Radical anion and dianion salts of titanyl macrocycles with acceptor substituents or an extended π-system

Article abstract of DOI:10.1039/c6dt04896j

Crystalline anionic salts of titanyl macrocycles with acceptor substituents or an extended π-system have been obtained for the first time: (PPN⁺)₂{O=Ti^IV(PcCl₈^4?)}^2? (1), (PPN⁺){O=Ti^IV(Nc^?3?)}^??·2C₆H₄Cl₂ (2) and (PPN⁺)₂{O=Ti^IV(AceTPrzPz^4?)}^2?·1.3C₆H₄Cl₂·0.8C₆H₅CN (3) where PPN⁺ is the bis(triphenylphosphoranylidene)ammonium cation, PcCl₈-2,3,9,10,16,17,23,24-octachlorophthalocyanine; Nc-2,3-naphthalocyanine, AceTPrzPz-tetra(acenaphthenopyrazino)porphyrazine. Salts 1-3 were obtained in the reduction of the parent titanyl macrocycles by fluorenone ketyl in the presence of an excess of PPNCl in o-dichlorobenzene with following precipitation of crystals with n-hexane. Reduction of macrocycles in 1-3 is accompanied by the appearance of intense NIR bands in the solid spectra at 963-1159 nm. It has been found that the extended π-system with linear annulation in {O=Ti^IV(Nc^?3?)}^?? provides the shift of the NIR band to smaller energies (1159 nm) in comparison with those in the spectra of {O=Ti^IV(Pc^?3?)}^?? (995-998 nm). Reduction of macrocycles leads also to the alternation of C-N_imine bonds due to partial disruption of their aromaticity. The disruption is higher for the dianions in 1 and 3 in comparison with the radical anions in 2. One-dimensional π-π stacking chains and layers are formed in 1 and 3 with diamagnetic {O=Ti^IV(PcCl₈^4?)}^2? and {O=Ti^IV(AceTPrzPz^4?)}^2? dianions, respectively. Salt 2 contains nearly isolated [{O=Ti^IV(Nc^?3?)}^??]₂ dimers with a strong π-π interaction between paramagnetic radical anion macrocycles. As a result, a transition from the triplet to singlet state with antiparallel ordering of spins within the dimers is observed in 2 below 200 K.

Full text of DOI:10.1039/c6dt04896j

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Efficient extraction of sulfate from water using
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Radical anion and dianion salts of titanyl macrocycles with
acceptor substituents or extended π-system†
Maxim A. Faraonov,a Dmitri V. Konarev,*a Alexey M. Fatalov,a, b Salavat S. Khasanov,c Sergey I.
Troyanov,b Rimma N. Lyubovskayaa
Crystalline anionic salts of titanyl macrocycles with acceptor substituents or extended π-system have been obtained for
the first time: (PPN+)2{O=TiIV(PcCl8 −)} − (1), (PPN ){O=Ti (Nc• −)}•−⋅2C6H4Cl2 (2) and (PPN )2{O=Ti (AceTPrzPz −)} ⋅1.3C6H4Cl2
4
2
+
IV
3
+
IV
4
2
−
⋅0.8C6H5CN (3) where PPN+ is bis(triphenylphosphoranylidene)ammonium cation, PcCl8
2,3,9,10,16,17,23,24-
-
octachlorophthalocyanine; Nc – 2,3-naphthalocynine, AceTPrzPz – tetra(acenaphthenopyrazino)porphyrazine. Salts 1-3
were obtained at the reduction of parent titanyl macrocycles by fluorenone ketyl in the presence of an excess of PPNCl in
o-dichlorobenzene with following precipitation of crystals by n-hexane. Reduction of macrocycles in 1-3 is accompanied by
the appearance of intense NIR bands in the solid spectra at 963-1159 nm. It has been found that extended π-system with
linear annulation in {O=TiIV(Nc• −)}•− provides the shift of the NIR band to smaller energies (1159 nm) in comparison with
3
Received 00th January 20xx,
Accepted 00th January 20xx
3
those in the spectra of {O=TiIV(Pc• −)}•− (995-998 nm). Reduction of macrocycles leads also to the alternation of C-Nimine
bonds due to partial disruption of their aromaticity. The disruption is higher for the dianions in 1 and 3 in comparison with
the radical anions in 2. One-dimensional π-π stacking chains and layers are formed in 1 and 3 with diamagnetic
DOI: 10.1039/x0xx00000x
4
2
IV
4
2
IV
3
{O=TiIV(PcCl8 −)} and {O=Ti (AceTPrzPz −)} dianions, respectively. Salt 2 contains nearly isolated [{O=Ti (Nc• −)}•−
]
2
−
−
www.rsc.org/
dimers with strong π-π interaction between paramagnetic radical anion macrocycles. As a result, transition from triplet to
singlet state with antiparallel ordering of spins within the dimers is observed in below 200 K.
2
were obtained at the reduction of MgII, NbIV, AlIII, GeIV and ZrIV
phthalocyanines by Na/Hg, potassium graphite (KC8) or LiCp*.7-11
Introduction
Salts with the reduced cobalt(II) and iron(II) phthalocyanines12-16
,
Metal phthalocyanine compounds can possess promising optical,
conducting and magnetic properties. Some phthalocyanine
derivatives can be used as sensors and materials for optical,
electronic and photoelectronic devices.1,2 Conducting compounds
can be obtained by oxidation of phthalocyanines or axially
substituted phthalocyanine anions {MIIIL2(Pc2−)}− (M = Co, Fe; L =
CN, Cl, Br) to produce crystalline salts with quasi-one-dimensional
metallic behavior down to liquid helium temperatures. These salts
have π-π stacking columnar arrangement of the macrocycles.3,4
Since some metal phthalocyanines contain paramagnetic metals
they also used as an active components in the design of magnetic
compounds. For example, oxidation of substituted manganese(II)
naphthalocyanine by tetracyanoethylene or reduction of iron(II)
phthalocyanine by decamethylchromocene yield compounds with
the alternation of the ions and ferrimagnetic ordering of spins.5,6
Several radical anion and dianion salts of metal phthalocyanines
were also synthesized as single crystals.7-21 Crystalline anionic salts
iron(II) hexadecachlorophthalocyanine17,18, large series of radical
3
−
anion {M(Pc• −)}• salts, M = CuII, NiII, H2, SnII, PbII, O=TiIV, O=VIV,
SnIVCl2 and InIIIBr were also obtained and structurally
characterized.19-22 Nevertheless, till now no anionic salts of such
type were obtained with other macrocycles excepting
phthalocyanines. These macrocycles can contain acceptor
substituents to stabilize their radical anions in the air or extended
π-system allowing the synthesis of structures with stronger π-π
interactions. Reduction of metal macrocycles can also be used to
obtain them in a crystalline form since in spite of large size of the
macrocycles they are well soluble in organic solvents in radical
anion and dianion states.
Titanyl phthalocyanine is a well-known organic photoconductor
which shows very good photoconductivity, excellent photostability,
wide absorption in the visible region with high absorbance.2,23-25 Up
to now several substituted titanyl and vanadyl phthalocyanines
were obtained.26-28 However, molecular structure was determined
for unsubsituted titanyl and vanadyl phthalocyanine only using
Rietweld method on powdered samples29,30 or crystal31,
respectively.
In this work we chose titanyl macrocycles to introduce acceptor
substituents or extended π-system. We dissolve them in o-
dichlorobenzene by their reduction and crystallize radical anion and
dianion
salts
of
titanyl
octachlorophthalocyanine
in
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4
(PPN+)2{O=TiIV(PcCl8 −)}2
(1), titanyl naphthalocyanine in Table S1. Titanyl macrocycles show absorption bands attributed to
−
(PPN+){O=TiIV(Nc• −)}•−⋅2C6H4Cl2 (2) and tetra(acenaphthenopyrazi- the Ti=O stretching mode. The absorption band of this mode is
3
2
2
(PPN+)2{O=TiIV(AceTPrzPz4−)} ⋅1.3C6H4Cl2 manifested at 946 cm-1 in spectra of O=TiIV(PcCl8 −) and salt 1. The
−
no)porphyrazine
in
⋅0.8C6H5CN (3) (Scheme 1). Preparation of single crystals of these Ti=O stretching mode is split into three bands manifested at 927,
salts allows to determine the molecular structures of titanyl 947 and 974 cm-1 in the spectrum of O=TiIV(AceTPrzPz2−). These
macrocycles including that of AceTPrzPz (Scheme 1) which is one of bands are shifted to lower wavenumbers at 917, 927 and 941 cm-1
the largest macrocycle among tetrapyrazinoporphyrazines.32 We in the spectrum 3 indicating the elongation of the Ti=O bonds in this
provide information on the reduction effect on molecular salt. Salt 2 was obtained at the reduction of TiIVCl2(Nc2−) by sodium
3
structures, optical and magnetic properties of titanyl macrocycles.
fluorenone ketyl with the formation of {O=TiIV(Nc• −)}•− and the
appearance of new Ti=O bond. That is accompanied by the
manifestation of new band at 974 cm-1. Earlier it was shown that
2
Scheme 1
2
Cl
Cl
IV
2
−
N
N
the
reduction
of
unsubstituted
O=Ti (Pc
)
in
Cl
Cl
N
N
N
N
N
N
N
O N
Ti
(Bu4N+){O=TiIV(Pc• −)}•− and (Et4N+){O=TiIV(Pc• −)}•−·C6H4Cl2 is
accompanied by the elongation of Ti=O bonds since corresponding
absorption bands are shifted from 962 to 923-928 cm-1.13
3
3
N
N
O N
Ti
N O
Ti
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
3
Cl
Cl
2
1
Cl
Cl
Spectra of starting titanyl macrocycles and salts 1-3 in KBr
pellets in the UV-visible-NIR range are shown in Fig. 1.
Unsubstituted O=TiIV(Pc2−) shows the Soret band at 347 nm and the
split Q-band at 654 and 708 nm.20 The Soret and Q-bands have
(PPN+)2{O=TiIV(PcCl84-)}2-
(PPN+){O=TiIVO(Nc.3-)}.-
(PPN+)2{O=TiIV(AceTPrzPz4-)}2-
Results and discussion
2
−
close position in the spectra of O=TiIV(PcCl8
)
and
Synthesis
O=TiIV(AceTPrzPz2−) manifesting at 353, 660, 706 nm and 331, 652,
710 nm, respectively. Unsubstituted TiIVCl2(Pc2−) shows absorption
bands at 352, 665 and 721 nm. Linear annulation in the
naphthalocyanine macrocycle of TiIVCl2(Nc2−) results in a blue shift
of the Soret band up to 340 nm and strong red shift of the Q-band
up to 753 and 834 nm (Fig. 1).
Titanium dichloride macrocycles were synthesized by
tetramerization of corresponding dicarbonitriles in the presence of
TiCl4 or TiCl4⋅2THF in 1-chloronaphthalene in 68-75% yield. Addition
of 2-methylnaphthalene prevents the formation of products with
chlorinated periphery of the macrocycle. Substitution of chlorine
atoms at titanium by oxygen with the formation of titanyl
macrocycles was made by boiling of titanium dichloride
macrocycles in wet pyridine (5% of H2O).33 Scheme 2 of the
reactions is shown below.
Cl
Cl
Cl
Cl
PPNCl
N
(Fluorenone.-)(Na+)
N
N
TiCl4
2-methylnaphthalene
Cl
Cl
Cl
N
N
N
N
Py/H2O
boiling
Ti
Cl
O=TiIV(PcCl8)
{O=TiIV(PcCl84-)}2- (1)
(PPN+)2
N
N
1-chloronaphthalene
250oC, 5 h
N
Obtained titanyl macrocycles are reduced by sodium
fluorenone ketyl in the presence of an excess of PPNCl. That leads
to the dissolution of all titanyl macrocycles in the form of anions
though, for example, neutral O=TiIV(AceTPrzPz2−) is completely
insoluble in o-dichlorobenzene. The reduction of TiIVCl2(Nc2−) by
sodium fluorenone ketyl is accompanied by the substitution of
chloride anions by oxygen at titanium(IV) atoms. Oxygen originates
Cl
Cl
Cl
Cl
TiIVCl2PcCl8
N
.
N
N
TiCl4 2THF
2-methylnaphthalene
PPNCl
(Fluorenone.-)(Na+)
N Cl N
Ti
Cl
(PPN+)
-
N
N
1-chloronaphthalene
250oC, 5 h
.
.
{O=TiIV(Nc 3-)} (2)
N
N
N
3
from fluorenone ketyl, and salt 2 with the {O=TiIV(Nc• −)}•− radical
(PPN+)2
TiIVCl2Nc
anions is formed.
{O=TiIV(AceTPrzPz4-)}2- (3)
According to redox potentials,34-36 naphthalocyanine
PPNCl
N
N
N
(Fluorenone.-)(Na+)
N
macrocycle
shows
weaker
acceptor
properties
than
TiCl4
2-methylnaphthalene
N
DANM
Cl
Ti
Cl
N
N
N
N
N
Py/H2O
tetrapyrazinoporphyrazine and phthalocyanine macrocycles with
electron- withdrawing chloro- and pyrazino-substituents. As a
result, the reduction of TiIVCl2Nc produces radical anion salt 2,
whereas the reduction of O=TiIV(PcCl8) and O=TiIV(AceTPrzPz) in the
same reaction conditions leads to the formation of dianion salts 1
and 3.
N
N
O=TiIVAceTPrzPz
boiling
N
N
1-chloronaphthalene
250oC, 5 h
CH3COOH
100oC, 1 h
O
O
N
N
N
N
N
N
Scheme2
TiIVCl2AceTPrzPz
Spectra of salts in the IR and UV-visible-NIR ranges
According to the composition titanyl naphthalocyanine should have
-1 charge since the titanyl macrocycle: cation ratio of 1:1 in salt 2,
whereas the titanyl macrocycle: cation ratio of 1:2 in salts 1 and 3
shows the formation of titanyl macrocycle dianions (2−).
Fig. 1 UV-visible-NIR spectra of starting titanyl macrocycles and salts 1- 3 in KBr
pellets prepared in anaerobic conditions. Charge transfer bands (CTB) are shown by
arrows.
IR spectra of parent compounds and their salts are shown in
Figures S1-S3 and the observed absorption bands are listed in
2 | J. Name., 2012, 00, 1-3
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Table 1. Data of UV-visible-NIR spectra of starting titanyl macrocycles and salts 1-3.
Compound
Position of absorption band of phthalocyanines, nm
Soret band, nm
Q-band, nm
654, 708
Bands in NIR, nm
IV
2
20
)
−
O=Ti (Pc
347
343
-
3
20
(TBA+){O=TiIV(Pc• −)}•−
597, 630, 701
844 (weak), 995
3
20
(TEA+){O=TiIV(Pc• −)}•−·C6H4Cl2
911 (weak), 998
340
353
340
600, 630, 698
660 (max), 706
637 (max), 703
1475 (CT band)
2
O=TiIV(PcCl8
)
-
−
4
(PPN+)2{O=TiIV(PcCl8 −)}2−](1)
818 , 916, 999
1550 (CT band)
IV
2
−
Ti Cl2(Pc
)
352
340
665(sh), 721 (max)
753, 834 (max)
-
IV
2
−
Ti Cl2(Nc
)
-
3
(PPN+){O=TiIV(Nc• −)}•−⋅(Solvent) (2)
1040 (weak),1159,
340
697 (max), 814
1672 (CT band)
O=TiIV(AceTPrzPz2
)
331
325
652 (weak), 710 (max)
607, 706 (max)
-
−
(PPN+)2{O=TiIV(AceTPrzPz4−)}2− (Solvent) (3)
963
sh – shoulder; max – maximum
Spectra of 1-3 (Table 1) allow one to study how the reduction
The reduction of the Pc macrocycle is accompanied by
affects optical properties of titanyl macrocycles. Analysis of these transition from aromatic 18 electron π-system to antiaromatic 19
spectra shows that Soret bands are blue shifted at the reduction of and 20 electron π-system for radical trianion and tetraanion
the macrocycle in 1 and 3 whereas maxima of the Q-bands are macrocycles, respectively. As
a result, partial disruption of
strongly blue shifted in the spectra of 1 and 2, but remain nearly aromaticity of the macrocycles is observed in the reduced state
unshifted in the spectrum of 3 (Table 1, Fig. 1). The most leading to the alternation of the C-Nimine bonds.7-11,20,21 Such
pronounced changes at the formation of radical anions and alternation is also observed for the reduced macrocycles in 1-3
dianions of titanyl macrocycles are the appearance of new intense (Table 2), but the difference between the shorter and longer C-
NIR bands. The presence of these bands unambiguously allows one Nimine bands in 1 and 3 with tetraanion macroheterocycles is nearly
3
3
−
to determine the formation of reduced macrocycle anions. The blue two times larger than those for the radical trianion Pc• 20 and Nc•
−
shift of the Soret and Q bands and the appearance of NIR bands are macrocycles (Table 2). Thus, disruption of aromaticity is more
3
characteristic of the radical anion salts of {O=TiIV(Pc• −)}•− and other pronounced for the dianion titanyl macrocycles. Alternation of
metal phthalocyanines.20, 21 It should be noted that the NIR band in bonds is realized in such a way that shorter and longer C-Nimine
the spectrum of 2 (1159 nm) is strongly red shifted in comparison bonds belong to two oppositely located isoindole units in 1 - 3 as is
3
with the spectra of the [O=TiIV(Pc• −)]•− salts (995-998 nm)20. At the also observed in the radical anions of other metal
same time these bands are observed almost at the same position in phthalocyanines.20, 21
4
2
−
the spectra of 1 and 3 (999 and 963 nm, respectively). Thus, linear
Half of {O=TiIV(PcCl8 −)} dianion and one PPN+ cation are
annulation in naphthalocyanine essentially stronger decreases the independent in 1. These dianions form layers in the ab plane
energy of the Q band and the NIR band of the radical anion even in (Fig. 2a), which are separated by the PPN+ cations (Fig. 2b). More
comparison with those for tetra(acenaphthenopyrazino)porphy- closely packed chains can be outlined along the a axis within the
razine which has essentially larger π-system but no linear phthalocyanine layers (Fig. 2a). Each phthalocyanine macrocycle has
annulation. Spectra of 1 and 2 also show broad low-energy bands at four short van der Waals (vdW) C⋅⋅⋅C and Cl⋅⋅⋅Cl contacts of about
1550 and 1672 nm (Fig. 1), respectively, which can be attributed to 3.5 Ȧ length with the neighboring dianions in these chains. The
charge transfer between macrocycles as it will be discussed in the interplanar distance in the chains is uniform and is rather short
next section. This band is not observed in the spectrum of 3 (Fig. 1), (3.38 Ȧ). Most probably namely close packing of the PcCl8
probably due to ineffective overlapping between the macrocycles in 1 provides the appearance of intense charge
{O=TiIV(AceTPrzPz4−)}2− dianions.
transfer band in the NIR spectrum (see above). Any vdW contacts
between phthalocyanines from the neighboring chains within the
layer are absent. The macrocycle is almost flat in 1 with only slight
Molecular and crystal structures of salts 1-3.
Geometric parameters of macrocycles in 1-3 are presented in deviations of atoms from the 24-atom Pc plane (less than 0.065 Å).
3
Table 2. The average lengths of the Ti-N(Pc) bonds in 1-3 are
One {O=TiIV(Nc• −)}•− radical anion, one PPN+ cation and two
2.068(2)-2.097(6) Å. That is slightly longer than those in solvent C6H4Cl2 molecules are independent in 2. There are
3
{O=TiIV(Pc• −)}•− (2.055(1)-2.062(1) Å.20 The elongation of the Ti- naphthalocyanine chains along a axis (Fig. 3) which are isolated by
3
N(Pc) bonds results in a stronger displacement of the Ti atoms from the PPN+ cations. The {O=TiIV(Nc• −)}•− radical anions form dimers in
the 24-atom Pc plane which is maximal for the these chains with multiple C,N⋅⋅⋅C,N vdW contacts, but macrocycles
2
{O=TiIV(AceTPrzPz4−)} dianions in 3. The length of the O=Ti bond in these dimers are only slightly shifted relative to each other. As a
−
also varies from 1.615(6) to 1.645(5) Å, and the shortest bonds are result, there are no short vdW contacts between the neighboring
observed for the macrocycles with extended π-system in 2 and 3.
dimers within the chains. The naphthalocyanine macrocycle has two
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Table 2. Geometric parameters of titanyl macrocycles in neutral, radical anion and dianion state.
Displacement of atoms from the 24-atom Pc
plane, Å
Average length of bonds and contacts, Å
Compound
C-Nimine
M-Npyrrole
C-Npyrrole
Metal
0.778
Npyrrole
,
short/long difference
O=TiIV(Pc2−) (P 21/c)
O=Ti (1.628(3) Å)24
O=TiIV(Pc2−) (C c)
2.067(6)
1.374(6)
1.330(6)
1.329(5)
0.091-0.184
O=Ti (1.643(3) Å)25
2.071(5)
1.375(5)
0.742
0.076-0.151
(both made by Rietveld analysis)
(Bu4N+){O=TiIV(Pc• −)}•−
1.325(2)/1.350(2),
0.025
3
2.062(1)
2.055(1)
2.072(3)
2.068(2)
2.097(6)
1.386(2)
1.388(2)
1.390(4)
1.397(3)
1.402(9)
0.711
0.595
0.602
0.556
0.741
0.084-0.135
0.004-0.031
0.015-0.019
0.007-0.088
0.067-0.166
O =Ti (1.640(1) Å)20
3
(Et4N+){O=TiIV(Pc• −)}•− ⋅C6H4Cl2
1.312(2)/1.351(2),
0.039
( O=Ti (1.657(1) Å))20
4
(PPN+)2{O=TiIV(PcCl8 −)}2− (1),
1.304(4)/1.375(4),
0.071
O=Ti (1.645(5) Å)
3
(PPN+){O=TiIV(Nc• −)}•−(Solvent) (2)
1.315(3)/1.353(3),
0.038
O=Ti (1.638(2) Å)
(PPN+)2{O=TiIV(AceTPrzPz4−)}2− (Solvent)
1.314(9)/1.374(9),
0.060
(3) (O=Ti (1.615(6) Å))
adjacent naphthalene groups located strictly above the 24-atom
plane, whereas two other groups are located almost in the plane.
The interplanar distance of 3.169 Ȧ is very short in the dimer
indicating effective π-π interaction between the macrocycles in 2
explaining the appearance of a charge transfer (CT) band in the NIR
spectrum. The interplanar distance in 2 is close to that in previously
a
+
IV
3
•
−
studied (Et4N ){O=Ti (Pc• −)} ⋅C6H4Cl2 salt (3.129 Ȧ) which also
shows an intense CT band in the NIR range.20
As a result of strong disorder of solvent molecules, the structure
of 3 was refined with relatively high R-factor value (0.1158).
a
b
3
Fig. 3 Crystal structure of (PPN+){O=TiIV(Nc• −)}•−⋅2C6H4Cl2 (2). View along a axis
and the naphthalocyanine chains (a) and veiw on these chains (b). Shortened vdW
C,N⋅⋅⋅C,N contacts are shown by green dashed lines. Solvent molecules are not
shown for clarity.
) 2
Nevertheless, the structure of the {O=TiIV(AceTPrzPz4
}
dianion
−
−
and the PPN+ cations were determined quite reliably. Dianions form
IV
4
2
−
the [{O=Ti (AceTPrzPz −)}
]
dimers with strong shift of the
2
macrocycles but effective π-π stacking between one of four
acenaphthenopyrazino groups of the {O=TiIV(AceTPrzPz4−)}2
−
dianions (Figs. 4a, b).
The interplanar distance between them is 3.38 Å and the
shortest C,N⋅⋅⋅C,N vdW contacts are in the 3.19-3.36 Å range. The
dihedral angle between the planes of the acenaphthenopyrazino-
groups of neighboring dianions in the dimer is only 0.22o showing
their parallel arrangement. Strong shift of the macroheterocycles
relative to each other in the dimers leads to the formation of chains
arranged along the [1-1-0] direction (Figs. 4c, d). There are 4 C⋅⋅⋅C
b
Fig.2 Crystal structure of (PPN+)2{O=TiIV(PcCl8 −)}2− (1). Views perpendicular (a) and
4
parallel (b) to the phthalocyanine layers. Shortened vdW C,Cl⋅⋅⋅C,Cl contacts are
shown by green dashed lines.
4 | J. Name., 2012, 00, 1-3
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vdW contacts between the neighboring dimers in these chains of of titanyl macrocycle). Therefore, the signals can be most probably
4
−
3.47-3.56
acenaphthene planes of two dianions involved in this interaction and {O=TiIV(AceTPrzPz4−)}2− dianions are diamagnetic
are nearly parallel (the dihedral angle between them is 8.12o) and
Salt 2 shows an asymmetric EPR signal which can be simulated
the interplanar distance is only 3.42 Å. There are also several side- well by two narrow lines (g1 = 2.0034 и H = 0.50 mT, g2 = 2.0014 и
Å
length. These contacts are of π-type since the attributed to paramagnetic impurities. Thus, the {O=TiIV(PcCl8 −)}2
ꢀ
by-side vdW C⋅⋅⋅C contacts of 3.31
Å
length between the
ꢀ
H = 0.88 mT ) and one broad line with g3 = 2.0018 and
ꢀH = 4.67
[{O=TiIV(AceTPrzPz4−)}2
] dimers from the neighboring chains (Fig. mТ at 300 K (Fig. 5).
2
−
4c, green dashed lines). The macrocycle in
3 has concave
conformation and deviates strongly from planarity in contrast to
the geometry of the macrocycles in 1 and 2.
a
b
Fig. 5 EPR spectrum of 2 at 300 K (a). Temperature dependence of main component
of EPR signal of salt 2 (b).
a
b
Narrow lines can be attributed to paramagnetic impurities due
to that their intensities are less than 3% from that of the broad
signal. The broad line decreases seven times in intensity upon
cooling the sample from 300 down to 200 K (Fig. 5b). Below 200 K
all three lines are of low intensity and show paramagnetic
temperature dependence down to 4 K. Thus, salt 2 is diamagnetic
3
below 200 K. Crystal structure of 2 shows that the {O=TiIV(Nc• −)}•−
3
radical anions form closely packed π-stacking [{O=TiIV(Nc• −)}•−]2
dimers that can provide strong coupling between them. As a result,
diamagnetic singlet state with an antiparallel arrangement of spins
in the dimers is formed below 200 K. Triplet state of the dimers
with a parallel arrangement of spins is populated above 200 K. The
observed singlet-triplet transition in 2 is similar to that observed in
3
(Et4N+){O=TiIV(Pc• −)}•−·C6H4Cl2 which also contains π-staking
c
3
[{O=TiIV(Pc• −)}•−
] dimers. However, temperature of the transition
2
to singlet state in
2 (200 K) is higher than that in
(Et4N+){O=TiIV(Pc• −)}•−·C6H4Cl2 (150 K).20 That can be explained by
stronger π-π interactions in 2, probably due to the larger π-system
of the naphthalocyanine macrocycle.
3
d
Conclusions
A series of the radical anion and dianion salts based on titanyl
macrocycles with acceptor substituents or an extended π-system
were obtained as single crystals for the first time. The reduction of
titanyl macrocycles in the presence of bulky PPN+ cations allows
their dissolution due to the formation of the radical anions or
dianions, whereas they are very weakly soluble in organic solvents
in the neutral state. Thus, titanyl macrocycles can be crystallized
and their molecular structures are determined from X-ray
diffraction on single crystals. Extension of a π-system by linear
annulation in naphthalocyanine leads to strong red shift of the Q-
band and NIR bands of the radical anions, whereas
tetra(acenaphthenopyrazino)porphyrazine with extended π-system
show Q-bands and a NIR band of the anions nearly at the same
Fig. 4 Crystal structure of (PPN+)2{O=TiIV(AceTPrzPz4−)}2−⋅1.2C6H4Cl2⋅0.8C6H4Cl2 (3):
4
2
view on (a) and along (b) the [{O=TiIV(AceTPrzPz −)}
] dimer, view on (c) and along
2
−
(d) the layers from the dimers. Shortened vdW C⋅⋅⋅C contacts are shown by green
dashed lines. Solvent molecules are not shown for clarity.
EPR studies of the salts
EPR spectra of salts 1 and 3 at 300 K contain weak asymmetric
signals which can be approximated by three lines with g = 1.9975-
2.0042 and the linewidth
(ꢀH) = 0.45-0.92 mT, which are
characteristic of radical anions of phthalocyanine species. Intensity
of these signals is very low (less than 1% of spins from total amount
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position as in the spectra of the salts with unsubstituted titanyl
Titanium (IV) 2,3-naphthalocyanine dichloride, TiIVCl2(Nc2−).
2,3-Dicyanonaphthalene (1 g, 5.612 mmol),
phthalocyanine radical anions, {O=TiIV(Pc• −)}•−. Partial disruption of
2-
3
aromaticity is observed at the reduction of the macrocycles. This methylnaphthalene (200 mg, 1.403 mmol) and TiCl4⋅2THF (468 mg,
effect is more pronounced for the dianions than for the radical 1.403 mmol) in 10 ml of 1-chloronaphthalene were heated up to
anions. Increased size of the macrocycle leads to the formation of 250 °C upon stirring for 5 hours in argon atmosphere. Then the
π-stacked structures. In case of 2 that provides effective magnetic reaction mixture was cooled down to 50 °C and precipitate was
3
coupling between the spins within the [{O=TiIV(Nc• −)}•−]2 dimers filtered under reduced pressure and washed with toluene and
and the transition of the dimers to the singlet ground state even methanol. TiIVCl2Nc was dried at 100 °C in vacuum for 2 hours to
below 200
K (at temperature higher than that in the yield 850 mg of dark green powder (73%). Anal. found: C, 69.01, N
[{O=TiIV(Pc• −)}•−]2 dimers). Macrocycles in 1 and 3 are packed in the 13.30, H 3.06, Cl 8.44 %. Calcd. for C48H24N8Cl2Ti: C, 69.26, N 13.47,
π-stacked chains. However, diamagnetic nature of the dianions H 2.89, Cl 8.54 %. IR (KBr), ν, cm-1: 1747w, 1639m, 1468w, 1358m,
does not allow one to expect the realization of conductivity or 1338m, 1318m, 1153w, 1125m, 1062s, 1011m, 1077s, 968m, 886m,
magnetic interactions in these chains. We suppose that the radical 863m, 798w, 752s, 733w, 716m, 690w, 656w, 514w, 488w, 469m.
anions of these titanyl macrocycles can provide more promising UV-VIS, KBr pellet λmax, nm: 340, 753, 834.
3
magnetic properties. Preparation of these salts is now in progress.
Acenaphtho[1,2-b]pyrazine-8,9-dicarbonitrile.
mixture of acenaphthenequinone (2 g, 11 mmol) and
A
equimolar quantity of diaminomaleonitrile (1.187 g, 11 mmol) in 30
ml acetic acid was heated at 100 °C upon stirring for 1 hours. The
residue was filtered off, washed with water and acetone (3 ml) and
dried at 100 °C in vacuum for 2 hours to yield 2.15 g of dark orange
powder (77%).
Experimental
Materials
4,5-Dichlorophthalonitrile (Aldrich, 99%), 2,3-dicyanonaphthalene
(TCI,
99%),
acenaphthenequinone
(Acros,
95%),
and
Titanyl tetra(acenaphthenopyrazino)porphyrazine,
O=TiIV(AceTPrzPz2−).
diaminomaleonitrile (Acros, 98%) were used as received. TiCl4
(Aldrich, 99%) and TiCl4⋅2THF (Aldrich, 97%) were used as received.
Bis(triphenylphosphoranylidene)ammonium chloride (PPNCl) was
purchased from Aldrich (98%). 1-chloronaphthalene (Aldrich,
technical grade) was used as received. Sodium fluorenone ketyl was
obtained as described.37 Solvents were purified in argon
atmosphere. o-Dichlorobenzene (C6H4Cl2) was distilled over CaH2
under reduced pressure; hexane was distilled over
Na/benzophenone, and benzonitrile (C6H5CN) was distilled over Na
under reduced pressure. The solvents were degassed and stored in
a glove box. The crystals of 1 – 3 were stored in a glove box. KBr
pellets for IR- and UV-visible-NIR measurements were also prepared
in the glove box. EPR measurements were performed on
polycrystalline samples of 1-3 sealed in 2 mm quarz tubes under 10-
5 Torr.
Acenaphtho[1,2-b]pyrazine-8,9-dicarbonitrile (1 g, 3.933 mmol),
2-methylnaphthalene (140 mg, 0.983 mmol) and TiCl4 (0.11 mL,
0.983 mmol) in 10 ml of 1-chloronaphthalene were heated up to
250 °C upon stirring for 5 hours in argon atmosphere. Then the
reaction mixture was cooled down to 50 °C, precipitate was filtered
under reduced pressure and washed with toluene and methanol.
TiIVCl2(AceTPrzPz2−) was converted to O=TiIV(AceTPrzPz2−) by boiling
in wet pyridine (5% of H2O) for two hours. O=TiIV(AceTPrzPz2−) was
filtered, washed with water and dried at 100 °C in vacuum for 2
hours to yield 800 mg of black powder (75%). Anal. found: C 70.88,
N 20.59, H 2.49 %. Calcd. for C64H24N16OTi: C 71.04, N 20.72, H 2.22
%. IR (KBr), ν, cm-1: 2921m, 2851m, 1615s, 1514m, 1458m, 1431s,
1369w, 1333s, 1262m, 1229s, 1179m, 1134s, 1099m, 1033s, 974w,
947m, 927m, 828m, 772s, 716m, 675m, 660m, 630m, 559w, 464s,
449m. UV-VIS, KBr pellet λmax, nm: 331, 652, 710.
Synthesis of titanyl macrocycles
Titanyl macrocycles (Scheme 2) were synthesized as described in
ref.33
Syntheses of crystalline salts 1-3
Crystals of 1-3 were obtained by diffusion technique. The reaction
solutions of salts 1-3 were filtered in a 50 mL glass tube of 1.8 cm
diameter with a ground glass plug, and 30 mL of hexane was layered
over the solution. Slow mixing of two solvents during 1.5 months
provided precipitation of crystals on the walls of the tube. The
solvent was decanted from the crystals and they were washed with
hexane.
Salts (PPN)2{O=TiIVPcCl8} (1) and (PPN){O=TiIVNc}⋅2C6H4Cl2 (2)
were obtained by reduction of 34.6 mg of TiIVOPcCl8 (0.042 mmol)
or 35.5 mg of TiIVCl2Nc (0.042 mmol) by sodium fluorenone ketyl (55
mg, 0.27 mmol) in the presence of PPNCl (75 mg, 0.131 mmol) in 16
ml of o-dichlorobenzene for two hours at 100oC till complete
dissolution of starting compounds and the formation of dark green
and deep-blue-green solutions, respectively. The final solutions
were filtered into a tube for diffusion. Black blocks of 1 and dark
violet elongated prisms of 2 were obtained in 25 and 45% yield,
respectively.
Titanyl
2,3,9,10,16,17,23,24-octachlorophthalocyanine,
2
O=TiIV(PcCl8 −).
4,5-Dichlorophthalonitrile
(1
g,
5.076
mmol),
2-
methylnaphthalene (180 mg, 1.269 mmol) and TiCl4 (0.14 ml, 1.269
mmol) in 10 ml of 1-chloronaphthalene were heated up to 250 °C
upon stirring for 5 hours in argon atmosphere. Then the reaction
mixture was cooled down to 50°C, precipitate was filtered under
reduced pressure and washed with toluene and methanol.
2
2
TiIVCl2(PcCl8 −) was converted to O=TiIV(PcCl8 −) by boiling in wet
pyridine (5% of H2O) for two hours. O=TiIV(PcCl8 −) was filtered,
2
washed with water and dried at 100 °C in vacuum for 2 hours to
yield 800 mg of blue powder (68%). Anal. found: C, 44.86, N 13.01,
H 1.12, Cl 33.21 %. Calcd. for C32H8N8Cl8OTi: C, 45.08, N 13.15, H
0.94, Cl 33.34 %. IR (KBr), ν, cm-1: 3087m, 2922m, 2849w, 2353w,
1603m, 1471m, 1413s, 1375m, 1320m, 1069s, 980w, 945m, 890m,
829m, 775m, 705m, 659m, 463w, 431w. UV-VIS, KBr pellet λmax
,
nm: 353, 660, 706.
6 | J. Name., 2012, 00, 1-3
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Salt (PPN)2{O=TiIVAceTPrzPz}⋅1.3C6H4Cl2⋅0.8C6H5CN (3) was groups within reasonable limits the displacement components were
obtained by the reduction of 36 mg of O=TiIVAceTPrzPz (0.033 restrained using the SIMU and DELU SHELXL instructions.
mmol) by sodium fluorenone ketyl (55 mg, 0.27 mmol) in the
Table 3. X-ray diffraction data for salts 1-3.
presence of PPNCl (75 mg, 0.131 mmol) in 18 ml of o-
Compound
1
2
3
dichlorobenzene/benzonitrile mixture (15:3) for two hours at 100oC
till complete dissolution of phthalocyanine and the formation of
dark green solution. The final solution was filtered into a tube for
diffusion. Black prisms were obtained in 15 % yield.
C149.4H93.2Cl2.6
N18.8OP4Ti
2431.57
Emp. formula
C104H68Cl8N10OP4Ti
C96H62Cl4N9OP2Ti
Mr [g⋅mol-1]
Color and shape
Crystal system
1929.06
Black block
triclinic
1609.18
Dark-violet prism
monoclinic
Black prism
monoclinic
The composition of 1-3 (Table 3) was determined from X-ray
diffraction on single crystals. The analysis of the obtained crystals
under microscope in a glove box as well as testing of several single
crystals from each synthesis by X-ray diffraction showed that only
one crystalline phase is formed. Elemental analysis cannot be used
to determine the composition of the obtained crystals due to their
high air sensitivity and an addition of oxygen during the procedure
of elemental analysis.
Space group
P1
P21/c
C2/c
a, Å
b, Å
c, Å
α, °
β, °
γ, °
11.3971(7)
14.8799(8)
15.0231(9)
63.130(6)
77.450(8)
78.459(8)
2203.1(3)
1
15.1213(3)
18.0169(3)
29.1976(6)
90
36.695(2)
25.1999(8)
27.4198(11)
90
General
98.402(2)
90
101.073(5)
90
UV-visible-NIR spectra were measured in KBr pellets on a Perkin
Elmer Lambda 1050 spectrometer in the 250-2500 nm range. FT-IR
spectra were obtained in KBr pellets with a Perkin-Elmer Spectrum
400 spectrometer (400-7800 cm–1). EPR spectra were recorded on
polycrystalline samples of 1-3 from 4 up to 295 K and back from 295
to 150 K for 2 with a JEOL JES-TE 200 X-band ESR spectrometer
equipped with a JEOL ES-CT470 cryostat.
V, Å3
7869.2(3)
4
24883.5(19)
8
Z
ρ
calc [g/cm3]
[mm-1]
1.454
1.358
1.298
ꢁ
0.888
0.343
0.239
F(000)
T [K]
988
3316
10043
100(2)
50.000
68100
20895
1529
100(2)
73.500
32780
8464
150(2)
58.748
100772
20327
1035
Max. 2
Θ , °
Crystal structure determination
Reflns measured
Unique reflns
Parameters
Crystallographic data for 1-3 are listed in Table 3. Synchrotron X-ray
data for 1 were collected at 100 K on the BL14.3 at the BESSY
storage ring (Berlin, Germany) using a MAR225 detector, λ =
0.8950 Å.
586
Restraints
0
1238
797
Reflns[Fo>2(Fo)]
R1 [Fo>2σ(Fo)]
WR2 (all data)a,
G.O.F
7252
15449
0.0818
0.1824
1.105
11354
0.1158
0.3277
1.063
The data for 2 and 3 were collected on an Oxford diffraction
"Gemini-R" CCD diffractometer with graphite monochromated
MoKα radiation at low temperature using an Oxford Instrument
Cryojet cooler. Experimental data were processed using CrysAlisPro
software, Oxford Diffraction Ltd, raw data reduction to F2 was
carried out using Bruker SAINT.38 The structures were solved by
direct method and refined by the full-matrix least-squares method
against F2 using SHELX-2013 and 2014.39 Non-hydrogen atoms were
refined in the anisotropic approximation. Positions of hydrogen
atoms were calculated geometrically.
0.0613
0.1468
0.998
CCDC number
1518488
1518412
1518411
Acknowledgements
The reported study was funded by RFBR according to the research
project No. 16-33-00588 mol_a.
The Ti1 and O1 atoms in structure 1 are disordered around an
inversion center. Structure of 2 contains one strongly disordered
C6H4Cl2 molecule with the 0.355(3)/0.275(3)/0.231(3)/0.139(3)
Notes and references
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Dalton Transactions
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DOI: 10.1039/C6DT04896J
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ARTICLE
Graphical abstract
Crystalline anionic salts of titanyl macrocycles with acceptor
substituents or extended π-system have been obtained:
4
2
+
IV
3
(PPN+)2{O=TiIV(PcCl8 −)} (1), (PPN ){O=Ti (Nc• −)}•−⋅solv (2) and
−
+
IV
4
2
−
(PPN )2{O=Ti (AceTPrzPz −)} ⋅solv (see figure, 3). Diamagnetic
{O=TiIV(PcCl8 −)} and {O=TiIV(AceTPrzPz4−)} dianions form chains
and layers. Transition from triplet to singlet state is observed in 2
below 200 K due to the antiparallel arrangement of spins in the
4
2
−
2
−
[{O=TiIV(Nc• −)}•−]2 dimers.
3
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