Synthesis, X-ray diffraction analysis and nonlinear optical properties of hexacoordinated organotin compounds derived from Schiff bases

Article abstract of DOI:10.1016/j.jorganchem.2014.07.002

The reaction of N,N-bis(2-hydroxy-4-R-benzylidene)-1,2-phenylendiimine (1 R = OH, 2 R = OMe) with R′₂SnO (R′ = Me, n-Bu, Ph) provided six new organotin derivatives: dimethyl-di-n-butyl- and diphenyl[N,N′-bis(3-hydroxysalicylaldehyde)-1,2-phenyl

Full text of DOI:10.1016/j.jorganchem.2014.07.002

Journal of Organometallic Chemistry 769 (2014) 64e71
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis, X-ray diffraction analysis and nonlinear optical properties
of hexacoordinated organotin compounds derived from Schiff bases
a
b
,
*
c
,
*
c
ꢀ
~
ꢀ
ꢀ
ꢀ
Blanca M. Munoz-Flores , Rosa Santillan , Norberto Farfan , Violeta Alvarez-Venicio ,
a
d
e
ꢀ
Víctor M. Jimenez-Perez , Mario Rodríguez , Omar G. Morales-Saavedra ,
Pascal G. Lacroix f, Christine Lepetit f g, Keitaro Nakatani h
,
a
ꢀ
ꢀ
ꢀ
ꢀ
Universidad Autonoma de Nuevo Leon, Facultad de Ciencias Químicas, Av. Universidad S/N, Ciudad Universitaria, San Nicolas de Los Garza Nuevo Leon, C.
ꢀ
P. 66451, Mexico
b
ꢀ
ꢀ
Departamento de Química, Centro de Investigacion y de Estudios Avanzados del IPN, 07000, Apdo. Postal. 14-740, Mexico D. F., Mexico
c
ꢀ
ꢀ
ꢀ
ꢀ
Facultad de Química, Departamento de Química Organica, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, 04510 Mexico D. F., Mexico
Centro de Investigaciones en Optica A.P. 1-948, 37000 Leon, Gto., Mexico
d
e
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Centro de Ciencias Aplicadas y Desarrollo Tecnologico, Universidad Nacional Autonoma de Mexico, CCADET-UNAM. Circuito Exterior S/N, Ciudad
ꢀ
ꢀ
Universitaria AP 70-186, C.P. 04510 Mexico D.F., Mexico
f Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, F-31077 Toulouse Cedex 4, France
Universite de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4, France
Laboratoire de Photophysique et Photochimie Supramoleculaires et Macromoleculaires (UMR 8531 du CNRS), Institut d'Alembert Ecole Normale
g
ꢀ
h
ꢀ
ꢀ
ꢀ
ꢀ
Superieure de Cachan, Avenue du President Wilson, 94235 Cachan, France
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of N,N-bis(2-hydroxy-4-R-benzylidene)-1,2-phenylendiimine (1 R ¼ OH, 2 R ¼ OMe) with
R02SnO (R0 ¼ Me, n-Bu, Ph) provided six new organotin derivatives: dimethyl-di-n-butyl- and diphenyl
[N,N0-bis(3-hydroxysalicylaldehyde)-1,2-phenylenediiminato]tin(IV) (1a), (1b), (1c) as well as dimethyl-
di-n-butyl- and diphenyl[N,N0-bis(3-methoxysalicylaldehyde)-1,2-phenylenediiminato]tin(IV), (2a), (2b),
(2c), respectively. All compounds were characterized by 1H, 13C and 119Sn-NMR, elemental analysis, UV,
IR, and mass spectrometry. Compounds 2a, 2b and 2c were characterized by single-crystal X-ray
structure analysis. In the solid state, 2a, 2b, and 2c showed the Schiff bases backbone in a bent
arrangement containing a tin atom with distorted octahedral geometry, where the ligand occupies the
four equatorial positions and the methyl, n-butyl, or phenyl groups occupy the trans axial positions. The
second-order nonlinear optical response of representative organotin compounds 2aec was estimated by
electric field induced second harmonic (EFISH) measurements where interesting bm values in the
promising range of 10e60 ꢀ 10ꢁ30 esu were evaluated.
Received 13 March 2014
Received in revised form
30 June 2014
Accepted 8 July 2014
Available online 17 July 2014
Keywords:
NLO
EFISH
119Sn-NMR
X-ray
Tin compounds
© 2014 Elsevier B.V. All rights reserved.
Introduction
application in materials chemistry where gelation [5], anticorrosion
[6], CO2 fixation [7], luminescent [8], and nonlinear optical (NLO)
More than one hundred and sixty years after their discovery by
Frankland [1], organotin derivatives are still one of the most
investigated areas in organometallic chemistry. As is well-known,
[9] properties have been reported. Metal-organic compounds
which show NLO properties play a very important role in the
chemistry of materials due to the potential applications in tele-
communications, image processing, as optical switches, optic pro-
cessing of data and generation of new frequencies [10], whereby
organic compounds have been the most widely investigated.
Organometallic materials which possess structures with electron-
organotin complexes have
a wide range of applications, in
biology, as anti-inflammatory and anti-microbial agents [2], in in-
dustry as homogeneous catalysts [3], and in organic chemistry as
well [4]. In the last decade there has been considerable interest in
the synthesis and characterization of organotin derivatives for
donor and electron-withdrawing groups bonded to a planar-
p
system, have gained considerable attention for nonlinear optics due
to their versatility and diversity, e.g., variation in metallic atoms,
different oxidation states, neutral and anionic complexes,
geometrical environment, variation of ligands, etc. Moreover, the
* Corresponding author. Tel.: þ52 55 50 61 37 25; fax: þ52 55 50 61 33 89.
ꢀ
E-mail addresses: rsantill@cinvestav.mx (R. Santillan), norberto.farfan@gmail.
ꢀ
com (N. Farfan).
http://dx.doi.org/10.1016/j.jorganchem.2014.07.002
0022-328X/© 2014 Elsevier B.V. All rights reserved.

~
B.M. Munoz-Flores et al. / Journal of Organometallic Chemistry 769 (2014) 64e71
65
metallic atoms may act as strong donor or acceptor groups being
Spectroscopy data
that, one of the basic requirements for NLO response. Also, organ-
ometallic complexes should be promising candidates as second-
order NLO materials by virtue of their low energy electronic
charge transfer excitations. Despite all these advantages, organo-
metallic complexes derived from the main group elements have
received less attention.
Our group has reported a series of “pushepull” boron com-
plexes (Fig. 1) whereby the possibility of switching NLO properties
taking advantage of the rotation of the phenyl ring attached to the
boron atom was studied using a semiempirical approach [11].
However, the organic skeleton responsible for NLO properties in
the boron derivatives has a bent geometry, leading to chromo-
phores with reduced NLO response. In order to overcome this
difficulty, and to extend the range of metal organic NLO materials,
we reported the syntheses of four “pushepull” diorganotin de-
rivatives [12]. This work showed that this kind of “pushepull”
diorganotin complexes can be easily prepared, and have better
NLO properties than the boron derivatives. The increase of the
Selected 1H, 119Sn and 13C NMR data for all compounds are
summarized in Table 1. The absence of the OH proton signals
bonded to C-2, (13.4 and 13.7 ppm for 1 and 2) in the complexes
evidenced binding of the tin atom to oxygen through the replace-
ment of the phenolic protons. In the 1H NMR spectra of 1aec and
2aec, the singlet signals between 8.04 and 8.79 ppm correspond to
the imine proton (H-7) and are slightly displaced compared with
those of the ligands (8.74 and 8.54 ppm in 1 and 2 respectively).
The 119Sn NMR spectra for 1aec and 2aec, show signals in
the ꢁ384 to ꢁ539 ppm range, which is characteristic for this type of
hexacoordinated tin derivatives containing N/Sn coordination
bonds [18]. For complexes 1c and 2c, which have phenyl sub-
stituents linked directly to the tin atom, the 119Sn chemical shift
signals appear at ꢁ530.8 and ꢁ539.1 ppm, respectively, while 1a,
1b, 2a and 2b, which possess methyl and n-butyl substituent, show
values in the range between ꢁ384.4 and ꢁ425.2 ppm, consistent
with the data reported in the literature [19].
quadratic hyperpolarizability (
from the boronate to the tin complexes, which can be attributed to
a better planarity of the -conjugated “pushepull” skeleton
responsible for the NLO behavior, as was established by X-ray
diffraction studies.
Chiral organotin complexes have also been reported by our
group and their nonlinear optical properties were measured
showing second harmonic generation (SHG) efficiencies equal to 11
times that of urea in the solid state (Fig. 2) [13]. Other organotin
Schiff base complexes exhibit sizeable second harmonic generation
(SHG) efficiencies which can be up to 8 times that of urea in the
solid state [14]. In turn, the coordination chemistry of mostly
bidentate Schiff bases with organotin compounds has received
increased attention because they show biological [15] and anti-
tumor activities [16].
b
) value is in the order of 1.5 times
The 13C NMR spectra of tin compounds 1aec and 2aec show the
imine signal between 161.2 and 163.0 ppm, similar to the corre-
sponding ligands (163.7 and 162.5). In turn C-2 is shifted to higher
frequency in the complexes, 172.4e174.2 ppm for 1aec and 2aec
compared to the ligands (164.2 and 164.7 for 1 and 2 respectively),
this is indicative that the phenolic hydrogen has been replaced by
the tin atom. The infrared spectra of ligands 1 and 2 (Table 1) show
the imine bands at 1609 and 1612 cmꢁ1, while the same band ap-
pears between 1600 and 1610 cmꢁ1 in 1aec and 2aec, due to the
SneN coordination. Mass spectra show the molecular ion in low
abundance for all compounds, and the presence of the tin atom is
easily detected from the isotopic pattern of tin [20].
p
Molecular structure
In continuation of our research, we designed a series of sym-
metric organotin complexes from tetradentate Schiff bases with
eOH and eOMe donors groups, in order to investigate their NLO
responses. The complexes 1aec and 2aec are stable and were ob-
tained in high yields (vide infra) (Scheme 1).
The details of the crystal data and summary of the collection
parameters for 2a, 2b and 2c are given in Table 2; selected bond
lengths and angles are summarized in Table 3. X-ray diffraction
studies of 2a, 2b and 2c (Figs. 3e5, respectively) corroborate that all
molecules contain a hexacoordinated tin atom and a bent ligand
skeleton; where both organic moieties are in trans position and
nitrogens and oxygens in equatorial disposition. The N/Sn dis-
tances are in the range of 2.229(3)e2.273(3) Å, in agreement with
the values observed in similar organotin compounds derivate from
tetradentate Schiff bases [21] [organotin compounds with butyl
2.266(2) and 2.279(19) Å and phenyl 2.22(2) and 2.20(2) Å]. Based
on the bond angles, the metallic atoms reside in a distorted octa-
hedral geometry. The two CeSn distances in 2c are 2.147(3) and
2.133(3) Å and are thus shorter compared to similar hexacoordi-
nated tin compound (CeSn 2.18(3) Å) reported in the literature
[21]. A water molecule is present in the asymmetric unit cell; which
shows a dimeric arrangement in compound 2a through hydrogen
bonds. Compound 2c also shows a dimeric arrangement due to
Results and discussion
Synthesis
The synthesis of the Schiff bases (1 and 2) was attained by
heating the corresponding 2-hydroxysalicylaldehyde derivative
with 1, 2-phenylenediamine in ethanol for 48 h under reflux. The
synthesis of compound 2 was previously reported in the literature
[17]. The reaction of the appropriate Schiff base and R2SnCl2
(R1 ¼ Me, Bu, or Ph) in triethylamine afforded the corresponding
organotin compounds (1aec and 2aec) (Scheme 1). The tin com-
plexes were obtained in good yields.
Fig. 1. Boron and tin derivatives of Schiff bases.

~
66
B.M. Munoz-Flores et al. / Journal of Organometallic Chemistry 769 (2014) 64e71
R1
R2
R
R3
R4
N
N
O
Sn O
Sn
O
Et2N
O
Et2N
O
Ph
Ph
Ph
Ph
R1 = Me, H
R2 = H, Ph
R = H, Me,tBu, nBu, CH2OH, Ph, Bz
R3 = H. Me, Ph
R4 = H, Ph
Fig. 2. Coordinated organotin compounds.
hydrogen bond interactions with the methanol molecule present in
the unit cell.
the m$b physical parameter in a ratio > 3, being the largest m$b value
found for the Sn(Ph)2 complex followed by the Sn(Bu)2 and Sn(Me)2
ones, respectively. This implies improved intramolecular charge
transfer properties between the donor groups and the central
acceptor imine moieties for the Sn(Ph)2 complex. The obtained
values are however in the same order of magnitude. We argue,
based on our experimental results and on the projected 3D mo-
lecular geometries, that the symmetrical monomeric bent shape of
these compounds and the nearly asymmetric “out-of-plane” posi-
tion of the R1 (Me, Bu, Ph) functional groups (considering for
instance a mirror-image symmetry), forming hexacoordinated
Sn(Me)2, Sn(Bu)2 and Sn(Ph)2 complexes, basically determine the
electronic and NLO-performance of the organotin derivatives,
delivering comparable NLO capabilities. Indeed, the overall non-
planar molecular structure of these compounds is expected to
deeply influence the delocalization of electron density over the
whole molecular architecture, giving rise to multi-dimensional
charge transfer systems and to complex hyperpolarizability bijk
tensors within triclinic space group symmetries. However, for the
current family of organotin derivatives under EFISH dipolar testing,
the dominant pseudo-one-dimensional and vectorial character of
the quadratic NLO-response results in similar charge transfer pro-
cesses occurring from the alkyl and aryl fragments through the tin-
coordinated system. However, there is an effect of the Sn(R1)2
moieties for the enhancement/variations of the quadratic NLO
properties of these compounds probably due to differences be-
tween the SneN and SneC distances. According to Table 3 and the
molecular architecture of the 2aec complexes, the most asym-
metric moiety is the Sn(Me)2/(2a) followed by the Sn(Bu)2/(2b) and
NLO properties
EFISH experimental results
According to the NLO/EFISH-technique [22] the cen-
trosymmetry of an isotropic organic dissolution comprising dipolar
molecules can be broken by applying strong DC electric fields to the
sample. This leads to a homogeneous dipolar alignment of the
organic compounds and to measurable SHG-signals. The resulting
quadratic susceptibility in EFISH experiments can be expressed in
terms of
per unit volume, F the local field factor and
hyperpolarizability given by )/5kT. Here ge represents
ge þ (
the cubic electronic contribution and /5kT the quadratic orien-
tational part, being the ground state dipole moment of the
studied chromophores and the vector component of the hyper-
polarizability tensor bijk along the dipole moment direction. In 1D
pushepull compounds and are parallel which implies a
straightforward theoretical analysis (assuming the Kleinman sym-
metry). The scalar dot product can then be inferred from a
c
(2) y NF
g
E0, where N represents the number of molecules
the overall EFISH
g
g
¼
m$b
m$b
m
b
b
m
m$b
careful analysis of the Maker Fringe experimental data, taking into
account the amplitude-period oscillations details. Accordingly, the
NLO/EFISH response of complexes 2aec were measured in chlo-
roform phases (see Table 4) where m$b values in the interesting
range of 10e60 ꢀ 10ꢁ30 have been estimated. It can be seen from
Table 4 that the incorporation of different functional R1 sub-
stituents (with R ¼ OMe fixed in this case) affects the magnitude of
Scheme 1. Synthesis of the Schiff bases and hexacoordinated tin compounds.

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B.M. Munoz-Flores et al. / Journal of Organometallic Chemistry 769 (2014) 64e71
67
Table 1
three compounds (1b, 2b, and 2c) was selected to rationalize the
effect of the ancillary R1 ligand on the tin atom, and to evaluate the
relative effect of R (OH, OMe) on the overall NLO responses of the
complexes. The computed NLO data are gathered in Table 4, in
Selected 1H, 119Sn and 13C (ppm) and stretching vibrations of the C]N bonds (cmꢁ1).
Comp.
1H
13C
119Sn
IR (C]N)
H-7
C-2
C-4
C-7
C-9
which
experimental section) and
moment by the projection along the dipole moment direction. At
first glance, it appears that the computed NLO response ( ) is
b
is the vectorial component of the hyperpolarizability (see
1
2
8.74
8.54
8.54
8.56
8.79
8.23
8.04
8.35
164.2
164.7
172.8
173.6
172.4
173.5
174.2
173.2
163.4
164.5
166.5
166.8
167.0
167.7
168.0
167.6
163.7
162.5
163.0
163.0
162.7
161.7
161.9
161.2
127.9
127.6
127.8
128.9
128.3
127.5
127.8
127.9
1609
1612
1602
1600
1600
1601
1610
1609
m
ꢀ
b
is the product of the dipole
b
1a
1b
1c
2a
2b
2c
ꢁ405.4
ꢁ425.2
ꢁ539.1
ꢁ384.4
ꢁ408.8
ꢁ530.8
m
ꢀ
b
far reduced versus that determined experimentally. Apart from the
possibility of NLO enhancement frequently observed experimen-
tally with respect to the computed static value (at
l
¼ ∞), it has to
be pointed out that the most relevant computed data has to be
found in the tendency observed for a set of substituents to modify
significantly the resulting NLO response within a series of related
molecules, such as the present tin derivatives.
the Sn(Ph)2/(2c), respectively. In this way, due to the lack of strong
and symmetrical Sn(R1)2 donor/acceptor groups, the EFISH/NLO-
properties of compounds 2aec are mainly governed by the over-
all molecular tendency to form polar structures from non-
centrosymmetric triclinic space groups, from the stationary
contribution of the R ¼ OMe functional group (similar to the R ¼ OH
group) strongly conjugated to the imine groups and from the
characteristic dipolar moment of the organotin derivatives; thus
Along this line, the first thing to observe is that
b is very weakly
influenced by the nature of the substituents. It has long been
known that, in molecular materials, the NLO effects arise from
intramolecular charge transfers between electron rich and deficient
substituents linked by p-conjugated bridges [24]. It is therefore not
surprising that two substituents of similar donating capabilities
(OH and OMe) conjugated to the same imine moieties lead to
producing
m$b values in the same order of magnitude. Besides,
according to theoretical results [9b], dipolar “pushepull” com-
pounds exhibiting similar UVevis absorbance spectra (as it is the
case for the 2aec complexes) should likely possess ß values lying in
the same order of magnitude. As the overall molecular structure
and electronic/optical properties of the 2aec complexes are grossly
preserved within the corresponding Sn(R1)2 substitutions, the ex-
pected NLO/EFISH modulations should likely arise from geometric
rather than Sn(R1)2 electronic modifications. Therefore the incor-
poration of asymmetric (in length) or fully symmetric (mirror-im-
age symmetry from the molecular “plane”) Sn(R1)2 moieties could
dramatically enhance or modify the NLO-performance of these
complexes of similar
transfer is anticipated from the alkyl and aryl fragments through
the tin atom, leading to Sn(Bu)2 and Sn(Ph)2 complexes of similar
(2b vs 2c). Finally, the main differences in the 1b, 2b and 2c series
would likely arise from dipole moments. The relative orientation of
b (1b vs 2b). Similarly, no significant charge
b
m
and
b
is a key parameter in the evaluation of the magnitude of the
value. In most “pushepull” NLO molecules, the computed
, which greatly simplify the
understanding of the origin of the NLO response ( ). In the
present case, and due to a lack of strong donor/acceptor character,
is far reduced and falls in the 1e2 D range. Moreover, its orientation
with respect to appears to strongly depend on small chemical and
conformational changes difficult to fully rationalize. All together
these computational insights lead to the idea that, if the values are
m
ꢀ
b
m
value is large (e.g. 10 D) and parallel to
b
m
ꢀ
b
m
kinds of complexes. The obtained m$b values are, in any case, in
good agreement compared with analogous nickel derivatives [23].
b
b
almost the same in these materials, the experimental EFISH values
would likely reflect various dipolar effects, considering the fact that
Theoretical studies
Theoretical insights for the understanding of the substituent
effects on the NLO response of the present complexes have been
targeted by density functional theory (DFT) computations. A set of
the
Conclusions
We have reported five new hexacoordinated tin compounds;
m magnitude will be modest in any cases.
Table 2
Crystal data for 2a, 2b and 2c.
the similarities in spectra of all compounds studied here and the X-
ray crystal structures for compounds 2a, 2b and 2c confirm hex-
acoordinated tin atoms with a distorted octahedral geometry.
Compounds 2aeb exhibit reasonably good quadratic NLO
Data
2a
2b
2c
Chemical
formula
Formula
weight
C24H24N2O4Sn$H2O C30H36N2O4Sn$H2O C34H28N2O4Sn$CH3OH
properties where
compounds have been found. In these studies, differences in the
experimental and theoretical NLO parameter larger than 300%
m$b values comparable to similar nickel-based
523.16
607.17
648.11
Crystal system Triclinic
Triclinic
P-1
Triclinic
P-1
m$b
Space group
a, [Å]
b, [Å]
P-1
have been determined according to the EFISH technique for the
Sn(R1)2 complexes. Such differences are more likely to arise from
10.4741(2)
11.0024(2)
11.0098(2)
82.7690(10)
76.1870(10)
68.9470(10)
1148.71(4)
2
11.245 (2)
11.451 (2)
11.813 (2)
96.223 (7)
99.189 (7)
99.579 (8)
1466.0 (4)
2
9.3181 (3)
10.1147(3)
17.24584(4)
87.247(2)
87.305(2)
74.2590(10)
1561.68(8)
2
the projection of
relative angles, considering similar
b
along the dipole moment (changes in the mb
values for the 2aec com-
c, [Å]
a
, [ꢂ]
b
b
, [ꢂ]
plexes) than from the Sn(R1)2 substitution.
g
, [ꢂ]
V, [Å3]
Z
Experimental section
Temp, [K]
293(2)
293(2)
293(2)
Refl. collected 24,411
Refl. unique 5465
Refl. observed 13,642
(4
Goodness
No. variables 305
13,664
4632
5994
8606
5841
7710
Instruments
All starting materials were commercially available. Solvents
were used without further purification. Melting points were
recorded on an Electrothermal 9200 apparatus and are uncorrec-
ted. Infrared spectra were measured on a FT-IR PerkineElmer
Spectrum GSX spectrophotometer using KBr pellets. 1H, 13C and
s)
1.048
1.067
403
0.0289
0.0688
1.061
371
0.0481
0.1253
Final R (4
s
)
0.0323
0.0732
Final wR2

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B.M. Munoz-Flores et al. / Journal of Organometallic Chemistry 769 (2014) 64e71
68
Table 3
Selected bond lengths (Å) and angles (ꢂ) for 2a, 2b, and 2c.
Lengths (Å)
Angles (ꢂ)
2a
2b
2c
2a
2b
2c
C(7)eN(1)
1.300(3)
1.303(3)
2.1975(17)
2.2187(18)
2.261 (2)
2.252(2)
2.126(3)
e
1.304(4)
1.294(4)
2.2139(18)
2.2212(17)
2.269(2)
2.273(3)
2.149(3)
2.131(3)
e
1.295(5)
1.313(5)
2.214(2)
2.165(2)
2.250(3)
2.229(3)
2.133(3)
e
CeSneC
OeSneO
NeSneN
166.12(11)
125.26(7)
72.64(7)
163.53(11)
127.10(7)
72.62(8)
167.15(14)
125.29(10)
72.83(11)
C(14)eN(2)
Sn(1)eO(2)
Sn(1)eO(3)
Sn(1)eN(1)
Sn(1)eN(2)
Sn(1)eC(23)
Sn(1)eC(27)
Sn(1)eC(29)
Sn(1)eC(24)
e
2.147(3)
e
2.126(3)
e
119Sn-NMR spectra were recorded on a Bruker advance DPX-300,
Jeol GSX 270 and Jeol Eclipse þ400 spectrometers. Chemical
shifts (ppm) are relative to (CH3)4Si for 1H and 13C and Sn(CH3)4 for
119Sn. Mass spectra were recorded on a Hewlett Packard 5989A
spectrometer. Elemental analyses were carried out on a Thermo
Finnigan Flash EA 1112 elemental microanalyzer.
studied compounds were performed according to the electric field
induced second harmonic (EFISH) technique [28]. In the current
case, chloroform-based solutions (at ~6.8 ꢀ 10ꢁ4 M) of compounds
2aec were prepared for EFISH measurements. A nanosecond-
pulsed Q-switched Nd:YAG laser system (at 10 Hz) was imple-
mented as the fundamental excitation beam (lu ¼ 1.064
mm)
inducing the representative SHG Maker-fringe patterns in the
organic liquid samples. The Maker-fringe amplitude oscillations
were obtained by translating a home-made wedge-shaped glass
X-ray data collection and structure determination
cell (BK7 glass blades fixed around
q
¼ 4ꢂ) orthogonally to the laser
In all cases the single crystals suitable for X-ray structural
studies were obtained by slow evaporation from a solution of each
compound in mixtures of CHCl3 and hexane. The crystal data were
beam direction. The glass cells were placed between two flat large-
area stainless steel electrodes connected to a high voltage supply
(at 5.7 kV) synchronized with the available laser source. The
recorded on an Enraf Nonius Kappa-CCD (
l
MoKa
¼ 0.71073 Å,
generated SHG-signals (l2 ¼ 0.532
mm) were conveniently filtered
graphite monochromator, T ¼ 293 K-CCD rotating images scan
mode). The crystals were mounted on a Lindeman tube. Absorption
corrections were performed using the SHELX-A program [25]. All
reflection data set were corrected for Lorentz and polarization ef-
fects. The first structure solution was obtained using the SHELXS-97
program and then SHELXL-97 program was applied for refinement
and output data [19]. All software manipulations were done under
the WIN-GX environment program set [26]. Molecular perspectives
were drawn under ORTEP3 drawing application [27]. All heavier
atoms were found by Fourier map difference and refined aniso-
tropically. Some hydrogen atoms were found by Fourier map dif-
ferences and refined isotropically. The remaining hydrogen atoms
were geometrically modeled and are not refined.
u
and detected by a photomultiplier tube connected to a digital
oscilloscope. Both a urea power sample and a pure chloroform
solution were used for reference and calibration purposes.
Computational details
The quadratic molecular hyperpolarizabilities (b) of the tin de-
rivatives were investigated computationally, at the B3PW91/6-
31G**/LANL2DZ(Sn) level [29], using the finite field (FF) proce-
dure available in the Gaussian09 package [30]. B3PW91 was
selected as the functional for the computations in relation to its
NLO/EFISH measurements
The second-harmonic generation (SHG) activity and the exper-
imental evaluation of the molecular hyperpolarizabilities (b) of the
Fig. 3. Crystal structure of compound 2a. Hydrogens were omitted for clarity.
Fig. 4. Crystal structure of compound 2b. Hydrogens were omitted for clarity.

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B.M. Munoz-Flores et al. / Journal of Organometallic Chemistry 769 (2014) 64e71
69
The following procedure was used in the syntheses of com-
pounds 1a-1c and 2aec, the ligands 1, 2 and the corresponding tin
compounds were stirred in ethanol for 12e24 h with triethylamine.
The precipitate was filtrated under vacuum and washed with
hexane, followed by recrystallization from chloroform-hexane
solution.
N,N-Bis(2,4-dihydroxybenzylidene)-1,2-phenylenediimine (1)
Compound 1 was obtained from 2.76 g (20 mmol) of 2, 4-
dihydroxybenzaldehyde and 1.08
g
(10 mmol) of 1,2-
phenylenediimine. The product was obtained as a yellow solid
(3.10 g), yield 89%, mp 224 ꢂC. IR (KBr) vmax (cmꢁ1): 3179 (OH), 3174
(OH), 2898, 2518, 1609 (C]N), 1574, 1545, 1500, 1356, 1307, 1231,
1209, 1181, 1153, 1122, 979, 845, 743, 697, 531. MS m/z (%): 349
(Mþþ1,12), 348 (Mþ, 43), 228 (26), 227 (55), 226 (100), 212 (21),119
(21); 1H NMR (300 MHz, DMSO-d6)
H-3), 6.39 (1H, dd, J ¼ 2.2, 8.5 Hz, H-5), 7.31 (1H, dd, J ¼ 7.5, 1.5 Hz,
H-9) 7.37 (1H, dd, J ¼ 7.5, 1.5 Hz, H-10), 7.43 (1H, d, J ¼ 8.5 Hz, H-6),
8.74 (1H, s, H-7), 10.40 (1H, s, OH), 13.42 (1H, s, OH); 13C NMR
d
(ppm): 6.29 (1H, d, J ¼ 2.2 Hz,
(75.4 MHz, DMSO-d6)
d (ppm): 103.2 (C-3), 108.7 (C-5), 113.1 (C-1),
120.3 (C-10), 127.9 (C-9), 135.3 (C-6), 142.8 (C-8), 163.4, 164.2 (C-4,
C-2), 163.7 (C-7). HRMS calc. m/z for C20H16N2O4 [MþþH]þ:
349.1183; Found 349.1183.
Fig. 5. Crystal structure of compound 2c. Hydrogens were omitted for clarity.
Dimethyl[N,N0-bis(3-hydroxysalicylaldehyde)-1,2-
phenylenediiminato]tin(IV) (1a)
previous use in related tin derivatives [12e14], the LANL2DZ
pseudo-potential being used to account for relativistic effects on
the tin atom. The molecular structures were first fully optimized
without any symmetry constraints. Vibrational analysis was per-
formed at the same level in order to check the obtention of a
minimum on the potential energy surfaces.
Compound 1a was obtained from the reaction of 0.348 g
(1 mmol) of compound 1 and 0.22 g (1 mmol) of dichlor-
odimethyltin. The product was obtained as a yellow solid (0.368 g),
yield 74%, m.p. >350 ꢂC. IR (KBr) vmax (cmꢁ1): 3350 (OH), 2909,
2597, 1602 (C]N), 1527, 1494, 1440, 1358, 1238, 1179, 1126, 978,
890, 844, 796, 756, 668. MS m/z (%): 497 (Mþþ1, 4), 476 (Mþ, 5), 481
(98), 466 (14), 348 (17), 329 (14), 226 (100), 212 (16), 165 (25), 132
The calculations of the hyperpolarizabilities were performed
with the default value of Field strength of 0.001 atomic units. In the
(27); 1H NMR (300 MHz, DMSO-d6)
d
(ppm): 0.39 [3H, s, 2J
FF approach,
b is obtained as the numerical partial derivative of the
(
119Sne1H) ¼ 104.6 Hz, CH3], 5.92 (1H, d, J ¼ 2.0 Hz, H-3), 6.09 (1H,
energy (W) with respect to the electric field (E), evaluated at zero
field according to the following equation:
dd, J ¼ 2.0, 8.8 Hz, H-5), 7.25 (1H, d, J ¼ 8.8 Hz, H-6), 7.29 (1H, dd,
J ¼ 7.5, 1.5 Hz, H-9), 7.38 (1H, dd, J ¼ 7.5, 1.5 Hz, H-10), 8.54 [1H, s, 3J
!
(
119Sne1H) ¼ 129.02 Hz, H-7],10.18 (1H, s, OH); 13C NMR (75.4 MHz,
v3W
vEivEjvEk
(ppm): 7.4 [1J
bijk ¼ ꢁ
(3)
DMSO-d6)
d
(
119Sne13C)
¼
1081.2 Hz, 1J
117Sne13C) ¼ 1036.2 Hz, CH3], 106.5 (C-3), 106.9 (C-5), 114.5 (C-1),
E¼0
(
118.6 (C-10), 127.8 (C-9), 139.6 (C-6), 140.0 (C-8), 163.0 (C-7), 166.5
an expression which is only valid for the static field limit. Following
(C-4), 172.8 (C-2); 119Sn-NMR (149.08 MHz, DMSO-d6)
this approach,
b
is the magnitude of the vectorial hyper-
d
(ppm): ꢁ405.4. HRMS calc. m/z for C22H20N2O4Sn [MþþH]þ:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
polarizability (b ¼ ðbxÞ2 þ ðbyÞ2 þ ðbzÞ2 with bi
after assumption of the Kleinman symmetry conditions [31].
¼
bixx
þ
biyy
þ
bizz,
497.0522; Found 497.0521.
Di-n-butyl[N,N'-bis(3-hydroxysalicylaldehyde)-1,2-
phenylenediiminato]tin(IV) (1b)
Compound 1b was obtained from 0.348 g (1.00 mmol) of com-
pound 1 and 0.304 g (1 mmol) of dichlorodibutyltin. The product
was obtained as a yellow solid (0.476 g), yield 82%, m.p. 203 ꢂC. IR
(KBr) vmax (cmꢁ1): 3246 (OH), 3071, 2953, 2922, 2858, 2608, 1600
(C]N), 1575, 1545, 1487, 1439, 1381, 1235, 1185, 1126, 976, 849, 796,
752, 663, 622, 485. MS m/z (%): 581 (Mþþ1,1), 580 (Mþ,1), 523 (34),
330 (12), 269 (9), 226 (100), 169 (28), 110 (17), 43 (22); 1H NMR
Syntheses
Ligands 1 [32] and 2 [33] were synthesized by reacting salicy-
laldehyde, or 4-methoxysalicylaldehyde with 2-phenylenediimine
in a 2:1 ratio, in ethanol under reflux.
(300 MHz, DMSO-d6)
d
(ppm): 0.59 (3H, t, J ¼ 9.7 Hz, H-14),
Table 4
1.02e1.15 (4H, m, H-13, H-12), 1.29e1.31 (2H, m, H-11), 5.91 (1H, d,
J ¼ 2.1 Hz, H-3), 6.09 (1H, dd, J ¼ 2.1, 8.8 Hz, H-5), 7.24 (1H, d,
J ¼ 8.8 Hz, H-6), 7.29 (1H, dd, J ¼ 7.5, 1.5 Hz, H-9), 7.51 (1H, dd,
J ¼ 7.5, 1.5 Hz, H-10), 8.56 (1H, s, H-7), 10.14 (OH); 13C NMR
DFT Computed and experimental NLO data for Representative Tin Schiff-base
Complexes.
Compounds
b
(cal)
m
(cal)
m
ꢀ
b
(cal)
m
$
b
(exp)
Angle: mb
(deg.)
(1064 nm)
(75.4 MHz, DMSO-d6)
d (ppm): 14.3(C-14), 26.6 (C-12), 26.7 (C-13),
1b
2a
2b
2c
19.0
2.07
1.23
1.35
1.64
25.7
49.3
28.3 (C-11), 106.8 (C-3), 107.1 (C-5), 114.9 (C-1), 118.6 (C-10), 128.8
(C-9), 140.0 (C-6), 140.7 (C-8), 163.0 (C-7), 166.8 (C-4), 173.6 (C-2);
14.8
48.2
56.4
19.0
19.9
12.0
13.2
117.9
66.2
119Sn-NMR (149.08 MHz, DMSO-d6)
d
(ppm): ꢁ425.2. HRMS calc. m/
b
in 10ꢁ30 cm5 esuꢁ1 and
m
in Debye.
z for C28H32N2O4Sn [MþþH]þ: 581.1463; Found 581.1463.

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B.M. Munoz-Flores et al. / Journal of Organometallic Chemistry 769 (2014) 64e71
70
Diphenyl[N,N0-bis(3-hydroxysalicylaldehyde)-1,2-
phenylenediiminato]tin(IV) (1c)
was obtained as a yellow solid (0.496 g), yield 82%, m.p. ¼ 202 ꢂC. IR
(KBr) vmax (cmꢁ1): 3445, 2926, 2861, 2346, 1610 (C]N), 1574, 1514,
1381,1314,1209,1122,1026, 974, 838, 750, 616, 521. MS m/z (%): 607
(Mþþ1, 0.5), 608 (Mþ, 0.2), 555 (16.6), 552 (28.6), 551 (100), 494
(18), 370 (11.4), 358 (12.7), 240 (4.8), 192 (4), 163 (6.8); 1H NMR
Compound 1c was obtained from 0.348 g (1 mmol) of com-
pound 1 and 0.344 g (1 mmol) of dichlorodiphenyltin. The product
was obtained as a yellow solid (0.47 g), yield 76%, m.p. 213 ꢂC. IR
(KBr) vmax (cmꢁ1): 3183 (OH), 2983, 2788, 2721, 1600 (C]N), 1594,
1575, 1541, 1475, 1435, 1390, 1221, 1178, 1125, 986, 852, 775, 736,
697. MS m/z (%): 621 (Mþþ1, 40), 620 (Mþ, 20), 619 (35), 543 (100),
541 (75), 307 (88), 289 (51), 255 (71), 242 (98), 219 (20) 165 (15); 1H
(270 MHz, CDCl3)
(4H, m, H-13, H-12), 1.39e1.57 (2H, m, H-11), 3.78 (OMe), 6.17e6.19
(2H, m, H-3, H-5), 7.04 (1H, d, J ¼ 9.4 Hz, H-6), 7.26e7.29 (2H, m, H-
d
(ppm): 0.63 (3H, t, J ¼ 7.2 Hz, H-14), 1.09e1.21
9, H-10), 8.24 (1H, s, H-7); 13C NMR (75.47 MHz, CDCl3)
d (ppm):
NMR (300 MHz, DMSO-d6)
d
(ppm): 5.94 (1H, d, J ¼ 1.9 Hz, H-3),
14.1 (C-14), 25.6, 26.8 (C-12, C-13), 28.5 (C-11), 55.8 (OMe),104.4 (C-
3), 107.4 (C-5), 114.9 (C-1), 117.9 (C-10), 127.8 (C-9), 137.9 (C-6), 141.3
(C-8), 161.9 (C-7), 168.0 (C-4), 174.4 (C-2); 119Sn-NMR (100.74 MHz,
6.07 (1H, dd, J ¼ 1.9, 8.8 Hz, H-5), 7.08e7.13 (3H, m, H-m, H-p), 7.23
(1H, d, J ¼ 8.8 Hz, H-6), 7.29 (1H, dd, J ¼ 7.5, 1.5 Hz, H-9), 7.57 (1H,
dd, J ¼ 7.5, 1.5 Hz, H-10), 7.45 (1H, m, H-o), 8.79 (1H, s, H-7), 10.59
CDCl3)
d
(ppm): ꢁ408.8. HRMS calc. m/z for C30H36N2O4Sn
(1H, s, OH); 13C NMR (75.4 MHz, DMSO-d6)
d
(ppm): 107.3 (C-3),
[MþþH]þ: 609.1776; Found 609.1773.
107.7 (C-5), 114.6 (C-1), 118.4 (C-10), 128.1 [4J (119Sne13C) ¼ 47.4 Hz,
C-p], 128.2 [3J(119Sne13C) ¼ 108.8 Hz, C-m), 128.3 (C-9), 135.4
[2J(119Sne13C) ¼ 60.5 Hz, C-o), 138.9 (C-6), 140.5 (C-8), 150.5 (C-i),
162.7 (C-7), 167.0 (C-4), 172.4 (C-2); 119Sn-NMR (149.08 MHz,
Diphenyl[N,N0-bis(3-methoxysalicylaldehyde)-1,2-
phenylenediiminato]tin(IV) (2c)
Compound 2c was obtained from 0.376 g (1 mmol) of compound
2 and 0.344 g (1 mmol) of dichlorodiphenyltin. The product was
obtained as a yellow solid (0.52 g), yield 80%, m.p. 229 ꢂC. IR (KBr)
vmax (cmꢁ1): 3063, 2938, 1609 (C]N), 1573, 1515, 1460, 1440, 1420,
1383, 1312, 1236, 1211, 1187, 1126, 1021, 975, 843, 795, 736, 697, 661,
618. MS m/z (%): 649 (Mþþ1, 1), 648 (Mþ, 2), 572 (33), 571 (100),
570 (49), 569 (79), 567 (44), 255 (6); 1H NMR (400 MHz, CDCl3)
DMSO-d6)
d
(ppm): ꢁ539.1. HRMS calc. m/z for C32H24N2O4Sn
[MþþH]þ: 621.0837; Found 621.0840.
N,N-Bis(2-hydroxy-4-methoxybenzylidene)-1,2-phenylenediimine
(2)
Compound 2 was obtained from 3.04 g (20 mmol) of 4-
methoxysalicylaldehyde and 1.08
g
(10 mmol) of 1,2-
d
(ppm): 3.73 (3H, s, OMe), 6.11 (1H, dd, J ¼ 2.4, 8.8 Hz, H-5), 6.16
phenylenediimine. The product was obtained as a yellow solid
(2.85 g), yield 76%, m.p. 176 ꢂC. IR (KBr) vmax (cmꢁ1): 3275 (OH),
3059, 3012, 2968, 2839, 1612 (C]N), 1585, 1568, 1512, 1464, 1439,
1371, 1341, 1293, 1244, 1203, 1169, 1136, 1115, 1032, 967, 888, 829,
747, 649. MS m/z (%): 377(Mþþ1, 17), 376 (Mþ, 64), 240 (100), 226
(1H, d, J ¼ 2.4 Hz, H-3), 6.95 (1H, d, J ¼ 8.8 Hz, H-6), 7.09e7.12 (3H,
m, H-m, H-p), 7.27 (1H, dd, J ¼ 7.5, 1.5 Hz, H-9), 7.33 (1H, dd, J ¼ 7.5,
1.5 Hz, H-10), 7.62 (2H, dd, J ¼ 1.7, 7.7 Hz, H-o), 8.35 (1H, s, H-7); 13
C
NMR (100 MHz, CDCl3)
d (ppm): 55.4 (OMe), 104.8 (C-3), 107.4 (C-
5), 114.4 (C-1), 117.3 (C-10), 127.5 [4J(119Sne13C) ¼ 148.6 Hz, C-p],
(17), 197 (2), 137 (6); 1H NMR (300 MHz, DMSO-d6)
d (ppm): 3.83
127.6 [3J(119Sne13C)
¼
450.0 Hz, C-m], 127.9 (C-9), 135.2
(3H, s, OMe), 6.48 (1H, dd, J ¼ 2.4, 8.6 Hz, H-5), 6.56 (1H, d,
J ¼ 2.4 Hz, H-3), 7.22 (1H, dd, J ¼ 7.5, 1.5 Hz, H-9), 7.28 (1H, dd,
J ¼ 7.5, 1.5 Hz, H-10), 7.27 (1H, d, J ¼ 8.6 Hz, H-6), 8.54 (1H, s, H-7),
[2J(19Sne13C) ¼ 247.7 Hz, C-o), 137.7 (C-6), 139.4 (C-8), 147.3 (C-i),
161.2 (C-7), 167.6 (C-4), 173.2 (C-2); 119Sn-NMR (120.48 MHz,
DMSO-d6)
d
(ppm): ꢁ530.8. Elemental analysis calc. for
13.65 (1H, s, OH); 13C NMR (75.4 MHz, DMSO-d6)
d (ppm): 55.86
C34H28O4N2SneH2O: C 61.38, H 4.54, and N 4.21%. Found: C 61.32, H
(OMe), 101.6 (C-3), 107.6 (C-5), 113.6 (C-1), 119.8 (C-10), 127.6 (C-9),
133.9 (C-6), 142.6 (C-8), 162.5 (C-7), 164.5164.7 (C-4, C-2);
Elemental analysis calc. for C22H20O4N2: C 70.27, H 5.32, and N
7.45%. Found: C 70.05, H 5.89, and N 7.31%.
4.99, and N 4.04%.
Appendix A. Supplementary material
Dimethyl[N,N0-bis(3-methoxysalicylaldehyde)-1,2-
phenylenediiminato]tin(IV) (2a)
CCDC 1009493, 990674 and 990675 contain 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.
Compound 2a was obtained from 0.376 g (1 mmol) of compound
2 and 0.219 g (1 mmol) of dichlorodimethyltin. The product was
obtained as a yellow solid (0.49 g), yield 94%, m.p. 245 ꢂC. IR (KBr)
vmax (cmꢁ1): 3006, 2931, 2833, 1601 (C]N), 1575, 1519, 1419, 1391,
1358, 1305, 1257, 1204, 1182, 1143, 1123, 1027, 974, 836, 791, 753,
616. MS m/z (%): 525 (Mþþ1, 1), 524 (Mþ, 2), 513 (17), 510 (25), 509
(100), 508 (43), 507 (74), 506 (33), 505 (41), 358 (8), 343 (13); 1H
Acknowledgments
Financial support from CONACyT, UNAM (PAPIIT IN-214513),
UNAM-DGAPA and ECOS program (ECOS action #M11PP01) is
acknowledged. Thanks are given to Marco A. Leyva for X-ray data
collection. The theoretical studies were performed using HPC re-
sources from CALMIP (Grant 2013 [0851]]).
NMR (300 MHz, DMSO-d6)
d
(ppm): 0.69 [3H, s,
2J(119Sne1H) ¼ 105.4 Hz, 2J(117Sne1H) ¼ 100.9 Hz, CH3), 3.79 (3H, s,
OMe), 6.17 (1H, d, J ¼ 2.4 Hz, H-3), 6.21 (1H, dd, J ¼ 2.4, 8.9 Hz, H-5),
7.05 (1H, d, J ¼ 8.9 Hz, H-6), 7.29 (1H, dd, J ¼ 7.5, 1.5 Hz, H-9), 7.34
(1H, dd, J ¼ 7.5, 1.5 Hz, H-10), 8.23 [1H, s, 3J (119Sne1H) ¼ 12.86 Hz,
H-7]; 13C NMR (75.4 MHz, DMSO-d6)
d
(ppm): 6.24
References
[1J(119Sne13C) ¼ 4099.1 Hz, 1J(117Sne13C) ¼ 3913.4 Hz, CH3), 55.33
(OMe), 103.9 (C-3), 107.2 (C-5), 114.3 (C-1), 117.7 (C-10), 127.5 (C-9),
137.4 (C-6), 140.4 (C-8), 161.7 (C-7), 167.7 (C-4), 173.5 (C-2); 119Sn-
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pound 2 and 0.304 g (1 mmol) of dichlorodibutyltin. The product

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B.M. Munoz-Flores et al. / Journal of Organometallic Chemistry 769 (2014) 64e71
71
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