N→Sn-Coordinated Stannaoxidoborates Containing a SnB4O6 Unit

Article abstract of DOI:10.1021/acs.inorgchem.5b02505

We report here the synthesis of new N→Sn-coordinated stannaoxidoborates H[LSnB₄O₆R₄] {L = [2,6-(Me₂NCH₂)C₆H₃]^- and R = Ph (6), 4-Br-Ph (7), 3,5-(CF₃)_2<

Full text of DOI:10.1021/acs.inorgchem.5b02505

Article
pubs.acs.org/IC
N→Sn-Coordinated Stannaoxidoborates Containing a SnB O Unit
4
†
6
†
‡
‡
§
§
,†
Barbora Mairychova,
́
I. V. Kityk, Artur Maciag, Filip Bures,
̌
Milan Klikar, Ales
̌
Ru
̊
zi
̌
ck
̌
a, Libor Dostal
́
,†
and Roman Jambor*
†Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, 53210 Pardubice, Czech
Republic
‡
Faculty of Electrical Engineering, Czestochowa University of Technology, Armii Krajowej 17, Czestochowa 42201, Poland
§
Department of Organic Chemistry, Faculty of Chemical Technology, University of Pardubice, 53210 Pardubice, Czech Republic
*
S Supporting Information
ABSTRACT: We report here the synthesis of new N→Sn-coordinated
−
stannaoxidoborates H[LSnB O R ] {L = [2,6-(Me NCH )C H ] and R =
4
6
4
2
2
6
3
Ph (6), 4-Br-Ph (7), 3,5-(CF ) -Ph (8), and 4-CHO-Ph (9)} containing a
3
2
nonsymmetric SnB O unit. Compounds 6−9 represent new derivatives of
4
6
−
the pentaborates [B O R ] in which the central boron is substituted by a tin
5
6 4
atom. Compounds 6−9 were characterized by means of elemental analysis,
electrospray ionization mass spectrometry, and NMR spectroscopy and in the
case of 6−8 also by single-crystal X-ray diffraction analysis. The structures of
N→Sn-coordinated stannaoxidoborates 6−8 consist of a spirobicyclic
arrangement, with two six-membered SnB O rings at the tin atom providing
2
3
−
the new stannaoxidoborate [LSnB O R ] motif, which is compensated for by
4
6 4
the proton atom coordinated to the Me N group of the ligand L. The linear and thermal properties of 6−9 were studied with the
2
help of electronic absorption spectra and differential scanning calorimetry. In addition, the presence of the nonsymmetric
stannaoxidoborate SnB O unit in 6, 7, and 9 prompted us to investigate their second-order nonlinear-optical properties.
4
6
INTRODUCTION
system by Lehmann and Teske, giving porous aluminoborate
analogues. In recent years, attempts to incorporate other
■
8
Borate compounds are of considerable interest because of their
rich structural chemistry and potential applications in
mineralogy, luminescence, and nonlinear-optical (NLO)
heteroatoms into a pure borate framework have resulted in
9
10
some intriguing systems, such as B−O−P, B−O−V, B−O−
2
b
11
12
13
14
1
Co, B−O−Zn, B−O−Ga, B−O−Ge, and B−O−Sn.
materials. The chemistry of inorganic borates is widely studied
As mentioned, borates have been studied as NLO materials
and quite complex. This complexity arises from the flexibility of
boron, which can form planar and nonplanar BO groups and
because of planar ionic groups with π-conjugated systems such
3
as BO trigonal planes, which are responsible for efficient SHG
3
tetrahedral BO groups. These units may further link together
4
15
coefficients of the materials. However, there are few
by sharing common oxygen atoms to form isolated rings and
cages or polymerize into infinite chains, sheets, and networks.
In the past, borates have formed the following systems: main-
1
,2
noncentrosymmetric structures that contain only BO units.
3
It was demonstrated that substitution of the central boron atom
5
−
3
4
in pentaborate [B O ] by a copper atom is possible to
5 10
group and transition-metal (TM) borates, rare-earth borates,
6−
16
5
6
provide a pseudosymmetric [CuB O ] unit. The isolated
4 10
and organic- and TM-complex- templated borates. Most metal
borates were made by high-temperature solid-state reaction
methods or boric acid flux methods. However, organic- or TM-
complex-templated borates were usually synthesized under
moderate-temperature hydrothermal conditions and demon-
strated that a useful property of metallo-templated borate can
complex Li [CuB O ] has been shown to be a new
6
4
10
1
6
congruently melting NLO material.
In addition, while the chemistry of the pentaborates
is well explored, analogous B-aryl-substituted
pentaborates [B O R ] are rare. In 2002, Nashihara et al.
5
−
[
B O ]
5
10
−
17
5
6 4
6
reported the reaction of organoboric acid with a parent
be the function of metal cations.
+
−
rhodium complex to yield [Rh(PMe ) ] [B O R ] , where the
One of the important applications of borates is based on
their optical properties, for example, second-order NLO
3 4
5
6 4
−
anionic part of the B-aryl-substituted pentaborate [B O R ] is
compensated for by the rhodium complex cation. During the
reaction, however, no substitution of the central boron atom in
5
6 4
1
7
1
e
properties. The most well-known examples are the discovery
of β-BaB O or LiB O as useful NLO materials for efficient
2
4
3
5
−
7
the B-aryl-substituted pentaborate [B O R ] has been
second harmonic generation (SHG) of Nd:YAG lasers. Their
excellent NLO properties and wide use in industry rekindled
the enthusiasm about the study of borates with NLO activities.
Being in the same group as boron, aluminum can exist in the
AlO , AlO , and AlO forms and was introduced into the borate
5
6 4
detected.
Received: October 30, 2015
4
5
6
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.5b02505
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Recently, it was demonstrated that the boron atom of the
boroxine ring can be easily substituted by metal atoms to give a
variety of metallaboroxines of the general formula M(O B R ),
to stand in air (see the Supporting Information). Reactions of
2−5 with 2 equiv of the parent organoboric acid RB(OH) or
2
of 1 with 4 equiv of RB(OH) provided 6−9 in moderate yield
3
2
2
2
1
8
19
20a
20a
20b
where M is Pt, Al, Sb, Bi, or Sn. Later on, we have
provided the easy preparation of new stannaboroxines of the
general formula (L-k N C)PhSn(O B R ), where L is 2,6-
(around 60%) along with the elimination of CO , H O, and
2
2
C H . The formation of 6−9 is remarkable in that the
6
6
diorganotin(IV) fragment of the starting 2−5 reacts with
organoboric acid under the elimination of a benzene molecule.
The formation of a monoorganotin(IV) fragment with new
Sn−O(B) bonds proceeds readily at ambient conditions despite
Sn−C bond cleavage reactions usually occur at elevated
3
2
3 2 2
bis(dimethylaminomethy)phenyl and R is an aryl substituent,
21
respectively, containing a six-membered SnB O ring. Our
2
3
extensive research in the field of stannaboroxine systems has
also provided the synthesis of a new type of stannaoxidoborate,
H[(L-k NC)SnB O R ], derivatives of the pentaborates
23
temperatures. This suggests that the presence of N→Sn
coordination in the starting 2−5 facilitates the elimination of a
benzene molecule to form a monoorganotin(IV) fragment in
6−9. In addition, the hydrolytic process is accompanied by
transformation of a L-k N C tridentate fashion in starting 2−5
2
4
6 4
−
[
B O R ] in which the central boron atom is substituted by
5 6 4
a tin atom. In this paper, we report the synthesis, X-ray crystal
structure, and optical properties of stannaoxidoborates H[(L-
−
k NC)SnB O R ] containing a [SnB O R ] unit.
2
4
6
4
4
6
4
3
2
to a L-k NC bidentate fashion of ligand L found in 6−9. A
2
RESULT AND DISCUSSION
Synthesis and Characterization of Compounds 2−9.
The treatment of organotin(IV) carbonate (L-k N C)PhSnCO
second Me N group of ligand L is protonated during the
■
2
reaction, and the Me
stannaoxidoborate [(L-k
This demonstrates the crucial role of ligand L for the formation
of 6−9. To give further support for the importance of ligand L,
the reaction of Ph SnCl or BuSnCl with 4 equiv of PhB(OH)
2
NH+ group compensates for the
2
−
NC)SnB
O
6
R
4
]
fragment in 6−9.
3
2
3
2
4
(
1) with organoboric acids RB(OH) at a 1:2 molar ratio
2
provided the corresponding organotin(IV) stannaboroxines (L-
−
k N C)PhSn(O B R ), where L = [2,6-(Me NCH )C H ]
3
2
3
2
2
2
2
6
3
2
2
3
2
1
21
and R = Ph (2), 4-Br-Ph (3), 3,5-(CF ) -Ph (4), and 4-
CHO-Ph (5) (Scheme 1). Compounds 2, 3, and 5 were
was performed. These reactions, however, provided the starting
3
2
2
1
1
119
compounds (detected by the H and Sn NMR spectroscopy)
and an insoluble ill-defined material only.
Scheme 1. Synthesis of Stannaboroxines 2−5 and
Stannaoxidoborates 6−9
It should be also noted that studies dealing with the reactions
of N→Sb-coordinated organoantimony and bismuth oxides
[
LMO] (M = Sb, Bi) with organoboric acids yielded the
2
24
−
pentaborates [B O R ] only. Similarly, the complex [Rh-
(
organoboric acids with a parent rhodium complex. This
suggests a specific role of the tin atom in the formation of a new
class of metalloborates, where substitution of the central boron
5
6 4
+
−
PMe ) ] [B O R ] has been prepared by the reaction of
3 4 5 6 4
17
−
atom of the pentaborates [B O R ] took place.
5
6 4
All prepared complexes 6−9 are moderately soluble in
chlorinated solvents. All of the prepared compounds were
characterized by NMR spectroscopy and electrospray ionization
mass spectrometry. The molecular structures of 6−8 have been
characterized by X-ray diffraction analysis.
1
The H NMR spectra of compounds 6−9 showed the
presence of ligand L and B-aryl substituents R in a 1:4 mutual
1
integration ratio. The H NMR spectra of compounds 6−9
revealed two AX spin systems of methylene CH N and four
2
signals for the NMe2 groups of ligand L, suggesting the
presence of nonsymmetric character of a tin coordination
polyhedron with nonequivalent CH NMe arms of ligand L. In
2
2
1
addition, the H NMR spectra of compounds 6−9 revealed one
broad downfield signal of the NHMe proton in the range of δ
2
1
1.71 (8) to 12.46 (7) in a 1:4 mutual integration ratio with
1
methylene CH N protons. The H NMR spectrum of 9 showed
2
2
1
prepared and characterized according to the literature.
four singlet resonances of CHO protons at δ 10.00, 10.03,
10.06, and 10.09. The nonequivalency of the B-aryl substituents
Compound 4 was characterized by NMR spectroscopy. The
H NMR spectrum of 4 revealed a AX spin system of
methylene CH N groups and a single resonance of NMe
protons of the chelating ligand L. The Sn NMR spectrum of
1
13
R was also proven by the C NMR spectra, where signals of
13
four B-aryl substituents were observed. The C NMR spectrum
of 9 showed four singlet resonances of CHO carbon atoms at δ
192.6, 192.8, 193.1, and 193.3. Similarly, four signals at δ −62.8,
2
2
1
19
4
showed single resonances at δSn −366.9, suggesting the
21,22
19
presence of a six-coordinated tin(IV) center.
−62.9, −63.0, and −63.2 were detected in the F NMR
Rather surprisingly, compounds 2−5 hydrolyze to give
stannaoxidoborates H[(L-k NC)SnB O R ] {L = [2,6-
Me NCH )C H ] , with R = Ph (6), 4-Br-Ph (7), 3,5-
CF ) -Ph (8), and 4-CHO-Ph (9); see Scheme 1}. These
compounds were isolated as crystalline materials in low yield
around 10%) when 2−5 were dissolved in toluene and allowed
spectrum of 8.
The 1 Sn NMR spectra revealed one signal at δ −554.2 for
6, δ −553.2 for 7, δ −550.1 for 8, and δ −553.2 for 9, and these
values are shifted upfield compared with the starting 2−5 (in
19
2
4
6
4
−
(
2 2 6 3
(
3
2
21
the range of δ −359.1 to −366.9), where a diorganotin(IV)
(
fragment is involved in the six-membered SnB O ring. On the
2
3
B
DOI: 10.1021/acs.inorgchem.5b02505
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
28
Figure 1. POV-ray schematic representation of the molecular structures of 6·C H , 7·C H , and 8, together with schematic atom numbering. The
7
8
7
8
hydrogen atoms and toluene molecules (for 6 and 7) are omitted for clarity. Selected bond lengths [Å] and angles [deg] for 6: Sn1−N1 2.345(3),
Sn1−N2 3.779(3), Sn1−O1 2.035(2), Sn1−O3 2.054(2), Sn1−O4 2.135(2), Sn1−O6 2.012(2). Selected bond lengths [Å] and angles [deg] for 7:
Sn1−N1 2.333(5), Sn1−N2 3.744(5), Sn1−O1 2.121(4), Sn1−O3 2.016(4), Sn1−O4 2.046(4), Sn1−O6 2.029(4). Selected bond lengths [Å] and
angles [deg] for 8: Sn1−N1 2.309(4), Sn1−N2 3.693(4), Sn1−O1 2.057(2), Sn1−O3 2.052(3), Sn1−O4 2.017(2), Sn1−O6 2.129(2).
other hand, the values are comparable with those found for Y→
atom N1 of the L-k NC ligand is coordinated to the tin atom, as
2
Sn-coordinated monoorganotin(IV) compounds
indicated from the Sn1−N1 bond distances [in the range of
2.309(4)−2.345(3) Å], the second nitrogen atom N2 is out of
the tin coordination sphere [in the range of 3.693(4)−3.779(3)
Å]. The values of Sn−O(B) bond distances in both SnB O
2
5
[
[
[
{ C H ( C H N M e ) - 2 , 6 } S n B r ] ( δ − 6 0 1 ) ,
6
3
2
2
2
3
26
{C H (CH OMe)-2-(CH NMe )-6}SnBr (δ −531.2), and
{C H [P(O) (OR) ] -1,3-t-Bu-5}SnBr ] (δ −885). The
6
3
2
2
2
3
27
6
2
2 2
3
2
3
NMR data thus support the transformation of the starting
diorganotin(IV) fragment to N→Sn-coordinated
monoorganotin(IV) moieties containing a negative tin center
with a nonsymmetric arrangement.
rings of 6−8 differ substantially. While the values of Sn−
O1(B), Sn−O3(B), and Sn−O6(B) [in the range of 2.012(2)−
2.054(2) Å] indicate the presence of the Sn−O covalent bonds
29
in 6 [Σ (Sn,O) = 2.03], the Sn−O4(B) bond distance is
cov
To establish unambiguously the structural feature of
compounds 6−9, single-crystal X-ray structural analysis was
carried out. Suitable single crystals of 6·C H , 7·C H , and 8
prolonged [2.135(2) Å] as a result of O4−H2−N2 hydrogen
bonding in 6 [the bond distance of O4−N2 is 2.776(4) Å in 6].
A similar situation has also been found in 7 and 8, where the
bond distances of Sn−O1(B) [2.121(4) Å] in 7 and Sn−O6(B)
[2.129(2) Å] in 8 are prolonged in comparison with the
remaining Sn−O(B) distances [in the range of 2.016(4)−
2.057(2) Å]. These oxygen atoms are again involved in the
O1−H2−N2 (7) and O6−H2−N2 (8) hydrogen bonding [the
bond distance of O1−N2 is 2.724(8) Å in 7, and that of O6−
N2 is 2.763(6) Å in 8].
7
8
7
8
were obtained from a saturated toluene solution of 6−8 at
room temperature, and molecular structures of 6·C H , 7·C H ,
7
8
7
8
and 8 are depicted together with relevant structural parameters
in Figure 1 (for crystallographic parameters, see Table S1 in the
Supporting Information).
The molecular structures of 6·C H , 7·C H , and 8 are
7
8
7
8
widely identical. The tin atom is six-coordinated by four oxygen
atoms of two O B R units and by nitrogen and carbon atoms
The structures of 6−8 consist of a spirobicyclic arrangement
3
2 2
of the ligand L. In fact, established structures of 6−8 showed
of two six-membered SnB O rings at the tin atom, providing
2
3
−
the presence of two central SnB O ring systems and one
the new stannaoxidoborate [(L-k NC)SnB O R ] motif,
2
3
2 4 6 4
organic substituent L-k NC coordinated to the tin atom,
which is compensated for by a proton atom coordinated to
2
providing the spirobicyclic arrangement. While the nitrogen
one Me N group of the L-k NC ligand. All covalent B−O(Sn)
2
2
C
DOI: 10.1021/acs.inorgchem.5b02505
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Figure 2. Distortion of the planarity of both the SnB O rings within SnB O unit in 6−8.
2
3
4
6
bonds within the SnB O unit are slightly shortened [in the
4
6
range of 1.323(5)−1.343(5) Å] in comparison with the
remaining B−O(B) covalent bond [in the range of
1
.380(7)−1.392(5) Å]. All of these values are, however, still
a bit shorter than the sum of the covalent radii Σ (B,O) =
1
cov
2
9
.48 Å.
The distortion of the planarity of both SnB O rings in the
2
3
SnB O unit depends on the B-aryl substituents R and provides
4
6
different mutual orientations of both the SnB O rings within
2
3
SnB O unit. In compounds 6 and 7, where R is Ph and 4-BrPh,
4
6
the oxygen atom O2 of the B1−O2−B2 moiety is bent out by
0
.740 Å from the mean plane defined by the O1−Sn1−O3
Figure 3. π−π stacking interaction between the two 3,5-CF -C H
3
6
3
backbone in 6 (0.604 Å in 7). Similarly, the oxygen atom O5 of
the B3−O5−B4 moiety is bent out by 0.663 Å from the mean
plane defined by the O4−Sn1−O6 backbone in 6 (0.609 Å in
−
groups within the stannaoxidoborate [(L-k NC)SnB O R ] unit of 8.
2
4
6 4
(
for a comparison of 6−8 with the structures of related
n−
7
; see Figure 2).
A different situation has been found in 8 containing the 3,5-
pentaborates [B O ] , see the Supporting Information).
5
10
In addition, the thermal behavior of stannaoxidoborates 6−9
was studied by differential scanning calorimetry (DSC). The
thermogram of selected compound 6 is shown in Figure 4; the
CF -Ph group as the B-aryl substituent. The oxygen atom O2 of
3
the B1−O2−B2 moiety is strongly bent out by 0.928 Å from
the mean plane defined by the O1−Sn1−O3 backbone in 8,
while the oxygen atom O5 of the B3−O5−B4 moiety is
strongly bent out by 0.737 Å from the mean plane defined by
the O4−Sn1−O6 backbone in 8 (see Figure 2). As a result of
this puckering of the SnB O unit, the O2−B3 and O5−B2
bond distances (the bond distance of the oxygen atoms O2 and
O5 involved in B−O−B bonding and the boron atoms B3 and
B2 of the opposite SnB O rings) are 3.859(7) and 3.930(7) Å,
4
6
2
3
respectively, in 8 [compared with similar bond distances of
O2−B4 and O5−B1 of 4.315(6) and 4.121(6) Å found in 6
and 4.465(10) and 4.317(10) Å in 7, respectively].
In addition, the bond distances of B2−B3 and B2C
−
ipso
B3C carbon atoms (C atoms of the B-aryl substituent) are
ipso
ipso
3
.289(9) and 3.559(7) Å, respectively, suggesting the presence
Figure 4. Representative DSC curve of 6 determined with a scanning
of a π−π stacking interaction between the two 3,5-CF -Ph
groups in 8 (see Figures 2 and 3).
3
−1
rate of 3 K min under N . Irreversible s−s transition followed by
2
thermal decomposition at the onset.
This phenomenon has not been, however, detected in 6 and
7, where the closest contacts of two boron atoms of the
opposite SnB O rings are 3.759(7) Å (6) and 3.945(12) Å (7),
respectively, with the bond distances of the parent Cipso atoms
of B-aryl substituents at 5.015(6) Å (6) and 5.402(10) Å (7)
fundamental thermal properties of all target complexes are
listed in Table 1. A joint feature of all of the target compounds
6−9 is their solid−solid (s−s) transition, followed by
decomposition. The monotropic irreversible s−s transitions
are being observed within the range of 170−200 °C and are
accompanied by sharp exothermic peaks. The irreversibility of
this transition has been verified by cooling the sample upon
reaching ca. 240 °C and repeated heating (see the onset in
Figure 4). Compounds 6−9 underwent thermal decomposition
2
3
(
see Figure 2). As a result of the different mutual orientations
of both the SnB O rings in SnB O unit, compound 6·C H
8
2
3
4
6
7
belongs to the noncentrosymmetric monoclinic space group
P2 , compound 7·C H belongs to the noncentrosymmetric
1
7
8
orthorhombic space group P21 21 21, and compound 8
crystallizes in the centrosymmetric triclinic space group P1
̅
D
DOI: 10.1021/acs.inorgchem.5b02505
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
3
0
Table 1. (Non)linear-Optical and Thermal Properties of 6−9
considered as the electron donor), while the nonconjugated
CF groups placed in positions 3 and 5 also have a diminished
effect. Compounds 6−9 showed very weak or no emissive
3
s−s
3
−1
λmax
ε (×10 mol
deff (pm transition
Td
(°C)
3
−1
−1
compound [nm (eV)]
dm cm
)
V
)
(°C)
properties, however.
As a result of the above-discussed coordination found in 6−
6
7
8
9
237 (5.23)
238 (5.21)
237 (5.23)
259 (4.79)
46.15
69.95
54.45
74.79
1.1
180
182
174
200
320
311
301
280
8
, all of the Sn−O bonds in the SnO polyhedra of 6−8 are of
1.4
4
different lengths. Each of the four boron atoms surrounding the
central tin atom is on a unique crystallographic site, and each
1.6
BRO polyhedron contains different B−O bond lengths with
2
various distortions. Additionally, none of the BRO groups are
2
in a similar range of 280−320 °C, which is relatively narrow
in the same plane. On the basis of the symmetry space groups
revealed by the X-ray measurements (Table S1 in the
Supporting Information), we have investigated the second-
order NLO properties of the noncentrosymmetric molecules 6
and 7 as well as 9 of an unknown arrangement. As mentioned
above, the stannaoxidoborate 8 possesses the centrosymmetric
(
ΔT ∼ 30−40 °C), indicating the thermal robust behavior of
these novel heteroborates.
Linear and NLO Properties. The linear-optical properties
of stannaoxidoborates 6−9 were investigated by electronic
absorption spectra, as shown in Figure 5.
space group P1
̅
and, therefore, delivered no SHG signal. Figure
6
shows the second-order susceptibility of 6, 7, and 9 as a
Figure 6. Dependence of the second-order susceptibility of 6, 7, and 9
versus the applied aligned dc electric field. The saturated dc electric
field alignment is indicated by the vertical lines.
Figure 5. UV/vis absorption spectra of 6 - 9 measured in CH Cl (2 ×
2
2
−
5
1
0
M).
function of the applied direct-current (dc) electric field
strength, and Table 1 lists the second-order susceptibilities
Table 1 lists the positions of the longest-wavelength maxima
d . As can be seen, saturation appears at the dc electric field
eff
−1
λmax and corresponding molar absorption coefficients ε. The
spectra of 6−9 are dominated by an intensive absorption band,
with a position that is a function of the peripheral R
substituents and most likely can be attributed to intramolecular
charge transfer (ICT) from the central stannaoxidoborate [(L-
strength of about 4 kV cm for all three samples, which
indicates the maximal alignment of the studied crystalline
powders. The maximal d value of 1.6 pm V was achieved for
−1
eff
compound 9, which correlates well with its bathochromically
shifted longest-wavelength absorption maxima and also
confirms its noncentrosymmetric arrangement. Compound 7
−
k NC)SnB O R ] electron-rich part to peripheral R sub-
2
4
6 4
−
1
stituents. Considering the R-substituents as electron deficient
ligands, this structural arrangement superficially resembles
metal-to-ligand charge transfer. Whereas the longest-wave-
length absorption maxima (λmax) of 6−8 are almost identical
showed susceptibility d equal to 1.4 pm V , whereas this is
eff
1.1 pm V− for 6. Although these values are less than those for
1
−
1
28,31
α-BiB O crystallites (about 4.2 pm V ),
they can further
3
6
be enhanced by appropriately changing the central anion and its
peripheral moieties, defining the principal NLO response. It
should be mentioned that in the case of α-BiB O as well as the
(
λmax = 237−238 nm) and differ mainly in the molar absorption
3 −1 −1
coefficient ε = (46.15−69.95) × 10 M cm , the formyl-
3
6
substituted derivative 9 showed a red-shifted band with the
well-known β-BaB O4 such opportunities were already
2
3
−1
−1
maximum appearing at 259 nm (ε = 74.79 × 10 M cm ).
exhausted. However, the SHG output signals are of the same
order, and their dc kinetics is almost the same, which confirms
the common origins of the observed effects. Some additional
effects such as fluorescence scattering, particularly for weakly
emissive 7, may also play a role. The second-order susceptibility
efficiency correlates with the position of the chrage-transfer
band; the less energy of the longest-wavelength absorption
maxima favors enhanced second-order susceptibility. It is also
−
Considering the stannaoxidoborate [(L-k NC)SnB O R ] unit
2
4
6 4
as electron donors, the peripheral formyl groups behave as
moderate acceptors placed in conjugated positions. This D−π−
A arrangement allows the most efficient ICT, and the most
bathochromically shifted charge-transfer band is being observed
for 9. Unsubstituted and bromine-substituted derivatives 6 and
7
do not bear any electron acceptors (bromine can rather be
E
DOI: 10.1021/acs.inorgchem.5b02505
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
worth noting that the SHG signals for 6, 7, and 9 not only
reveal promising and tunable NLO properties but also provide
a highly sensitive and definitive test for the absence of the
7.35 (d, 2H, ArH), 7.52 (m, 3H, ArH), 7.78 (d, 2H, ArH), 7.97 (s, 2H,
ArH), 8.53 (s, 4H, ArH). 13C{ H} NMR (CDCl , 25 °C): δ 44.7
1
3
(
CH ), 62.9 (CH N), 123.4 (B-Ar-C), 123.9 (CF ), 127.9 (Ph-C-3,5),
3
2
3
32
128.9 (L-C-3,5), 130.1 (Ph−C4), 130.3 (L-C-4), 130.6 (B-Ar-C),
center of symmetry.
1
1
34.3 (B-Ar-C), 134.5 (Ph-C-2,6), 138.5 (L-C1), 140.0 (B-Ar-C),
40.9 (Ph-C-1), 144.9 (L-C-2,6). 19F NMR (CDCl , 25 °C): δ −62.9.
3
CONCLUSION
119
■
Sn NMR (CDCl
Synthesis of H[(L-k
.71 mmol) was added to a stirred solution of 1 (303 mg, 0.67 mmol)
in CH Cl (20 mL) at room temperature. The reaction mixture was
3
, 25 °C): δ −366.9.
In conclusion, we report here an easy and straightforward
synthesis of new N→Sn-coordinated stannaoxidoborates H[(L-
k NC)SnB O R ] (6−9) containing a nonsymmetric SnB O
2
NC)SnB Ph
4
O
6
] (6). PhB(OH) (330.1 mg,
4 2
2
2
2
2
4
6
4
4
6
stirred for an additional 5 days at this temperature and then evaporated
in vacuo. The resulting white solid was washed with toluene (10 mL)
and dried in vacuo to give 6 as a white crystalline solid. Yield: 303.8
mg, 59%. Mp: 171−173 °C. Anal. Calcd for C H B N O Sn (MW
unit. Compounds 6−9 represent new derivatives of the
−
pentaborates [B O R ] in which the central boron atom is
5
6 4
substituted by a tin atom. Compounds 6−9 were characterized
by means of elemental analysis and NMR spectroscopy and in
the case of 6−8 also by single-crystal X-ray diffraction analysis.
The structures of 6−8 consist of a spirobicyclic arrangement of
two six-membered stannaboroxine SnB O rings at the tin
3
6
40
4
2
6
1
7
58.65): C, 56.9; H, 5.3. Found: C, 56.7; H, 5.2. H NMR (CDCl , 25
3
°C): δ 2.34 (s, 3H, CH N), 2.48 (d, 3H, CH N), 2.68 (d, 3H, CH N),
3.07 (s, 3H, CH N), 3.20 and 4.82 (AX pattern, J
CH
3
3
3
2
= 13.6 Hz, 2H,
3
H−H
2
N), 3.43 and 5.41 (AX pattern, JH−H = 11.6 Hz, 2H, CH
N), 7.02
2
2
3
2
(
4
t, 1H, ArH), 7.16−7.51 (m, 14H, ArH),7.74 (d, 2H, ArH), 8.11 (d,
atom, providing a new SnB O motif. The presence of a tin
4
6
+
13
1
H, ArH), 8.22 (d, 2H, ArH), 12.39 (s, 1H, NH ). C{ H} NMR
atom provided distortion of the planarity of both SnB O rings
2
3
(
(
CDCl , 25 °C): δ 41.1 (CH N), 43.9 (CH N), 44.1 (CH N), 47.3
3 3 3 3
CH N), 63.4 (CH N), 63.7 (CH N), 127.2 (B-Ar-C), 127.3 (B-Ar-
within the SnB O unit in 6−8. The distortion of the planarity
4
6
3
2
2
depends on the B-aryl substituents R and provides different
mutual orientations of both SnB O rings within the SnB O
6
C), 127.4 (B-Ar-C), 127.7 (L-C-3), 128.1 (L-C-5), 128.7 (B-Ar-C),
129.5 (B-Ar-C), 129.6 (B-Ar-C), 129.7 (B-Ar-C), 130.0 (B-Ar-C),
2
3
4
unit. The linear and thermal properties of 6−9 were studied
further, and it was shown that it differs mutually depending on
the B-aryl substituents R as well. It is evident that required
properties of this new class of heteropentaborates can be tuned
by the appropriate B-aryl substituents R. In addition, single-
crystal X-ray diffraction analysis and NMR studies in solution
suggested a nonsymmetrical arrangement of the tin atom in the
stannaoxidoborate SnB O unit. For this reason, the second-
1
30.7 (L-C4), 133.4 (B-Ar-C), 134.8 (B-Ar-C), 135.2 (B-Ar-C), 135.6
(B-Ar-C), 137.9 (B-Ar-C), 138.9 (B-Ar-C), 141.4 (L-C2), 144.4 (L-
C6), 150.0 (L-C1). 1 Sn NMR (CDCl , 25 °C): δ −554.2. Positive-
19
3
+
+
ion ESI-MS: 782.2 ([M + Na] , 29%), 798.0 ([M + K] , 14%).
Synthesis of H[(L-k NC)SnB O (4−Br-C H ) ] (7). (4-Br-C H )-
2
4
6
6
4 4
6
4
B(OH) (568.7 mg, 2.83 mmol) was added to a stirred solution of 1
2
(316.5 mg, 0.71 mmol) in CH Cl (20 mL) at room temperature. The
2 2
reaction mixture was stirred for an additional 5 days at this
temperature and then evaporated in vacuo. The resulting white solid
was extracted with toluene (10 mL) and dried in vacuo to give 7 as a
white crystalline solid. Yield: 441.5 mg, 58%. Mp: 194−195 °C. Anal.
Calcd for C H B Br N O Sn (MW 1074.26): C, 40.2; H, 3.4.
Found: C, 40.1; H, 3.2. H NMR (CDCl , 25 °C): δ 2.38 (s, 3H,
CH
4
6
order NLO properties of complexes 6, 7, and 9 were
−1
investigated. The maximal deff of 1.6 pm V was measured
for 9 with the peripheral formyl groups, which also showed the
most bathochromically shifted λmax. Unsubstituted and
bromine-substituted stannaoxidoborate 6 and 7 possess
36
36
4
4
2
6
1
3
N), 2.56 (d, 3H, CH N), 2.78 (d, 3H, CH
N), 3.03 (s, 3H,
= 14.0 Hz, 2H, CH N), 4.58
3
3
3
2
−1
CH N), 3.48 and 4.72 (AX pattern, J
and 5.55 (AX pattern, J
susceptibilities of 1.1 and 1.4 pm V . However, it is crucial
that the SHG output signals are of the same order for all of the
samples.
3
H−H
2
2
= 11.5 Hz, 2H, CH N), 7.12 (t, 1H,
H−H
2
ArH), 7.14−7.57 (m, 10H, ArH), 7.80−7.91 (m, 8H, ArH), 12.46 (s,
+
13
1
1
H, NH ). C{ H} NMR (CDCl , 25 °C): δ 41.6 (CH N), 44.2
3
3
(
CH N), 44.4 (CH N), 47.3 (CH N), 63.6 (CH N), 64.0 (CH N),
3 3 3 2 2
24.4 (B-Ar-C), 124.5 (B-Ar-C), 124.9 (B-Ar-C), 127.3 (B-Ar-C),
EXPERIMENTAL PART
1
■
General Methods. All reactions were carried out under argon,
using standard Schlenk techniques. Solvents were dried by standard
methods and distilled prior to use. Compounds 1−3 and 5 were
128.7 (B-Ar-C), 129.2 (L-C-3), 129.7 (L-C-5), 130.2 (B-Ar-C), 130.5
(B-Ar-C), 130.7 (L-C-4), 131.0 (B-Ar-C), 134.5 (B-Ar-C), 134.8 (B-
Ar-C), 135.1 (B-Ar-C), 136.3 (B-Ar-C), 136.5 (B-Ar-C), 136.8 (B-Ar-
2
1
0,21
prepared according to the literature,
and organoboric acids were
C), 141.5 (L-C-2), 142.5 (L-C-6), 145.1 (B-Ar-C), 149.6 (L-C-1).
13
119
119
purchased from Sigma-Aldrich. The H, C, and Sn NMR spectra
Sn NMR (CDCl , 25 °C): δ −553.2. Positive-ion ESI-MS: 1096.8
3
+
+
were recorded on a Bruker Avance500 spectrometer at 300 K in
([M + Na] , 100%), 1112.0 ([M + K] , 21%).
Synthesis of H{(L-k NC)SnB [3,5-(CF
(CF ) -C H ]B(OH) (691.3 mg, 2.68 mmol) was added to a stirred
1
13
119
CDCl . The H, C, and Sn NMR chemical shifts δ are given in
2
O
4
6
) -C H )] } (8). [3,5-
3 2 6 3 4
3
ppm and referenced to external Me Si and Me Sn. Elemental analyses
4
4
3
2
6
3
2
were performed on a LECO-CHNS-932 analyzer. The positive- and
negative-ion electrospray ionization mass spectrometry (ESI-MS)
spectra were measured on an Esquire 3000 ion-trap analyzer (Bruker
Daltonics, Bremen, Germany) in the range m/z 50−2000. The
samples were dissolved in acetonitrile and analyzed by direct infusion
solution of 1 (299.5 mg, 0.67 mmol) in CH Cl (20 mL) at room
2 2
temperature. The reaction mixture was stirred for an additional 5 days
at this temperature and then evaporated in vacuo. The resulting white
solid was extracted with toluene (10 mL) and dried in vacuo to give 8
as a white crystalline solid. Yield: 458.6 mg, 65%. Mp: 194−195 °C.
Anal. Calcd for C H B F N O Sn (MW 1302.67): C, 40.5; H, 3.3.
−1
at a flow rate of 5 μL min . The ion-source temperature was 300 °C,
4
4
32
4
24
2
6
1
the tuning parameter compound stability was 100%, and the flow rate
Found: C, 40.2; H, 3.1. H NMR (CDCl , 25 °C): δ 2.46 (s, 3H,
NCH ), 2.69 (d, 3H, NCH ), 2.91 (d, 3H, NCH ), 3.07 (s, 3H,
NCH ), 3.20 and 4.76 (AX pattern, J
and 5.62 (AX pattern, J
3
−1
and pressure of N were 4 L min and 10 psi, respectively.
2
3
3
3
2
Synthesis of (L-k N C)PhSn{O B [3,5-(CF ) C H )] } (4). 3,5-
= 14.5 Hz, 2H, CH N), 4.55
H−H 2
3
2
3
2
3 2
6
3
2
3
2
(
(
CF ) C H B(OH) (412 mg, 1.6 mmol) was added to a solution of 1
= 11.5 Hz, 2H, CH N), 7.20 (t, 1H,
3
2
6
3
2
H−H 2
357 mg, 0.80 mmol) in CH Cl (20 mL) at room temperature. The
ArH), 7.70 (d, 2H, ArH), 7.83−8.00 (bs, 4H, ArH), 8.20−8.44 (m,
2
2
+ 19
reaction mixture was stirred for an additional 24 h at this temperature
and then evaporated in vacuo. The resulting white solid was washed
with hexane (10 mL) and dried in vacuo to give 4 as a white crystalline
solid. Yield: 460 mg, 65%. Mp: 172−175 °C. Anal. Calcd for
C H B F N O Sn (MW 882.92): C, 46.1; H, 3.3. Found: C, 46.2;
8H, ArH), 11.71 (s, 1H, NH ). F (400 Hz, CDCl ) = δ −62.8,
119
3
−62.9, −63.0, −63.2. Sn NMR (CDCl , 25 °C): δ −550.1. Positive-
3
+
+
ion ESI-MS: 1326.1 ([M + Na] , 8%), 1342.1 ([M + K] , 16%).
Synthesis of H[(L-k NC)SnB O (4-CHO-C H ) ] (9). (4-CHO-
2
4
6
6
4 4
C H )B(OH) (482.2 mg, 3.22 mmol) was added to a stirred solution
3
4
30
2
12
2
3
6
4
2
1
H, 3.4. H NMR (CDCl , 25 °C): δ 2.44 (s, 12H, NCH ), 3.20 (AX
pattern, 2H, CH N), 4.62 (AX pattern, 2H, CH N), 7.21 (t, 1H, ArH),
of 1 (359.4 mg, 0.80 mmol) in CH Cl (20 mL) at room temperature.
3
3
2 2
The reaction mixture was stirred for an additional 2 weeks at this
2
2
F
DOI: 10.1021/acs.inorgchem.5b02505
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
temperature and then evaporated in vacuo. The solid residue was
extracted with toluene (10 mL) and filtered off, and toluene was
evaporated in vacuo. The resulting white solid was extracted with
CHCl (10 mL), and CHCl was evaporated in vacuo to give 9 as a
have been deposited with the Cambridge Crystallographic Data Centre
as CCDC 1413714−1413716 and 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 and are given in the Supporting
Information.
3
3
white crystalline solid. Yield: 420 mg, 60%. Mp: 227−228 °C. Anal.
Calcd for C H B N O Sn (MW 870.67): C, 55.1; H, 4.6. Found: C,
4
0
40
4
2
10
1
5
3
4.9; H, 4.3. H NMR (CDCl , 25 °C): δ 2.45 (s, 3H, NCH ), 2.62 (d,
3 3
H, NCH ), 2.80 (d, 3H, NCH ), 3.10 (s, 3H, NCH ), 3.58 and 4.80
AX pattern, J
3
3
3
ASSOCIATED CONTENT
Supporting Information
2
■
(
= 13.8 Hz, 2H, CH N), 4.14 and 5.60 (AX pattern,
H−H 2
*
S
2
JH−H = 11.4 Hz, 2H, CH N), 7.19 (t, 1H, ArH),7.29 (d, 2H, ArH),
2
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.5b02505.
7
.78−7.92 (m, 8H, ArH), 8.14 (d, 4H, ArH), 8.21 (d, 4H, ArH), 10.00
(
1
2
s, 1H, CHO), 10.03 (s, 1H, CHO), 10.06 (s, 1H, CHO),
+
13
1
0.09 (s, 1H, CHO), 12.27 (s, 1H, NH ). C{ H} NMR (CDCl ,
3
5 °C): δ 41.6 (NCH ), 44.3 (NCH ), 44.4 (CH ), 47.4 (NCH ), 63.5
3
3
3
3
Proposed mechanism of the hydrolytic reactions of
stannaboroxines 2−5, crystal data and structure refine-
ment for 6·C H , 7·C H , and 8, and a comparison of the
(CH N), 64.1 (CH N), 125.3 (L-C3), 128.3 (L-C5), 128.4 (B-Ar-C),
2 2
1
1
28.6 (B-Ar-C), 128.7 (B-Ar-C), 129.1 (B-Ar-C), 129.4 (B-Ar-C),
33.9 (B-Ar-C), 135.1 (B-Ar-C), 135.5 (B-Ar-C), 130.9 (L-C4), 133.8
7
8
7
8
structures of 6−8 with the related pentaborates
(
B-Ar-C), 137.5 (B-Ar-C), 137.7 (B-Ar-C), 137.9 (B-Ar-C), 141.6 (L-
C2), 142.6 (L-C6), 143.2 (B-Ar-C), 146.0 (B-Ar-C), 149.0 (L-C1),
92.6 (CHO), 192.8 (CHO), 193.1 (CHO), 193.3 (CHO).
n−
[
B O ] (PDF)
5 10
1
X-ray crystallographic data in CIF format (CIF)
1
19
Sn NMR (CDCl , 25 °C): δ −553.2. Positive-ion ESI-MS: 894.2
3
+
+
(
[M + Na] , 17%), 910.2 ([M + K] , 13%).
Second-Order NLO Measurements. Second-order NLO suscep-
tibilities were evaluated using a method similar to that where a
AUTHOR INFORMATION
Corresponding Author
*E-mail: roman.jambor@upce.cz.
■
33
polymer served as the matrix for the titled powder. The 20-ns-pulsed
Q-switch Nd:YAG laser generating a 1064 nm wavelength and a pulse
repetition of about 10 Hz was applied as a fundamental one. Detection
of the doubled frequency signal was done using a monochromator of
about 2 nm spectral resolution directly connected to the photo-
multiplier. The latter eliminated the parasitic fluorescence scattering
background. As a reference, we applied δ-BiB O crystals with known
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We are grateful to the Ministry of Education of the Czech
Republic and to the Czech Science Foundation (Project P207/
■
3
6
34
parameters of a second-order optical susceptibility. The powdered 6,
7
, and 9 were embedded in liquid photopolymer oligoether acrylate
1
3-00289S) for supporting this work.
35
composites, which were aligned by an external dc electric field.
Thermal Properties. The thermal properties of 6−9 were
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−1
°
C min within the range 25−400 °C.
5
Crystallography. Suitable single crystals of 6·C H , 7·C H , and 8
7
8
7
8
were obtained from a saturated toluene solution of 6−8 by slow
evaporation of the solvent at room temperature. The X-ray data (Table
S1 in the Supporting Information) for colorles crystals 6·C H , 7·
7
8
C H , and 8 were obtained at 150 K using an Oxford Cryostream low-
7
8
temperature device on a Nonius Kappa CCD diffractometer with Mo
Kα radiation (λ = 0.71073 Å), a graphite monochromator, and ϕ and χ
(
7
1
3
6
scan modes. Data reductions were performed with DENZO-SMN.
37
The absorption was corrected by integration methods. Structures
38
were solved by direct methods (SIR92) and refined by full-matrix
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temperature factors H (H) = 1.2U (pivot atom) or 1.5Ueq for the
39
iso
eq
methyl moiety, with C−H = 0.98, 0.97, and 0.93 Å for methyl,
methylene, and hydrogen atoms in the aromatic rings, respectively.
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4
0
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7
8
7
8
correct the data for the presence of disordered solvent. Potential
3
3
solvent volumes of 353 Å in the case of 6·C H and 1020 Å in the
7
8
case of 7·C H were found. A total of 81 electrons (6·C H ) and 270
7
8
7
8
electrons (7·C H ) per unit cell worth of scattering were located in the
7
8
void. The calculated stoichiometries of the solvent were calculated to
be one and four molecules of toluene per unit cell, respectively.
Thermal ellipsoids of the F3, F9, F10, F18, F22, F23, and F24 atoms in
8
were treated with standard ISOR instruction implemented in the
39
SHELXL97 software. Crystallographic data for structural analysis
G
DOI: 10.1021/acs.inorgchem.5b02505
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
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DOI: 10.1021/acs.inorgchem.5b02505
Inorg. Chem. XXXX, XXX, XXX−XXX