinement data for Lu (LЈ) .
7
Empirical formula
Formula weight
Crystal system
Space group
a [Å]
b [Å]
c [Å]
62 4 2 6 14
C H68Cl Lu N O
1612.96
monoclinic
P2 /n
4
H, 5Ј-H), 3.26–3.13 (m, 2 H, 5a-H, 11a-H), 3.13–2.93 (m, 6 H, 5b-
H, 11b-H, 4Ј-H, 12Ј-H) ppm.
1
13.909(3)
15.507(3)
14.86(3)
98.86(3)
3158 (1)
2
1.696
3.347
1608
2 3 2
[Lu(H -L)(NO )]·2H O: IR: ν˜ = 1658 (νC=N uncoordinated), 1636
–
1
(νC=N coordinated), 1455–1340 (νNO ) cm . ESI-MS: m/z =
3
β [°]
V [A ]
3
+
8
4
86.92 [Lu(H
.29, N 9.94; found C 47.94, H 4.32, N 9.52.
2
L)] . C38
H
42Cl
2
LuN
7
O
9
(986.68): calcd. C 46.26, H
Z
D
–3
2 3 2
˜
[Gd(H -L)(NO )]·2H O: IR: ν = 1656 (νC=N uncoordinated), 1639
calcd. [gcm ]
–
1
–1
µ (Mo-K
F(000)
α
) [mm ]
3 2 7 9
(νC=N coordinated), 1450–1345 (νNO ) cm . C38H42Cl GdN O
(968.96): calcd. C 47.11, H 4.37, N 10.12; found C 48.22, H 4.29,
N 9.69.
2
θ max [°]
50
5520
5172
409
No. of measured reflections
No. of observations [IϾ2σ(I)]
Parameters
Synthetic Route B
Preparation of [LnM(L)](X)·nS·mH
of [Ln(H -L)(NO )]·mH O (Ln = Y, m = 3; Ln = Lu, m = 2)
0.6 mmol) was added Zn(CH COO) ·2H O, Cd(NO ·4H O,
O or Ni(CH COO) ·4H O (0.6 mmol), and
2
O: To a hot methanol solution
R
1
, wR
Goodness of fit
(max, min) [eÅ ]
2
0.0395, 0.0961
1.197
0.902, –0,929
2
3
2
(
3
2
2
3
)
2
2
–3
∆
Mn(CH
3
COO)
2
·4H
2
3
2
2
NaOH (1.2 mmol). The resulting solution was heated at reflux for
2 h, then allowed to stand. The solvent was evaporated to dryness,
and the resulting residue was dissolved in methanol. The clarified
solution was evaporated to dryness, and the residue was washed
The morphology, homogeneity and the Ln/Cl or Ln/LnЈ/Cl ratio
of the complexes were investigated by using a Fei-Esem FEI
Quanta 200 FEG instrument, equipped with a field emission gun,
operating under high-vacuum conditions at an accelerating voltage
variable from 0 to 30 keV, depending on the observation needs.
EDX analyses and X-ray mapping (elemental mapping) were ob-
tained by using an EDAX Genesis energy-dispersive X-ray spec-
trometer at an accelerating voltage of 25 keV.
with Et
ZnY(L)(CH
IR: ν˜ = 1658 (νC=O acetate), 1648 (νC=N coordinated), 1635
2
O or EtOH, then collected by filtration and dried in vacuo.
[
3
COO)]·2H O: Et O was used as precipitating solvent.
2
2
–1
+
(
νC=N coordinated) cm . ESI-MS: m/z = 865.00 [YZn(L)] .
YZn (961.04): calcd. C 50.00, H 4.51, N 8.75;
40 2 6 8
C H43Cl N O
found C 50.41, H 4.60, N 8.53. TG weight loss to final oxide Y
calcd. 88.3%; found 85.43%.
2 3
O :
Synthetic Route A
Preparation of [Ln(H
2
-L)(NO
3
)]·nS: A methanolic solution of
·nH O (0.3 mmol), and NaOH
1.8 mmol) was slowly added to a warm CHCl
0.6 mmol). The resulting solution was heated at reflux for 15 min
3 2 2
[CdY(L)(NO )]·5H O: Et O was used as precipitating solvent. IR:
HAЈ·3HCl (0.6 mmol), Ln(NO
(
(
3
)
3
2
A
ν˜ = 1648 (νC=N coordinated), 1634 (νC=N coordinated), 1448–
3
solution of H-L
+
1342
(νNO ESI-MS:
3
).
m/z
=
913.00
[YCd(L)] .
C
38
H
46CdCl N O12Y (1065.06): calcd. C 42.86, H 4.35, N 9.21;
2 7
and after a further addition of NaOH (0.6 mmol) was maintained
under reflux for 2 h. The mixture was then clarified by filtering
when hot and allowed to stand. The resulting precipitate was fil-
tered, washed with methanol, and dried in vacuo. When the precipi-
tate did not form, the solvent was evaporated to dryness, and the
found C 44.38, H 4.19, N 8.60. TG weight loss to final oxide Y
calcd. 89.4%; found 92.2%.
2 3
O :
[MnY(L)(CH COO)]·3H O: Et O was used as precipitating sol-
3
2
2
vent. IR: ν = 1653 (νC=O acetate), 1648 (νC=N coordinated), 1636
˜
–
1
+
residue was treated with CH
2
Cl
2
. The solid was filtered, washed
(νC=N coordinated) cm . ESI-MS: m/z = 854.17 [YMn(L)] .
with the appropriate alcohol, and dried in vacuo.
C H Cl MnN O Y (968.60): calcd. C 49.60, H 4.68, N 8.68;
4
0
45
2
6
9
found C 50.72, H 4.60, N 8.30. TG weight loss to final oxide
YMnO : calcd. 79.89%; found 79.93%.
[
1
C
La(H -L)(CH COO)]·Et O: IR (KBr): ν˜ = 1660 (νC=O acetate),
640 (νC=N uncoordinated), 1630 (νC=N coordinated) cm .
LaN (985.73): calcd. C 53.61, H 5.22, N 8.53; found
C 54.22, H 5.05, N 8.92.
La(H -L)(NO )]·0.5CH
nated), 1634 (νC=N coordinated), 1414–1331 (νNO
LaN : calcd. C 48.32, H 4.11, N 10.24; found C
6.80, H 3.77, N 10.96. H NMR (300 MHz, CD
2
3
2
–
1
3
44
H
51Cl
2
6
O
7
3 2
[NiY(L)(NO )]·H O·EtOH: EtOH was used as precipitating sol-
vent. IR: ν˜ = 1646 (νC=N coordinated), 1634 (νC=N coordinated),
–
1
+
1
445–1340 (νNO ) cm . ESI-MS: m/z = 895.08 [YNi(L)] .
3
[
2
3
2 2
Cl : IR (KBr): ν˜ = 1656 (νC=N uncoordi-
–
1
C
40
H44Cl
2
N
7
NiO Y (985.34): calcd. C 48.76, H 4.50, N 9.95; found
9
3
) cm .
C 48.30, H 4.07, N 9.25. TG weight loss to final oxide YNiO2.5
calcd. 80.96%; found 81.01%.
:
C
38.5
H39Cl
3
7 7
O
1
4
2
2
7
3
OD): δ = 8.40 (s,
3 2 2
H, 3-H, 3Ј-H), 8.14 (s, 2 H, 13-H, 13Ј-H), 7.62 (br. s, 2 H, 2-H, [ZnLu(L)(CH COO)]·3.5H O: Et O was used as precipitating sol-
Ј-H), 7.48 (d, 2 H, 1-H, 1Ј-H), 7.12 (d, 1 H, 7Ј-H), 7.02 (d, 1 H, vent. IR: ν˜ = 1656 (νC=O acetate), 1648 (νC=N coordinated), 1636
–
1
+
-H), 6.97–6.85 (m, 2 H, 8Ј-H, 9-H), 6.71 (d, 1 H, 10Ј-H), 6.61 (t, (νC=N coordinated) cm . ESI-MS: m/z = 951.50 [LuZn(L)] .
1
862 Eur. J. Inorg. Chem. 2010, 1853–1864
www.eurjic.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Dinuclear Ln Complexes
C
40
H
46Cl
2
LuN
6
O
9.5Zn (1074.09): calcd. C 44.73, H 4.32, N 7.82;
H), 3.61 (s, 2 H, 6Ј-H), 3.28–3.13 (m, 2 H, 5a-H, 5b-H), 3.13–2.99
(m, 4 H, 4Ј-H, 12Ј-H), 3.02–2.95 (11a-H, 11b-H) ppm.
found C 46.91, H 4.40, N 7.81.
[
LuNi(L)](CH COO)·5H O: Et
3
2
2
O was used as precipitating sol-
[Y
(νC=N coordinated) cm . ESI-MS: m/z = 800.92 [Y(H-L) + H] .
40 8 6 4 2
C H40Cl N O Y (1130.30): calcd. C 42.51, H 3.57, N 7.44; found
2 2 2 2
(L)](Cl) ·2CH Cl : IR: ν˜ = 1658 (νC=N coordinated), 1639
–
1
+
vent. IR: ν˜ = 1658 (νC=O acetate), 1647 (νC=N coordinated), 1634
(
C
–1
+
νC=N coordinated) cm . ESI-MS: m/z = 945.50 [LuNi(L)] .
1
H49Cl
2
LuN NiO11 (1094.44): calcd. C 43.90, H 4.51, N 7.68;
6
3
C 44.10, H 3.36, N 7.53. H NMR (300 MHz, CD OD): δ = 8.69
40
found C 46.04, H 4.78, N 7.77. TG weight loss to final oxide
LuNiO2.5: calcd. 74.98%; found 74.65%.
(s, 2 H, 13-H, 13Ј-H), 8.37 (s, 2 H, 3-H, 3Ј-H), 7.80 (br. s, 2 H, 2-
H, 2Ј-H), 7.63 (br. s, 2 H, 1-H, 1Ј-H), 7.11 (d, 1 H, 7-H), 7.07–6.90
(
1
m, 2 H, 7Ј-H, 10-H), 6.68–6.39 (m, 5 H, 8-H, 9-H, 8Ј-H, 9Ј-H,
0Ј-H), 4.22–3.94 (m, 6 H, 12-H, 4-H, 11Ј-H), 3.90 (s, 2 H, 6-H),
Synthetic Route C
Preparation of [LnM(L)(X)]·nNaZ (Template): A methanolic solu-
3.76–3.58 (m, 4 H, 6Ј-H, 4Ј-H), 3.25–3.18 (m, 2 H, 5a-H, 11a-H),
3.15–3.00 (m, 6 H, 5b-H, 11b-H, 5Ј-H, 12Ј-H) ppm.
tion of HAЈ·3HCl (0.6 mmol), Y(NO
3 3 2 3 3 2
) ·xH O or Lu(NO ) ·yH O
(
0.3 mmol), and NaOH (1.8 mmol) was added slowly to a warm
[
(
Lu
2 2 2
(L)](Cl) ·3.5H O: IR: ν˜ = 1657 (νC=N coordinated), 1640
A
chloroform solution of H-L (0.6 mmol). To the resulting solution,
after heating at reflux for 10 min, was added Zn(CH COO) ·2H
0.3 mmol) and the remaining NaOH (0.6 mmol), and the mixture
–1
νC=N coordinated) cm . ESI-MS: m/z = 887.25 [Lu(H-L) +
3
2
2
O
+
H] . C38
7
H43Cl
4
Lu
2 6
N O7.5 (1094.44): calcd. C 38.18, H 3.63, N
(
1
.03; found C 38.61, H 3.54, N 6.75. H NMR (300 MHz,
was heated at reflux for 2 h, then clarified by filtration. Removal
of the solvent under reduced pressure gave a residue, which was
washed with methanol, filtered, and dried in vacuo.
3
CD OD): δ = 8.78 (br. s, 2 H, 13-H, 13Ј-H), 8.42 (s, 2 H, 3-H, 3Ј-
H), 7.83 (d, 2 H, 2-H, 2Ј-H), 7.68 (br. s, 2 H, 1-H, 1Ј-H), 7.16 (d,
H, 7-H), 7.05 (t, 1 H, 9-H), 6.93 (d, 1 H, 7Ј-H), 6.69–6.57 (m, 2
1
[
(
YZn(L)(NO
3
)]·2CH
3
COONa: IR: ν˜ = 1656 (νC=O acetate), 1648
H, 8-H, 10-H), 6.52 (d, 1 H, 10Ј-H), 6.47–6.37 (m, 2 H, 8Ј-H, 9Ј-
H), 4.30–3.99 (m, 6 H, 4-H, 12-H, 11Ј-H), 3.96 (s, 2 H, 6-H), 3.77–
[YZn(L)] . 3.52 (m, 4 H, 6Ј-H, 4Ј-H), 3.33 (m, 2 H, 5a-H, 11a-H), 3.18–2.94
νC=N coordinated), 1635 (νC=N coordinated), 1450–1345
–1
+
(
νNO
3
)
cm .
Na
found C 46.31, H 3.59, N 8.15.
ESI-MS:
m/z
=
865.50
C
42
H42Cl
2
N
7
2
O11YZn (1092.04): calcd. C 46.20, H 3.88, N 8.98;
(m, 6 H, 5b-H, 11b-H, 5Ј-H, 12Ј-H) ppm.
Synthetic Route E
[
(
=
4
LuZn(L)(CH COO)]·NaCl: IR: ν˜ = 1656 (νC=O acetate), 1648
3
Preparation of [LnLnЈ(L)](X)
0.6 mmol) and NaOH (1.2 mmol) were added to a hot methanolic
solution of the desired mononuclear complex [Ln(H -L)(NO )]·
nH O (Ln = Y, n = 3; Ln = Lu, n = 2; 0.6 mmol). The resulting
solution was heated at reflux for 2 h and then allowed to stand.
The residue, derived from the evaporation of the solvent, was
treated with methanol, and the residue was discharged by filtration.
The solution was evaporated to dryness. The resulting residue was
2 3 2
·nS (Step by Step): LnX ·nH O
–1
νC=N coordinated), 1637 (νC=N coordinated) cm . ESI-MS: m/z
(
+
3 6 6
951.50 [LuZn(L)] . C40H39Cl LuN NaO Zn (1069.52): calcd. C
2
3
4.92, H 3.68, N 7.86; found C 43.88, H 3.62, N 8.42. TG weight
2
loss to final oxide 80% of Lu
found 81%.
2 3
O and 20% ZnO: calcd. 83.6%;
Synthetic Route D
Preparation of [LnLnЈ(L)(X)
LnЈ)
2
]·nS (Template, Ln = LnЈ and Ln ϶
3
treated with CHCl or EtOH. The precipitate was filtered, washed,
and dried in vacuo.
Ln ϶ LnЈ: A methanolic solution of HAЈ·3HCl (0.6 mmol),
Y(NO (0.3 mmol), and NaOH (1.8 mmol) was added slowly to
a hot CHCl
and NaOH (0.6 mmol) were added to the resulting solution, which
was heated at reflux for 2 h, then clarified by filtration. Removal
of the solvent afforded a residue, which was treated with MeOH or
[
(
(
LuY(L)(NO ]·NaNO
3
)
2
3 3
·1.5CHCl : IR: ν˜ = 1648 (νC=N), 1640
3
)
3
νC=N), 1442–1338 (νNO
) cm . ESI-MS: m/z = 1036.92 [LuY-
–1
3
B
3
solution of H-L (0.6 mmol). LuCl
3
·6H
2
O (0.3 mmol)
L)(NO )] . C39.5H37.5Cl6.5LuN NaO13Y (1363.64): calcd. C 34.85,
+
3
9
1
H 2.78, N 9.26; found C 31.47, H 2.73, N 10.05. H NMR
300 MHz, CD OD): δ = 8.6 (br. s, 2 H, 13-H, 13Ј-H), 8.32 (s, 2
H, 3-H, 3Ј-H), 7.76 (d, 2 H, 2-H, 2Ј-H), 7.56 (d, 2 H, 1-H, 1Ј-H),
(
3
CHCl
Ln = LnЈ: A methanolic solution of HAЈ·3HCl (0.6 mmol), Ln-
Cl) (Ln = Y, Lu; 0.6 mmol), and NaOH (3.0 mmol) was added
slowly to a warm CHCl
3
, filtered, again washed with methanol, and dried in vacuo.
7
6
4
.17 (d, 1 H, 7-H), 7.05 (t, 1 H, 9-H), 6.89 (d, 1 H, 7Ј-H), 6.74–
.50 (m, 3 H, 8-H, 10-H, 10Ј-H), 6.44–6.29 (m, 2 H, 8Ј-H, 9Ј-H),
.26–3.77 (m, 6 H, 4-H, 12-H, 6-H), 3.74–3.44 (m, 6 H, 11Ј-H, 5Ј-
(
3
B
H, 6Ј-H), 3.19–2.89 (m, 8 H, 4Ј-H, 12Ј-H, 5a-H, 5b-H, 11a-H, 11b-
H) ppm. TG weight loss to final oxide LuYO
found 75.02%.
3
solution of H-L (0.6 mmol). The solution
3
: calcd. 72.01%;
was heated at reflux for 2 h then allowed to stand. The yellow pre-
cipitate, obtained for the yttrium(III) complex by addition of
CHCl
CH Cl
3
and CH
2
Cl
2
, was collected by filtration, washed with
3 2 3
[LaY(L)(NO ) ]·CH OH: IR: ν˜ = 1648 (νC=N), 1637 (νC=N),
–
1
2
2
, and dried in vacuo. The solution containing the lute-
3 39 40 2 8 11
1456–1326 (νNO ) cm . C H Cl LaN O Y (1095.53): calcd. C
1
tium(III) complex was evaporated to dryness, and the yellow crys-
talline powder obtained was treated with fresh methanol, filtered,
washed again with methanol, and dried in vacuo.
42.76, H 3.68, N 10.23; found C 45.62, H 3.81, N 10.54. H NMR
(300 MHz, [D ]DMSO): δ = 9.00 (s, 2 H, 13-H, 13Ј-H), 8.26 (s, 2
6
H, 3-H, 3Ј-H), 7.73 (d, 2 H, 2-H, 2Ј-H), 7.41 (d, 2 H, 1-H, 1Ј-H),
7
1
.14 (d, 1 H, 7-H), 7.09 (t, 1 H, 9-H), 6.98 (d, 1 H, 7Ј-H), 6.88 (t,
H, 9Ј-H), 6.76 (d, 1 H, 10-H), 6.71 (t, 1 H, 8-H), 6.34 (t, 1 H, 8Ј-
[
(
YLu(L)(NO
3
)
2
]·5CH
3
OH: IR: ν˜ = 1660 (νC=N coordinated), 1642
νC=N coordinated), 1658.71 (νC=N coordinated), 1385.61
–1
+
H), 6.19 (t, 1 H, 10Ј-H), 3.82 (s, 2 H, 6-H), 3.79–3.45 (m, 10 H, 4-
H, 12-H, 4Ј-H, 12Ј-H, 6Ј-H), 3.21–2.98 (m, 2 H, 5Јb-H, 11Јb-H),
2.98–2.59 (m, 6 H, 5b-H, 11b-H, 5Јa-H, 11Јa-H, 5a-H, 11a-H)
ppm.
(
νNO
3
)
cm . ESI-MS: m/z
LuN
found C 40.92, H 4.40, N 8.81. H NMR (300 MHz, CD
=
1035.92 [LuY(L)(NO
3
)] .
C
43
H56Cl
2
8
O15Y (1259.76): calcd. C 41.00, H 4.48, N 8.90;
1
3
OD): δ
8.63 (br. s, 2 H, 13-H, 13Ј-H), 8.34 (s, 2 H, 3-H, 3Ј-H), 7.76 (d,
H, 2-H, 2Ј-H), 7.56 (d, 2 H, 1-H, 1Ј-H), 7.15 (d, 1 H, 7-H), 7.05 [YLu(L)(NO
=
2
(
6
4
3
)
2
]·H
2
O: IR: ν˜ = 1648 (νC=N), 1640 (νC=N), 1450–
–
1
t, 1 H, 9-H), 6.91 (d, 1 H, 7Ј-H), 6.72–6.58 (m, 2 H, 8-H, 10-H), 1330 (υ NO
3
) cm . ESI-MS: m/z = 949.92 {[Lu(H
2
L)(NO
LuN
H, 4-H, 12-H), 3.94 (s, 2 H, 6-H), 3.79–3.54 (m, 4 H, 11Ј-H, 5Ј- (1117.56): calcd. C 40.84, H 3.43, N 10.03; found C 41.06, H 3.17,
3
)] +
O Y
8 11
+
+
.56 (d, 1 H, 10Ј-H), 6.51–6.29 (m, 2 H, 8Ј-H, 9Ј-H), 4.22–3.96 (m,
H} , 863.92 {[Y(H
2
L)(NO
3
)]
+
H} .
C
38
H
38Cl
2
Eur. J. Inorg. Chem. 2010, 1853–1864
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1863

S. Tamburini, V. Peruzzo, F. Benetollo, P. A. Vigato
FULL PAPER
N 9.77. TG weight loss to final oxide LuYO
3
: calcd. 72.1%; found
[3] a) D. E. Fenton, H. Okawa, Chem. Ber./Recueil 1997, 130, 433;
b) S. R. Collinson, D. E. Fenton, Coord. Chem. Rev. 1996, 148,
1
7
1
2
5%. H NMR (300 MHz, CD
3Ј-H), 8.31 (s, 2 H, 3-H, 3Ј-H), 7.76 (d, 2 H, 2-H, 2Ј-H), 7.56 (d,
H, 1-H, 1Ј-H), 7.15 (d, 1 H, 7-H), 7.05 (t, 1 H, 9-H), 6.91 (d, 1
3
OD): δ = 8.59 (br. s, 2 H, 13-H,
19; c) D. E. Fenton, Pure Appl. Chem. 1986, 58, 1437.
[
4] a) V. McKee in Advanced in Inorganic Chemistry (Ed.: A. G.
Sikes), Academic Press, San Diego, USA, 1993, vol. 40, p. 323;
b) J. Nelson, V. McKee, G. Morgan in Progress in Inorganic
Chemistry (Ed.: K. D. Karlin), Wiley, New York, USA, 1998,
vol. 47, p. 167.
H, 7Ј-H), 6.75–6.52 (m, 3 H, 8-H, 10-H, 10Ј-H), 6.49–6.29 (m, 2
H, 8Ј-H, 9Ј-H), 4.20–3.82 (m, 6 H, 4-H, 12-H, 6-H), 3.73–3.49 (m,
6
H, 11Ј-H, 5Ј-H, 6Ј-H), 3.27–3.14 (m, 2 H, 5a-H, 5b-H), 3.14–2.87
(m, 6 H, 4Ј-H, 12Ј-H, 11a-H, 11b-H) ppm.
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[
(
YEr(L)(NO ]: IR: ν˜ = 1648 (νC=N), 1639 (νC=N), 1455–1337
3 2
)
–
1
+
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νNO ) cm . ESI-MS: m/z = 879.83 [Er(H-L) + H] , 800.92
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[Y(H-L) + H] . C38
2 8
H36Cl ErN O10Y (1091.83): calcd. C 41.81, H
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3.32, N 10.26; found C 45.26, H 3.50, N 9.86.
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[
1
(
2
LuEr(L)(NO ]·NaNO : IR: ν˜ = 1649 (νC=N), 1638 (νC=N),
3
)
2
3
–1
452–1339 (νNO
3
) cm . ESI-MS: m/z = 1114.92 [LuEr(L)-
ErLuN NaO13 (1262.89): calcd. C 36.14, H
.87, N 9.98; found C 39.16, H 2.74, N 9.42.
+
NO
3
)] . C38
H36Cl
2
9
CCDC-755076 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
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[
Supporting Information (see footnote on the first page of this arti-
cle): IR spectra, SEM data, and NMR spectra of selected com-
pounds.
[
11] S. Tamburini, P. AVigato, unpublished results.
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Acknowledgments
We thank the Ministero dell’Istruzione, dell’Università e della
Ricerca (MIUR), Programmi di ricerca di Rilevante Interesse Na-
zionale (PRIN) (project code 2007W7M4NF) for financial support.
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Published Online: March 23, 2010
1864
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Eur. J. Inorg. Chem. 2010, 1853–1864