A vanadium porphyrin with temperature-dependent phase transformation: Synthesis, crystal structures, supramolecular motifs and properties

Article abstract of DOI:10.1002/asia.201000822

A vanadium porphyrin, V(O)TMeOPP (1; TMeOPP=5, 10, 15, 20-tetrakis(4- methoxyphenyl)-21 H, 23H-porphyrin), has been synthesized by solvothermal reactions and characterized by single-crystal X-ray diffractions at room temperature and low temperature to reveal two different structures 1 R and 1 L, respectively. Both 1 R and 1 L crystallized in the orthorhombic system, but their space groups were different: Pbca and Pca2₁ for 1 R and 1 L, respectively. The cell parameters of a, b, and c were different and the cell volume of 1 R was larger than that of 1 L by circa 200 A³. 1 R and 1 L were characteristic of an isolated motif with a five-coordinate vanadium(IV) ion and a saddle-distorted nonplanar porphyrin macrocycle. Molecules of 1 R were interconnected through hydrogen-bonding interactions to yield a 3D framework; whilst for the low-temperature phase 1 L, there were more hydrogen-bonding interactions that link the molecules to construct a more-complex 3D supramolecular network. In a solution of acetone, the title compound exhibited purple and green colors at room temperature and low temperature, respectively, which is unprecedented for vanadium porphyrins. The spectral data of UV/Vis, FT-IR, and MALDI-TOF-MS of 1 R and 1 L are reported together with the electrochemical data. Copyright

Full text of DOI:10.1002/asia.201000822

FULL PAPERS
DOI: 10.1002/asia.201000822
AVanadium Porphyrin with Temperature-Dependent Phase Transformation:
Synthesis, Crystal Structures, Supramolecular Motifs and Properties
Wentong Chen,[a, b] Tomoyoshi Suenobu,[a] and Shunichi Fukuzumi*[c]
Abstract:
A
vanadium porphyrin,
and the cell volume of 1R was larger
than that of 1L by circa 200 ꢀ3. 1R
and 1L were characteristic of an isolat-
ed motif with a five-coordinate vana-
dium(IV) ion and a saddle-distorted
nonplanar porphyrin macrocycle. Mole-
cules of 1R were interconnected
through hydrogen-bonding interactions
to yield a 3D framework; whilst for the
low-temperature phase 1L, there were
more hydrogen-bonding interactions
that link the molecules to construct a
more-complex 3D supramolecular net-
work. In a solution of acetone, the title
compound exhibited purple and green
colors at room temperature and low
temperature, respectively, which is un-
precedented for vanadium porphyrins.
The spectral data of UV/Vis, FT-IR,
and MALDI-TOF-MS of 1R and 1L
are reported together with the electro-
chemical data.
V(O)TMeOPP (1; TMeOPP=5, 10,
15, 20-tetrakis(4-methoxyphenyl)-21H,
23H-porphyrin), has been synthesized
by solvothermal reactions and charac-
terized by single-crystal X-ray diffrac-
tions at room temperature and low
temperature to reveal two different
structures 1R and 1L, respectively.
Both 1R and 1L crystallized in the or-
thorhombic system, but their space
groups were different: Pbca and Pca21
for 1R and 1L, respectively. The cell
parameters of a, b, and c were different
Keywords: phase transformation ·
porphyrins
· saddle distortion ·
supramolecular chemistry · vana-
dium
Introduction
side, such as heat, pressure, optical, electronic, or magnetic
field and so forth. Until now, many compounds that display
phase transformations have been documented, among
which, many are inorganic compounds, such as Cul2Sb4S13,[10]
In recent years, the phase transformations of compounds
have attracted increasing interest owing to their application
in forming well-defined nano-sized apparatus and functional
supramolecules at the molecular level.[1–9] In general, a
phase transformation of a compound would take place when
the compound is stimulated by a proper stimulus from out-
Ba4ÀxSrxNaSb3O12,[11]
SrZrO3,[12,13]
Ba2Bi2O6,[14]
Sr2CoWO6,[15,16] LaSeTe2
and so on. However, organic
[17]
compounds that show phase transformations are relatively
rare.[18,19]
Porphyrins are one of the most-widely studied chemical
systems owing to their plentiful properties, and the crucial
roles they play in nature, such as in green leaves and red
blood cells, have been discovered for many years, as well as
their applications in optics, catalysis, magnetism, medicine,
solar-energy conversion, conductive materials and so
forth.[20–31] The coordination of a metal ion at the center of a
porphyrin ring, as well as the substitution of the periphery
of a porphyrin ring by suitable organic groups, provides vari-
ous programming elements for the design of novel porphy-
rin compounds. Therefore, extensive efforts have been de-
voted to preparing a variety of metalloporphyrin compounds
that bear reformative characteristics that may have possible
practical applications.[32–36] However, to the best of our
knowledge, there are no reports of metalloporphyrins with
phase transformations. Among various metalloporphyrins,
vanadium porphyrins merit special attention because they
[a] Dr. W. Chen, Dr. T. Suenobu
Department of Material and Life Science
Graduate School of Engineering
Osaka University, Suita
SORST (Japan) Science Technology Agency
Osaka 565-0871 (Japan)
Fax : (+81)6-6879-7370
[b] Dr. W. Chen
School of Chemistry and Chemical Engineering
Jinggangshan University
Ji’an, Jiangxi 343009 (China)
[c] Prof. S. Fukuzumi
Department of Bioinspired Science
Ewha Womans University
Seoul 120-750 (Korea)
Supporting information for this article, including X-ray crystallo-
graphic files in CIF format for 1, IR spectra, MALDI-TOF-MS spec-
tra, UV/Vis absorption spectra, and photos, is available on the WWW
under http://dx.doi.org/10.1002/asia.201000822.
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Chem. Asian J. 2011, 6, 1416 – 1422

are known as a new class of anti-HIV agents.[37] Compared
with other vanadium complexes as potential therapeu-
tics,[38,39] vanadium porphyrins are stable and seldom
become demetalated.
Herein, we report the synthesis, X-ray crystal structures,
and properties of V(O)TMeOPP (1), which displays temper-
ature-controlled phase transformation. V(O)TMeOPP was
characterized in detail by single-crystal X-ray diffraction, el-
emental analysis, UV/Vis, FT-IR, MALDI-TOF-MS, and
electrochemical techniques, such as cyclic voltammetry (CV)
and differential pulse voltammetry (DPV).
It should be pointed out that compound 1 exhibits differ-
ent supramolecular motifs, 1R and 1L, at room temperature
and low temperature, respectively. Such a temperature-de-
pendent change in the supramolecular motif has rarely been
observed.[40] It is also noteworthy that compound 1 showed
purple and green colors at room temperature and low tem-
perature, respectively.
Crystal Structures of V(O)TMeOPP (1): Room-
Temperature Phase (1R)
The molecular structure of 1R is depicted in Figure 1
(ORTEP). X-ray diffraction analysis reveals that compound
1R consists of one neutral V(O)TMeOPP molecule and
crystallizes in the space group Pbca. All crystallographically
independent atoms are in general positions. The vanad-
AHCTUNGTREGUNiNN um(IV) ion is bound by four nitrogen atoms and one
oxygen atom to form a five-coordinate square pyramid. The
bond lengths from the vanadium ion (at the center of a
saddle-distorted nonplanar porphyrin macrocycle) to the
pyrrole nitrogens are within 2.043(2)–2.082(2) ꢀ in 1R,
which is comparable with that found in the literature.[43] The
bond length between the vanadium and oxygen atoms is
1.582(1) ꢀ, normal for a V=O double bond and comparable
with those reported.[44] Bond-valence calculations indicate
that the vanadium ion is in the +4 oxidation state [V(1):
4.041].[45] The porphyrin macrocycle in 1R displays a saddle
conformation and the four pyrrole rings appreciably distort
in an alternant fashion either upward and downward with
respect to the mean plane of the saddle-like porphyrin core.
The displacement of the four pyrrole nitrogen atoms are
within Æ0.008 ꢀ from their mean N4 plane. The dihedral
angles between the planes of the four pyrrole rings distorted
in the same direction with respect to the N4 plane are
19.478 and 25.578. The dihedral angles between the neigh-
Results and Discussion
General Characterization
The IR spectra of the title compound exhibit similar charac-
teristics to TMeOPP and the bands mainly appeared in the
range of 700–1600 cmÀ1 (see the Supporting Information,
Figure S1). The IR spectra of the free base of TMeOPP
showed two bands at n~3319 and n~965 cmÀ1, correspond-
ing to the nNÀH and dNÀH vibrations of the pyrrole rings, re-
spectively. However, in the IR spectra of 1 these two bands
vanished owing to the deprotonation and the metalation of
the pyrrole rings. These results provide evidence for the con-
version of the free-based porphyrin into a metalloporphyrin.
The strong peak at around 1005 cmÀ1 can be assigned to the
V=O stretch.
For 1, MALDI-TOF-MS analysis in chloroform (matrix:
CHCA; reflectron mode) showed a molecular ion peak,
which was in good agreement with the corresponding calcu-
lated exact mass number (see the Supporting Information,
Figure S2). This result implies that compound 1 retained its
structure in solution as in the solid state.
Abstract in Chinese:
Figure 1. ORTEP drawing of 1R with 10% thermal ellipsoids. Hydrogen
atoms were omitted for clarity. a) perspective view; b) side view.
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1417

S. Fukuzumi et al.
FULL PAPERS
boring pyrrole rings are 17.008, 12.108, 21.328, and 12.658.
With respect to the N4 plane, which may represent the
mean plane of the porphyrin core, the twisted angles of the
aryl rings are 78.748, 70.498, 68.098, and 110.218. In 1R,
À
À
some C H···p and C H···O interactions link the molecules
to construct a 3D supramolecular network (Figure 2).
Figure 3. ORTEP of 1L with thermal ellipsoids set at the 20% probabili-
ty level. Hydrogen atoms were omitted for clarity.
an average value of 2.066(3) ꢀ, which is close to that of 1R
[2.063(2) ꢀ] and comparable to that found in the litera-
ture.[43] The V=O bond lengths are 1.593(2) and 1.594(3) ꢀ,
approximately 0.01 ꢀ longer than that of 1R. The dihedral
angles between the porphyrin macrocycle and the mean
planes of the aryl rings are in a wide range of 55.248–
117.358. The assignment of the oxidation states for the vana-
dium atoms is consistent with the electronic charge, and was
confirmed by bond valence sum calculations. The BVS
values for the crystallographically independent vanadium
atoms, V(1) and V(2), are 3.970 and 3.965, respectively,
thereby indicating that the oxidation state for each vanadi-
um atom is +4.[45] The porphyrin macrocycles in 1L show a
saddle conformation and the pyrrole nitrogen atoms exhibit
displacements of Æ0.012 ꢀ from their mean N4 plane. With
respect to the N4 plane, the dihedral angles between the
planes of the pyrrole rings (that are distorted in the same di-
rection) are in the range 18.728–22.088. In comparison with
Figure 2. Packing diagram of 1R with the dashed lines representing hy-
drogen-bonding interactions. Geometry of represented hydrogen-bonding
À
1R, 1L has more C H···p and C-H···O interactions, which
allow 1 L to form a more-complex 3D supramolecular
framework (Figure 4). It should be pointed out that the
supramolecular motifs of 1R and 1L differ greatly when
they viewed along the same direction, for instance, along
the a axis in Figure 2 and 4.
interactions:
C(22)-H
(DHA)=134.468; C(33)-H
(DHA)=118.188; C(34)-H
(DHA)=134.238; C(39)-H(39A)···Cg(3) with
G
with
d
C···Cg =3.634(3) ꢀ
and
a
a
a
a
G
R
d
d
d
C···Cg =3.517(3) ꢀ and
C···Cg =3.516(4) ꢀ and
C···Cg =3.780(4) ꢀ and
E
G
N
ACHTUNGTRENNUNG
G
ACHTUNGTRENUN(NG DHA)=1468;
C(14)-H
N
aACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
UV/Vis Absorption Spectroscopy
C10) and C21-C26, respectively]. V: magenta; O: red; N: blue; C: gray.
According to Goutermanꢂs four-orbitals model,[46] metallo-
porphyrins generally show two types of strong absorption
bands: strong Soret bands (B bands) at around 400 nm with
an absorption coefficient e~105 mÀ1 cmÀ1, and several weaker
Q bands at around 450–650 nm with e~103-104 mÀ1 cmÀ1. The
UV/Vis absorption spectra for compound 1 and free-based
TMeOPP are given in the Supporting Information, Fig-
ure S3 and S4, respectively. The B and Q bands for free-
based TMeOPP are observed at 422, 454, 519, 556, 595, and
649 nm (e422 nm =7.82ꢃ105 mÀ1 cmÀ1). The B band of com-
pound 1 appears at 427 nm (e=7.51ꢃ105 mÀ1 cmÀ1), which is
Low-Temperature Phase (1L)
Low temperature X-ray diffraction analysis shows that com-
pound 1L (Figure 3) crystallizes in the space group Pca21,
which differs from that of 1R (Pbca). There are two crystal-
lographic independent vanadium ions in the crystal structure
of 1L. Each vanadium ion is located at the center of the
porphyrin macrocycle and coordinated by four nitrogen
atoms and one oxygen atom to yield a square pyramid. The
À
V N bond lengths range from 2.038(3) to 2.091(3) ꢀ with
1418
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Chem. Asian J. 2011, 6, 1416 – 1422

A Vanadium Porphyrin with a Temperature-Dependent Phase Transformation
Figure 4. Packing diagram of 1L with the dashed lines representing hy-
drogen bonding interactions. Geometry of represented hydrogen bonding
interactions:
C(27)-H
(DHA)=118.318; C(87)-H
(DHA)=128.898; C(88)-H
(DHA)=122.978; C(77)-H
(DHA)=136.448; C(22)-H
(DHA)=125.238; C(23)-H
(DHA)=121.938; C(43)-H
(DHA)=125.918; C(75)-H
(DHA)=89.608; C(75)-H(75C)···Cg(4) with
(DHA)=132.468; C(29)-H(29A)···Cg(5) with
(DHA)=158.908; C(92)-H(92A)···Cg(6) with
(DHA)=128.968; C(41)-H(41C)···Cg(7) with
G
with
d
C···Cg =3.545(5) ꢀ
and
a
a
a
a
a
a
a
a
a
a
a
a
G
E
d
d
d
d
d
d
d
C···Cg =3.661(4) ꢀ and
R
E
C···Cg =3.761(4) ꢀ and
C···Cg =3.530(4) ꢀ and
C···Cg =3.833(4) ꢀ and
C···Cg =3.853(4) ꢀ and
C···Cg =3.612(4) ꢀ and
C···Cg =3.436(4) ꢀ and
E
ACHTUNGTRENNUNG
N
ACHTUNGTRENNUNG
N
ACHTUNGTRENNUNG
R
ACHTUNGTRENNUNG
E
ACHTUNGTRENNUNG
N
U
dC···Cg =3.436(4) ꢀ and
R
A
d
d
d
C···Cg =3.574(4) ꢀ and
C···Cg =3.541(4) ꢀ and
C···Cg =3.788(4) ꢀ and
Figure 5. CV and DPV profiles for a) 1, and b) free-based TMeOPP
under an argon atmosphere.
E
A
E
G
A
ACHTUNGTRENUN(NG DHA)=1458;
C(19)-H
N
aACHTUNGTRENNUNG
A
a
R
ACHTUNGTRENNUNG
has been researched by several groups.[47] In general, each
vanadyl porphyrin undergoes two reactions at the porphyrin
p-ring system, yielding a p-anion and a dianion upon reduc-
tion and a p-cation and a dication upon oxidation. Similarly,
as shown in Figure 5a, slow sweep CV of 1 exhibits two
quasi-reversible waves (E1/2 =0.63 and 0.90 V), which are
close to the values of DPV (0.62 and 0.88 V). Besides these
two quasi-reversible waves, there are two successive and
well-defined anodic waves (À0.46 and À0.91 V), but no cor-
responding cathodic bands are observed on the inversed
scan. Unlike 1, the CV of free-based TMeOPP is character-
ized by two oxidation peaks at 0.50 V and 0.71 V and a re-
versible redox couple (E1/2 =À1.54 V), which are close to
the values of DPV (0.47, 0.66, À1.55 V), as shown in Fig-
ure 5b. It should be pointed out that the potentials of free-
based TMeOPP are negatively shifted compared to those of
1. The difference in the electrochemical properties between
free-based TMeOPP and metalloporphyrins 1 is probably
due to the metalation effect.
G
ACHTUNGTRENNUNG
a
R
G
ACHTUNGTRENNUNG
N
G
G
ACHTUNGTRENNUNG
C68), C21-C26, C42-C47, and C83-C88, respectively.] V: magenta;
O: red; N: blue; C: gray.
red-shifted by 5 nm compared with that of TMeOPP. Com-
pound 1 has only two Q bands, at 550 and 590 nm, as com-
pared with five Q bands in the free-based TMeOPP. This
difference is ascribed to an increase in the molecular sym-
metry, resulting from the metalation of the free-based
TMeOPP. The absorption coefficient of the B band for met-
alloporphyrin 1 is circa 105 mÀ1 cmÀ1, which is in good agree-
ment with the conclusion drawn by Gouterman.[46] The e
values of the B bands for compound 1 and free-based
TMeOPP are similar, thus indicating that the metalation of
a porphyrin hardly affects the absorption coefficient.
Electrochemical Studies
Cyclic voltammetry (CV) and differential pulse voltammetry
(DPV) measurements (benzonitrile solvent, room tempera-
ture, 0.1m TBAPF6) were performed for 1 and free-based
TMeOPP to investigate their redox properties (Figure 5).
Hitherto, the electrochemistry of many vanadyl porphyrins
Experimental Section
Measurements
Elemental analyses of carbon, hydrogen, and nitrogen were carried out
on an Elementar Vario EL III microanalyser. The infrared spectra were
Chem. Asian J. 2011, 6, 1416 – 1422
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S. Fukuzumi et al.
FULL PAPERS
recorded on a Thermo Nicolet NEXUS 870 FT-IR spectrophotometer
over the frequency range 4000–400 cmÀ1 (KBr pellet). The UV/Vis ab-
sorption spectrosa were recorded at room temperature on a computer-
controlled Hewlett Packard 8453 UV/Vis spectrophotometer equipped
with 89090 A Peltier temperature controller with the wavelength range
of 190–1100 nm. Matrix-assisted laser desorption/ionization (MALDI)
time-of-flight (TOF) mass spectra were measured on a Kratos Compact
MALDI I (Shimadzu).
Table 1. Crystal parameters for 1 measured at room temperature (1R)
and low temperature (1L).
Compound
1R
1L
formula
Fw
C48H36N4O5V
799.75
C48H36N4O5V
799.75
color
purple
purple
crystal size/mm3
crystal system
space group
a [ꢀ]
0.46 0.21 0.17
orthorhombic
Pbca
22.387(6)
15.572(8)
22.677(8)
7905(6)
8
0.46 0.21 0.17
orthorhombic
Pca21
15.633(3)
21.429(1)
23.068(2)
7728(2)
8
Cyclic voltammetry (CV) and differential pulse voltammetry (DPV)
measurements were performed at 298 K using a BAS 100W electrochemi-
cal analyzer in a deaerated solvent containing 0.1m TBAPF6 (tetra-n-bu-
tylammonium hexafluorophosphate) as a supporting electrolyte. A con-
ventional three-electrode cell was used with a platinum working elec-
trode and a platinum wire as a counter electrode. The measured poten-
tials were recorded with respect to Ag/AgNO3 (1.0ꢃ10À2 m). All electro-
chemical measurements were carried out under an atmospheric pressure
of argon.
b [ꢀ]
c [ꢀ]
V [ꢀ3]
Z
2qmax [8]
reflections collected
50
47581
50
43252
independent, observed reflections 6843, 5929
12819, 7610
(0.2337)
1.375
0.312
3320
(Rint
dcalcd. [gcmÀ3
(mmÀ1
(000)
)
(0.0435)
1.344
0.305
Syntheses
]
All reactants of analytical reagent grade were obtained commercially and
used without further purification. The title compound was prepared by
mixing VCl3 (0.1 mmol, 15.7 mg), TMeOPP (0.1 mmol, 73.5 mg), and
10 mL ethanol in a 23 mL Teflon-lined stainless-steel autoclave and heat-
ing the mixture at 453 K for 4 days. After slowly cooling the mixture to
room temperature at 6 K/h, purple crystals suitable for X-ray analysis
were obtained. The yield was 20% (based on vanadium). Anal. Calcd.
for C48H36N4O5V: C 72.02, H 4.50, N 7.00. Found: C 72.12, H 4.82, N 7.06.
Fourier transform IR (KBr): n˜ =2996(w), 2928(w), 2834(w), 2359(w),
1606(s), 1512(s), 1460(m), 1440(m), 1340(s), 1288(s), 1246(vs), 1173(vs),
1105(m), 1073(w), 1037(m), 1005(vs), 849(m), 807(s), 729(m), 666(m) and
635 cmÀ1(w) (Figure S1). m/z (MALDI-TOF-MS in CHCl3; matrix:
CHCA, that is, a-cyano-4-hydroxycinnamic acid) 799.42 (C48H36N4O5V
requires 799.21). See the Supporting Information, Figure S2.
m
N
)
F
A
3320
R1, wR2
S
0.0968, 0.2486
0.967
0.0802, 0.1538
0.868
largest and mean D/s
D1
(max, min) (e/ꢀ3)
0.001, 0
1.144, À0.584
0.001, 0
0.536, À0.775
AHCTUNGTRENNUNG
Table 2. Selected bond lengths (ꢀ) and bond angles (8).
Compound 1R
V(1)-O(5)
V(1)-N(1)
V(1)-N(2)
V(1)-N(3)
V(1)-N(4)
1.582(1)
2.082(2)
2.072(2)
2.043(2)
2.053(2)
O(5)-V(1)-N(3)
103.37(7)
103.99(6)
86.07(6)
151.64(6)
86.09(6)
87.80(6)
85.86(6)
150.71(6)
O(5)-V(1)-N(4)
N(2)-V(1)-N(1)
N(3)-V(1)-N(1)
N(3)-V(1)-N(2)
N(3)-V(1)-N(4)
N(4)-V(1)-N(1)
N(4)-V(1)-N(2)
X-ray Crystallographic Studies
The X-ray intensity data sets were collected for the same single crystal at
two different temperatures (123 and 293 K) on a Rigaku AFC-8 X-ray
diffractometer with graphite monochromated MoKa radiation (l=
0.71073 ꢀ) using a w-scan technique. CrystalClear software was used for
data reduction and empirical absorption corrections.[41] The structures
were solved by direct methods using the Siemens SHELXTL Version 5
package crystallographic software.[42] The difference Fourier maps based
on these atomic positions yielded the other non-hydrogen atoms. The po-
sitions of the hydrogen atoms were generated theoretically, being allowed
to ride on their respective parent atoms, and were included in the struc-
ture-factor calculations with assigned isotropic thermal parameters. The
structures were refined using a full-matrix least-squares refinement on F2.
All atoms except for hydrogen atoms were refined anisotropically. The
summary of crystallographic data and structure analysis is given in
Table 1. The selected bond lengths and bond angles are listed in Table 2.
O(5)-V(1)-N(1)
O(5)-V(1)-N(2)
104.99(7)
105.29(6)
Compound 1L
V(1)-O(5)
V(1)-N(1)
V(1)-N(2)
V(1)-N(3)
V(1)-N(4)
V(2)-O(10)
V(2)-N(5)
V(2)-N(6)
V(2)-N(7)
1.593(2)
2.059(3)
2.064(3)
2.067(2)
2.075(3)
1.594(3)
2.073(3)
2.091(3)
2.063(3)
2.038(3)
102.4(1)
104.7(1)
105.3(1)
104.3(1)
88.1(1)
N(1)-V(1)-N(3)
N(1)-V(1)-N(4)
N(2)-V(1)-N(3)
N(2)-V(1)-N(4)
N(3)-V(1)-N(4)
O(10)-V(2)-N(5)
O(10)-V(2)-N(6)
O(10)-V(2)-N(7)
O(10)-V(2)-N(8)
N(5)-V(2)-N(6)
N(7)-V(2)-N(5)
N(7)-V(2)-N(6)
N(8)-V(2)-N(5)
N(8)-V(2)-N(6)
N(8)-V(2)-N(7)
152.3(1)
85.8(1)
85.9(1)
151.0(1)
86.5(1)
104.7(1)
105.6(1)
104.3(1)
102.7(1)
86.7(1)
151.0(1)
85.5(1)
86.6(1)
151.8(1)
87.2(1)
CCDC 772465 (1L) and CCDC 772466 (1R) 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.
V(2)-N(8)
O(5)-V(1)-N(1)
O(5)-V(1)-N(2)
O(5)-V(1)-N(3)
O(5)-V(1)-N(4)
N(1)-V(1)-N(2)
Conclusions
In conclusion, we have synthesized a vanadium porphyrin,
V(O)TMeOPP, by using a solvothermal method, whose crys-
tal structures at room temperature and low temperature
were compared by using the same single-crystal. The com-
pound has been characterized by X-ray structural analysis,
UV/Vis, FT-IR, MALDI-TOF-MS, and CV/DPV. V(O)T-
MeOPP showed purple and green colors at room tempera-
ture and low temperature (see the Supporting Information,
Figure S5), respectively, which is unprecedented for vanadi-
um porphyrins. Future research in our laboratory will focus
on other vanadium porphyrins, to gain new insights into the
synthesis, crystal structure, and properties, as well as the re-
lationship among them.
1420
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Chem. Asian J. 2011, 6, 1416 – 1422

A Vanadium Porphyrin with a Temperature-Dependent Phase Transformation
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Received: November 16, 2010
Published online: April 7, 2011
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