Synthesis, characterization and computational investigation of novel metalloporphyrazines containing 15-membered O2 S2-donor macrocyclic moieties

Article abstract of DOI:10.1142/S1088424618500104

New metalloporphyrazines (MgPz, ZnPz) containing peripheral tetrasubstitutions derived from 7,8-dihydro-6H,14H,19H-dibenzo[bj][1,12,5,8]-dioxadithiacyclopentadecine-16,17-dicarbonitrile (6) have been synthesized by a multistep reaction sequence and charac

Full text of DOI:10.1142/S1088424618500104

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2018; 22: 1–14
DOI: 10.1142/S1088424618500104
Published at http://www.worldscinet.com/jpp/
Synthesis, characterization and computational investigation
of novel metalloporphyrazines containing 15-membered
O2S2-donor macrocyclic moieties
·
Yasemin Baygua, BurakYıldızb,Izzet Karac, Hakan Dald andYas¸ar Göke*
aTavas Vocational School of Higher Education, Pamukkale University, Denizli, Turkey
·
bDepartment of Chemistry, Yıldız Technical University, Istanbul, Turkey
cDepartment of Physical Education, Pamukkale University, Denizli, Turkey
dDepartment of Chemistry, Anadolu University, Eskisehir, Turkey
eDepartment of Chemical Engineering, Us¸ak University, Us¸ak, Turkey
Received 27 November 2017
Accepted 19 December 2017
Dedicated to Professor Kazuchika Ohta on the occasion of his retirement
ABSTRACT: New metalloporphyrazines (MgPz, ZnPz) containing peripheral tetrasubstitutions derived
from 7,8-dihydro-6H,14H,19H-dibenzo[bj][1,12,5,8]-dioxadithiacyclopentadecine-16,17-dicarbonitrile
(6) have been synthesized by a multistep reaction sequence and characterized. Compound 6 has been
prepared by the reaction of 1,3-di(2-bromomethyl phenoxy) propane (3) or 1,3-di(2-iodomethylphenoxy)
propane (4) which were prepared via bromination or iodination of {2-[3-(2-hydroxymethylphenoxy)
propoxy]-phenyl} methanol (2) and cis-1,2-dicyano-1,2-ethylenedithiolate (5). The novel magnesium
porphyrazine was prepared by the cyclotetramerization reaction of 6 with magnesium butoxide. The
one-step synthesis of porphyrazinato zinc complex has been achieved without a reaction sequence by
using dicyano compound (6) and zinc butoxide. The prediction of the geometry optimization, normal
mode frequencies, 1H, 13C NMR, UV absorption spectra, chemical shifts, electronic properties and NBO
analysis of the compound were examined by using B3LYP method with a 6-31G(d, p) basis set. These
1
novel compounds were characterized by a combination of elemental analysis, H, 13C NMR, FT-IR,
UV-vis and MS spectral data. An X-ray crystal structure of dicarbodinitrile compound (6) was also
investigated.
KEYWORDS: mixed-donor macrocycle, porphyrazine, template reaction, green chemistry, X-ray
investigation, computational chemistry.
their first synthesis, which took place almost 60 years
INTRODUCTION
ago [2–4]. Porphyrazines have found vast applications
One of the most important cornerstones in tetrapyr-
in diverse areas such as industrial dyes and pigments,
rolic macrocyclic system is porphyrazine [1]. Porphyr-
electrocatalysts, electrochromic displays, PDT applica-
azines are similar to phthalocyanines, so they can
tions, chemical sensors, Langmuir–Blodgett films,
also be used in similar applications. In contrast, the
liquid crystals and non-linear optics, including their
similarities among porphyrazines and their derivatives
application in material science [5–7]. The first synthesis
such as aminoporphyrazines, porphyrazinols and
of crown-fused porphyrazines has been accomplished by
porphyrazine thiolates have been less studied since
the groups of Hoffman and Nolte [8–10]. Porphyrazine
derivatives, which contain soft sulfur donor atoms, play
an important role in affecting the solid-state interactions,
and the sulfur atoms in the macrocyclic unit also give
*Correspondence to: Yas¸ar Gök, tel.: +90 258 2963567; fax:
+90 248 2963535; email gyasar@pau.edu.tr.
Copyright © 2018 World Scientific Publishing Company

2
Y. BAYGU ET AL.
the opportunity to bind soft transition metal cations [11–
13]. In addition, the electron-withdrawing effect of the
maleonitrile moiety may reduce the electron–donating
ability of sulfur donors in macrocyclic units, and this
kind of heteroatoms strongly perturb the porphyrazine
grand state transition and shifting to visible-to-near-IR
region [14].
The chemistry of macrocycles containing mixed-
donor multidentate ligands and their cation complexation
abilities has been explored extensively over the past
49 years [15–17]. Another rapidly emerging topic of
chemical interest in recent years concerns the synthesis of
polynucleating ligands and the coordination chemistry of
these kinds of macrocycles [18, 19]. Mixed donor crowns
such as O2S2 type may be considered to lie between the
two macrocyclic categories, and their properties also tend
to span those of each class. These kinds of macrocycles
form stable complexes with heavy metal cations while
their complexes with main group metal cations become
less stable.
Density Functional Theory methods have been
widely used to predict the properties of molecules and
bulk materials at an atomic scale, and the developments
in the methodological innovations, and ab initio and
DFT approaches have turned into an inter-disciplinary
approach combining molecular sciences and chemistry
[20].ItisknownthattheDFT(B3LYP)methodadequately
takes into account electron correlation contributions,
which are especially important in systems containing
extensive electron conjugation and/or electron lone pairs.
DFT methods are extensively used in order to simulate
the electronic spectra of metal complexes despite the
fact that the most appropriate method to describe the
ground state and excited state properties of these kind
of compounds seems to be the multiconfigurational self-
consistent-field one including relativistic effects. The
most popular among them is the time-dependent DFT
(TD-DFT) approach [21].
In the present study, we synthesized and characterized
a novel metalloporphyrazine having symmetrically
four 15-membered dioxadithia (O2S2) crown ether
moieties. X-ray crystal structural analyses concerning
dicyano compound has also been performed. In
addition to the detailed synthesis procedures, we also
theoretically investigated the geometry optimization of
precursor dicyano compound (5), magnesium and zinc
porphyrazines by means of the B3LYP method with a
6-31G(d, p) basis set.
cis-1.2-dicyano-1.2-ethylene dithiolate sodium salt [23]
were synthesized according to the literature procedures.
All solvents were freshly purified by standard procedures
before use [24]. Anhydrous CH3CN and DMF were
obtained by a 4 Å molecular sieve activated under
1
500°C for 5 h. H and 13C NMR were recorded on an
Agilent NMR-vnmrs 400 and on a Varian Mercury Plus
300-MHz spectrometer using TMS as internal standard.
Infrared spectra were recorded on a Perkin Elmer UATR
Two spectrometer. Mass spectra were determined on
a Bruker Daltonicis Microflex Mass Spectrometer
equipped with a nitrogen UV-Laser operating at 337 nm
and Thermo TSQ Quantum Access Max. LC-MS/MS
instruments. Electronic absorption spectra were recorded
using a Shimadzu UV-1601 spectrophotometer. All
measurements were in made a sealed 1 ml quartz cuvette.
Elemental analysis were performed on a Costech ECS
4010 instrument. All products were dried under vacuum
before analysis. The transition metal content of the
porphyrazine was measured on a Perkin Elmer Analyst
700 Atomic Absorption Spectrometer by using the
emission method (signal type) at l = 285.2 nm. Melting
points were determined on an electrothermal apparatus
and are uncorrected.
X-ray crystallography
The suitable crystals of the title compound were
crystallized from ethanol at room temperature.
Crystallographic data were recorded on a Bruker Kappa
APEXII CCD area-detector diffractometer using Mo Ka
radiation (l = 0.71073 Å) at T = 120 (2) K. Absorption
correction by multi-scan [25] was applied. The structure
was solved by direct methods and refined by full-
matrix least squares against F2 using all data [26]. All
non-H atoms were refined anisotropically. Aromatic
and methylene H atoms were positioned geometrically
at distances of 0.95 (aromatic) and 0.99 (CH2) from
the parent C atoms; a riding model was used during
the refinement process and the Uiso (H) values were
constrained to be 1.2 Ueq (for aromatic and methylene
carrier atoms). The crystallographic data are given in
Table 3.
Theoretical calculations
One of the most successful quantum chemistry tools
in describing the ground state properties of compounds
is hybrid density functional theory (DFT). B3LYP
(Becke3-Parameter method for calculating that part of
the molecular energy due to overlapping orbitals plus the
Lee–Yang–Parr method of accounting for correlation) is
one of the most popular DFT methods [20–21, 27]. The
molecular structures of compound 6, MgPz and ZnPz
were optimized to obtain the global minima at B3LYP/6-
31g (d, p) level. The 1H and 13C NMR chemical shielding
constants were calculated by applying the GIAO-B3LYP;
the electronic structure and NBO analysis in gas phase
EXPERIMENTAL
General
All reactions were carried out under an argon
atmosphere using Schlenk techniques connected vacuum
line. 1.5-Bis(2′-formylphenyl)-1.5-dioxapentane [22] and
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SYNTHESIS, CHARACTERIZATION AND COMPUTATIONAL INVESTIGATION OF NOVEL METALLOPORPHYRAZINES
3
were also calculated using the same procedure. All
calculations were performed by using the Gaussian 09
Revision C1 program [28]. In addition, GaussView 5.0.9
was used for visualization of the structure and simulated
vibrational spectra [29].
Tables S2–S4 (Table S2 (LP-Compound 6), Table S3
(LP-MgPz) and Table S4 (LP-ZnPz), see Tables S2,
S3 and S4 in the Supplementary information) show
the intramolecular, rehybridization NBO analysis of
compound 6 and metalloporphyrazines. NBO analysis
supplies a capable method for studying intra- and
intermolecular bonding and charge transfer in molecular
systems [30]. The second order Fock matrix was
fulfilled to interpret the donor–acceptor interactions in
the NBO analysis [29]. For each donor and acceptor
(j), the stabilization energy E(2) associated with the
delocalization i → j is estimated using Eq. 1
J = 7.24 Hz, 2H, Ar-H), 6.92 (d, J = 7.89 Hz, 2H, Ar-H),
4.67 (s, 4H, CH2-OH), 4.24 (t, J = 5.70 Hz, 4H, CH2O),
2.56 (s, 2H, OH), 2.35–2.31 (m, 2H, CH2). 13C NMR (75
MHz, CDCl3): d 156.48, 129.26, 128.94, 120.99, 111.28,
65.04, 61.70, 29.34. FT-IR (ATR), nmax/cm-1: 3293, 3062,
3043, 3008, 2947–2880, 1602, 1590, 1493, 1451, 1236,
1039, 998, 744. MS (ESI): m/z 310.71 [M + Na – H]+.
Anal. calcd. for C17H20O4: C, 70.83; H, 6.94. Found: C,
70.72; H, 7.04.
Synthesis of {2-[3-(2-bromomethylphenoxy)propoxy]
phenyl}methanol (3). To PBr3 (24.36 g, 90 mmol)
in dry diethyl ether (20 mL) was added dropwise a
solution of 1,3-di(2-hydroxy-methylphenoxy)propane
(2) (5 g, 17.35 mmol) in a mixture of diethyl ether
(270 mL) and ethyl acetate (30 mL) in cryostate under
argon atmosphere at -3°C. The mixture was stirred under
the above mentioned condition for 10 min and then
stirring was continued at room temperature for 70 h.
At the end of this period, the mixture was evaporated to
dryness under reduced pressure and the crude product
was mixed with ethanol (100 mL). The mixture was
filtered off and washed several times with diethyl ether
and then dried in vacuo. The fine desired product was
obtained by recrystallization from ethyl acetate. Yield:
E(2) = DEij = qiF(i, j)2/(ej−ei′)
(1)
where qi is the donor orbital occupancy, ei and ej are
diagonal elements and F (i, j) is the off diagonal NBO
Fock matrix element [31, 32]. The hyperconjugative
s → s* interactions play a substantial role. These
interactions express the weak separation from a
properly localized natural Lewis structure that forms
the primary “noncovalent” effect [33]. NBO analysis
was performed on the molecule at the B3LYP/6-31G
(d, p) level in order to clarify the intra-molecular
rehybridization and delocalization of electron density
within the molecule [34].
1
3.15 g (43.85%); mp. 101–102°C. H NMR (300 MHz,
CDCl3): d 7.30 (t, J = 8.05 Hz, 4H, Ar-H), 6.94–6.89 (m,
4H, ArH), 4.57 (s, 4H, BrCH2), 4.33 (t, J = 6.06 Hz, 4H,
OCH2), 2.41–2.38 (m, 2H, CH2). 13C NMR (75 MHz,
CDCl3): d 156.75, 130.78, 130.29, 126.06, 120.6, 111.81,
64.61, 29.27. FT-IR (ATR), nmax/cm-1: 3042, 2963–2879,
1599, 1494, 1466, 1454, 1314, 1290, 1244, 1221, 1197,
1144, 1065, 1045. MS (ESI): m/z 415 [M + H]+, 432
[M + H2O]+, 452.92 [M + K]+. Anal. calcd. for
C17H18O2Br2: C, 49.27; H, 4.34. Found: C, 49.41; H, 4.46.
Synthesis of {2-[3-(2-iodomethylphenoxy)propoxy]
phenyl}methanol (4). A round bottomed flask which
contains compound 2 (1.44 g, 5 mmol) and NaI (4.475 g,
29.85 mmol) in dry acetonitrile (100 mL) and which was
fitted with a condenser was evacuated refilled three times
with argon and connected to the vacuum line. To a solution
of the corresponding alcohol, bromotrimethylsilane
(4.54 g, 29.7 mmol) was added dropwise while
continuously stirring. The reaction mixture was stirred
at room temperature for 20 min and monitored by
thin layer chromatography (silica gel (chloroform:
methanol) (95:5)]. A mixture of dichloromethane and
water [100 mL (1:1)) was added to the reation mixture
and the organic phase was separated and then washed
with water (50 mL), Na2S2O3 solution (50 mL, 10%),
brine and water and then dried over MgSO4. The
organic phase was evaporated to dryness under reduced
pressure yielding a pale yellow solid that was purified by
column chromatagraphy on silica gel using the mixture
of hexane: chloroform (3:2) as eluent to give a pale
yellow solid. Yield: 2.15 g (84.64%): mp. 99–100°C.
1H NMR (300 MHz, CDCl3): d 7.30 (d, J = 7.43, 2H,
Ar-H), 6.92 (d, J = 8.22, 2H, Ar-H), 6.87 (t, J = 7.43,
Synthesis
Synthesis of {2-[3-(2-hydroxymethyl-phenoxy)-
propoxy]-phenyl}-methanol (2). Water (2.7 mL) was
poured into silica [5.42 g (70–230 mesh) 90 mmol)
which was charged in a round-bottomed flask (100 mL)
and the mixture was stirred to produce wet silica at
room temperature. 1.5-Bis (2′-formylphenyl)-1.5-dioxa-
pentane (1) (7.7 g, 27.1 mmol) was then added to the
prepared wet silica and the reaction mixture was stirred
for an additional 5 min. A fine powdered NaBH4 (1.03 g,
27.1 mmol) was added to this mixture and then the
reaction mixture was stirred for an additional 1 min at
room temperature while the reaction was performed
in an explosive manner and monitored by a thin layer
chromatography (silica gel (chloroform:methanol)
(98:2)). Then dichloromethane (30 mL) was added
and stirred to this reaction mixture for 30 min at room
temperature. At the end of this period, the mixture was
filtered off and washed with dichloromethane (3 × 8 mL)
and the combined solvents were dried over anhydrous
Na2SO4. The pure product was obtained by column
chromatography on silica gel using the mixture of
chloroform:methanol (98:2) as eluent to give a colorless
1
solid. Yield: 6.19 g (79%); mp. 95–96°C. H NMR
(300 MHz, CDCl3): d 7.30–7.28 (m, 4H, Ar-H), 6.96 (t,
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Y. BAYGU ET AL.
4H, Ar-H), 4.49 (s, 4H, ICH2), 4.37 (t, J = 4.70, 4H,
OCH2), 2.45 (m, 2H, CH2). 13C NMR (75 MHz. CDCl3):
d 156.44, 129.99, 129.68, 127.30, 120.68, 111.81, 64.66,
29.45, 1.59. FT-IR (ATR), nmax/cm-1: 3077, 3055, 3029,
2926–2972, 1597, 1493, 1451, 1247, 1154, 1044, 745.
MS (ESI): m/z 509 [M + H]+. Anal. calcd. for C17H18O2I2:
C, 40.15; H, 3.54. Found: C, 40.37; H, 3.38.
ethanol to give 6 as pale yellow crystals. Yield: 0.35 g
(33.6%). mp.159°C.
Synthesis of metallo porphyrazines (MgPz, ZnPz).
Metal powders (0.0086 g, 0.36 mmol Mg 0.0376 g,
0.579 mmol Zn) and I2 (one small crystal) and n-butanol
(4 mL) were charged in a Schlenk system connected
with a vacuum line under argon atmosphere. The
reaction mixture was refluxed and stirred for 24 h until
all metal was dissolved. The suspension was cooled to
room temperature and dicyano compound (6) (0.23 g,
0.584 mmol for Mg(BuO)2 0.37 g, 0.93 mmol for
Zn(BuO)2) was added, then the mixture was further
heated at reflux temperature. The reaction mixture
turned a turquoise color after approximately 10 min.
This suspension was stirred and refluxed for 24 h. The
reaction was monitored by thin layer chromatography
(silica gel (hexane: chloroform) (2:1)). The deep dark
blue suspensions were cooled to room temperature,
filtered and washed with methanol. The solution was
concentrated in vacuo and the residue was purified
by column chromatography over silica gel ((hexane:
chloroform) (2:1)) to obtain a dark blue solid.
Synthesis of 7.8-dihydro-6H,14H,19H-dibenzo[bj]
[1,12,5,8]dioxadithiacyclo pentadecine-16,17-dicarbo-
nitrile (6).
Method A. cis-1.2-Dicyano-1.2-ethylene dithiolate
sodium salt (5) (0.93 g, 5 mmol) and compound 3
(2.07 g, 5 mmol) were dissolved in dry DMF (40 mL), and
these solutions were placed in two syringes. The contents
of the syringes were added dropwise (a rate of 0.5 cm3 h-1)
as synchronized under an argon atmosphere at 45°C
for 80 h by using a syringe pump. The reaction mixture
was stirred at this temperature for a further 4 days and
monitored by thin layer chromatography (silica gel
(chloroform:methanol) (98:2)). At the end of this period,
the reaction mixture was cooled to room temperature
and filtered. The filtrate was evaporated to dryness under
reduced pressure and the residue was partitioned between
water and chloroform (100 mL (1:1)). The aqueous
phase was separated and extracted with chloroform
(20 mL × 3). The combined organic phases were dried
over anhydrous MgSO4 and then evaporated to dryness
under reduced pressure. The pure product was obtained
by column chromatography on silica gel using the
mixture of chloroform: methanol (98:2) as eluent to give
a pale yellow solid. Yield: 0.43 g (22%); mp. 157°C. 1H
NMR (300 MHz, CDCl3): d 7.32 (d, J = 6.65 Hz, 4H,
Ar-H), 6.96 (t. J = 7.43 Hz, 4H, Ar-H). 4.27 (d. J = 2.95
Hz, 4H, OCH2). 4.23 (s, 4H, SCH2). 2.39 (m, 2H, CH2).
13C NMR (75 MHz, CDCl3): d 157.72, 131.64, 130.23,
124.60, 123.70, 121.69, 114.50, 113.20, 67.25, 35.62,
29.93. FT-IR (ATR), nmax/cm-1: 3068, 3038, 2958–2868,
2204 (C≡N), 1597, 1493, 1452, 1315, 1291, 1242, 1187,
1158, 1094. MS (ESI): m/z: 395.08 [M + 1]+, 417.07
[M + Na]+. Anal. calcd. for C21H18N2O2S2: C, 63.95; H,
4.46; N, 7.10. Found: C, 63.84; H, 4.59; N, 6.98.
Method B. A mixture of compound 4 (1.34 g, 2.64
mmol) and cis-1.2-dicyano-1.2-ethylene dithiolate
disodium salt (5) (0.49 g, 2.64 mmol) in dry acetonitrile
(150 mL) in a round-bottom two necked flask was heated
and stirred at reflux temperature under argon atmosphere
for 24 h. The reaction was monitored by a thin layer
chromatography (silica gel (hexane: chloroform) (3:2)).
At the end of this period, the reaction mixture was filtered
while hot and then allowed to cool to room temperature.
The solvent was evaporated to dryness under reduced
pressure and the residue was solidified with water
(80 mL) at room temperature overnight. The brown solid
was filtered and the solids washed with water and then
dried in vacuo. The solid was chromatographed on silica
gel ((hexane: chloroform) (3:2)) and recrystallized from
1
MgPz: Yield: 0.04 g (17.12%), mp > 300°C. H
NMR (300 MHz, CDCl3): d 7.33 (s, 8H, Ar-H), 7.12
(s, 10H, Ar-H), 6.95 (s, 8H, Ar-H). 6.61 (s, 6H, Ar-H),
4.40–4.29 (m, 32H, Ar-CH2O, CH2S), 2.43–2.27 (m, 8H,
CH2). 13C NMR (75 MHz, CDCl3): d 157.42, 145.96,
137.47, 128.49, 121.16, 114.01, 67.30, 36.63, 34.60,
29.53. FT-IR (ATR), nmax/cm-1: 3064, 3025, 2960–2872,
1666, 1598, 1490, 1452, 1257, 1095, 1011, 792. UV-vis
(CHCl3): lmax, nm (log e): 683 (4.49), 625 (sho, 4.07),
506 (br, 3.76), 358 (4.53). MS (ESI) m/z: 1601 [M+H]+.
Anal. calcd. for C84H72N8O8S8Mg: C, 63.00; H, 4.50; N,
7.00. Found: C, 63.16; H, 4.69; N, 6.83.
1
ZnPz: Yield: 0.08 g (21%). Mp > 300°C. H NMR
(300 MHz. CDCl3): d 7.23 (m, 24H, Ar-H), 6.89 (m, 8H,
Ar-H), 4.24–4.16 (m, 32H, OCH2, SCH2), 2.40 (m, 8H,
CH2). 13C NMR (75 MHz, CDCl3): d 156.74, 144.61,
130.64, 129.27, 123.62, 120.71, 113.51, 66.26, 34.83,
29.95. FT-IR (ATR), nmax/cm-1: 3062, 3031, 2952-2866,
1648, 1598, 1490, 1452, 1236, 1100, 1019, 743. UV-vis
(CHCl3): lmax, nm (log e): 685 (4.86), 627 (sho, 4.43),
519 (br, 4.04), 378 (4.76). MS (ESI) m/z: 1642.830
[M + H]+. Anal. calcd. for C84H72N8O8S8Zn: C, 61.40;
H, 4.38; N, 6.82; Zn, 3.99. Found: C, 61.25; H, 4.56; N,
7.62; Zn, 4.16.
RESULTS AND DISCUSSION
Synthesis
Salicyl aldehyde as a starting material underwent an
etherification reaction with 1,3-di-bromopropane in high
yield using a well-known synthetic route as outlined in
Scheme 1. There are several reports for the synthesis of
1,5-bis(2-benzyl alcohol)-1,5-dioxapentane (2). One of
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5
O
O
PBr3
Ar
Br
Br
O
O
O
O
SiO2, H2O
NaBH4
NaS
NaS
CN
CN
OH
OH
O
O
(3)
+
NaI,
Me3SiBr
Ar
I
I
(5)
O
O
(1)
(2)
(4)
Ar,
reflux
MeCN
O
O
O
O
S
N
S
N
S
S
S
N
N
N
Mg/Zn, I2
n-Butanol
Ar, reflux
O
O
S
S
CN
M
N
N
CN
S
N
S
S
O
O
(6)
O
O
M: Mg, Zn
Scheme 1. The synthesis of MgPz and ZnPz
them mentions the compound being prepared by using
a nucleophilic substitution reaction of 2-hydroxy benzyl
alcohol and 1,3-dibromopropane. Compound 2 has been
previously obtained in considerable amount yield via
the reduction reaction of aldehyde groups by sodium
borohydride [35]. Recently, wet silica as an inexpensive
and readily available reagent has been frequently used for
some organic syntheses such as cleavage of azomethine
moieties or oxidation of alcohols [36]. The present
reduction reaction is high-yielding compared with the
above-mentioned reduction reactions and should prove
to be extremely productive for synthesis. This reduction
reaction, carried out in green chemistry media, has
received great attention with advantages such as energy
savings, avoidance of solvent waste and a short reaction
period. The rate of reduction of aldehyde groups was
dramatically accelerated and the reduction procedure
was completed in 1 min (Fig. 1). 1H, 13C NMR, FT-IR and
MS spectral data (see the Supplementary information,
Fig S1–S3) concerning structural characteristics of this
compound are in accordance with the proposed structure
and with the literature [37].
The alcohol groups of compound 2 were substituted
by bromine moieties through use of boron tribromide
to give {2-[3-(2-bromomethylphenoxy)propoxy)phenyl}
methanol (3). This product has recently been prepared
from compound 2 by means of a similar one-step proce-
dure, but no experimental details and characterization
have been furnished [38]. Phosphor tribromide in dry
diethyl ether was added dropwise to a cooled (-3°C)
dry diethyl ether/ethyl acetate solution. After stirring at
this temperature for 10 min and letting stand a further
70 h at room temperature, the bromination derivative (3)
was isolated as a yellow colored solid and then purified
1
by column chromatography in 43.85% yield. The H
NMR spectrum of 3 showed the characteristic emerged
signal at d = 4.57 ppm related to bromide substitution.
1
The other H NMR signals of 3 closely resemble those
of the starting compound (2). In the proton-decoupled
13C NMR spectrum of this compound, the signal for the
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Y. BAYGU ET AL.
bromination of two hydroxy group carbons at d = 29.27
ppm indicated the substitution reaction was completed
(Figs S4–S5). The resonances for the benzylic alcohol
groups of precursor compound at 3293 cm-1 in the FT-IR
spectrum of 2 were not observed in compound 3. The
absence of these stretching vibrations also indicate
the displacement of hydroxy groups with bromines.
The mass spectrum of this compound (Fig. S6) shows
the molecular ion peak as m/z = 415 [M + H]+, and the
other, bigger fragments are observed together with the
corresponding leaving groups such as 333.0498 [M–
Br–1]+ and 253.1225 [M–2Br–1]+.
Compound 4 was prepared by reacting NaI with
precursor benzylic alcohol (2) in the presence of
bromotrimethyl silane. The iodine derivative of 2 was
obtained in a good yield (84.64%) in a very convenient
reaction route and period. Iodination of different types
of alcohols were investigated in the presence of KI/
BF3. Et2O [39], Ph3/I [40] or trimethyl silyl chloride
[40]. The choice of this route to obtain iodine derivative
was essentially easier, giving an advantage in terms of
yield, short reaction time and easy work-up. In addition,
the macrocyclization reaction with cis-1,2-diethylene
dithiolate sodium salt is moderately easier than other
Fig. 1. The reduction process of compound 1
1
halogen derivatives of 2. The H NMR spectrum of 4,
the disapperance of OH chemical shifts belonging to the
precursor compound (2) and, along with the appearance
of the resonance at d = 4.49 ppm corresponding to
CH2-I moieties, support the formation of iodination
reaction. A similar change of carbon resonance of
13C NMR spectrum of this compound is due to the
displacement of hydroxy groups with iodides (see in the
Supplementary information, Figs S7–S8). The absence
of O–H resonances at 3293 cm-1 in FT-IR spectrum of
the same compound also indicate the displacement of
hydroxy groups with iodine. The occurrence of the
(M + H) peak at m/z = 509 in the ESI mass spectrum of
this compound (see Fig. S9) indicated the formation of
the desired compound.
C5
C4
C3
C6
C9
C2
C11
C7
C8
O
C10
CN
S
C1
S
O
CN
Dicyano compound (6) was synthesized via two similar
routes. In one of them, the target compound was prepared
by a condensation reaction for macrocyclization from
dibromo derivative (3) with cis-1,2-dicyano-1,2-ethylene
dithiolate (5) under high dilution conditions. In the other,
the reaction of diiodo derivative (4) and one equivalent
of compound 5 in refluxing acetonitrile gave the product
(6) in 33.6% yield as pale yellow crystals after column
chromatography (silica gel (chloroform: methanol)
(98:2)).Inthe1HNMRspecrumof6, theresonancesignals
for the OCH2 and SCH2 protons appeared at d = 4.27
and 4.23 ppm as combined signals, respectively, which
indicates the formation of the expected macrocycle Fig. 2.
The chemical shifts of the other protons were similar to
those of the corresponding precursor. In the 13C NMR
spectrum of this compound (Figs S10–S11), the signal for
the C≡N carbon atoms appears at d = 113.20 ppm, which
are similar to those of the known dicyano compounds [42].
Fig. 2. The structure of compound 6
According to the FT-IR spectrum of 6, the characteristic
vibrations for the C≡N groups at 2204 cm-1 supported
the formation of the macrocycle. The ESI mass spectrum
of this compound (6) also confirmed the proposed
structure, with the molecular ion peak (Fig. S12) easily
identified at m/z = 395.0871 [M + H]+. This 15-membered
O2S2-macrocycle was also characterized by single-crystal
X-ray crystallography technique. Pale yellow single
crystals of this compound suitable for X-ray analysis
were obtained by column chromatography.
In the synthesis of metalloporphyrazines (MgPz,
ZnPz), equivalent amounts of dicyano compound (6)
were reacted with Mg(OBu)2 or Zn(OBu)2 [43] in
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SYNTHESIS, CHARACTERIZATION AND COMPUTATIONAL INVESTIGATION OF NOVEL METALLOPORPHYRAZINES
7
Table 1. Values of the 1H NMR and 13C NMR chemical shifts
disappeared and the new resonances appeared at 1666
and 1648 cm-1. Those are attributed to the C=N moieties
of compound 6 as computed using the B3LYP method with the
6-31G (d, p) basis set and available experimental data
for the metalloporphyrazines in the FT-IR spectra. These
results and the color changing to dark blue after the
Atoms
Exp
2.48
Gas phase
Chloroform
cyclotetramerization reaction also indicate porphyrazine
formation. The mass spectra of porphyrazines obtained
by the MALDI-TOF technique confirmed the proposed
structures, with the molecular ion being easily identified
at m/z = 1601 [M + H]+ for MgPz (Fig. S15) and 1642.830
[M + H]+ for ZnPz (Fig. S18),
2.89
4.00
2.82
4.12
H1
H2
H3
H4
H5
H6
H9
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
4.27
7.33
6.81
6.98
6.95
7.35
7.48
6.97
7.00
7.09
Correlation analysis between the experimental
and theoretical results has been conducted to observe
experimental consistency with the chemical shifts
calculated by using B3LYP/6-31G (d, p) level.
Correlation analysis has been done to gather a full set
of the chemical shifts for compound 6 considered in gas
phase and chloroform (see Table 1) in order to check
the performance of the experimental and theoretical
approach adopted. Theoretical 1H and 13C chemical shift
values calculated with GIAO-DFT with respect to TMS
of compound 6 are significantly in agreement with the
experimental values in that the correlation parameters
of compound 6 were calculated to be R2 = 0.9856 in
gas phase and R2 = 0.9852 in solvent (Fig. 3). There is
compatibility between experimental and theoretical
results for the chemical shifts of the chemical compounds.
7.31
7.35
7.44
4.24
4.33
4.41
29.93
67.25
123.70
130.23
131.64
124.60
121.69
157.72
35.62
114.50
113.20
35.45
68.80
110.91
125.46
116.52
126.66
119.26
155.33
43.74
125.19
104.14
35.96
69.06
111.77
126.35
116.80
127.00
118.78
155.75
44.36
126.20
105.52
Electronic properties and NBO analysis
The absorption spectra of metalloporphyrazines
(Fig. 6) show the typical structures of porphyrinoid
systems and consist of two regions: a strong low-energy
absorbance (Q) at 686–681 that is accompanied with a
slightly higher energy shoulder at 630–620 nm, a less
intense peak at 500–510 nm and another intense peak
at 380–395 nm which is known as the Soret band [45].
These characteristic bands strongly resemble those
of symmetrical porphyrazine analogs [46]. Metallo-
derivatives of porphyrazines have D4h symmetry for this
reason: their p1* and p2* orbitals are doubly degenerate.
The above-mentioned single sharp bands relate to the p1
and p2 → p1.2* transition [47]. The Soret transitions at
known p → p* regions in porphyrazines are assigned
to an a1u → eg transition. The broad absorption at the
500–510 nm region should be assigned to the n→p*
transitions of the nonbonding electrons of the peripheral
sulfur atoms and meso nitrogen atoms which are
associated with the porphyrazine core p system [48].
Some of the most important parameters in molecular
orbital theory are the highest occupied molecular orbital
(HOMO) and the lowest unoccupied molecular orbital
(LUMO) energies. The electron conductivity and the
spectroscopic properties of the molecules show the
characteristics of the energy gap between the HOMO–
LUMO orbitals.
n-butanol under reflux for 24 h. At the end of this period,
novel solid products were obtained and purified by
column chromatography using hexane/chloroform (2:1)
as the eluent to afford dark blue target compounds in
17.12 and 21% yields, respectively. Attempts to obtain
good quality single crystals of metalloporphyrazines
were unsuccessful. The 1H NMR spectra of MgPz
(Fig. S13) and ZnPz (Fig. S16) exhibited the charac-
teristic sharp signals concerning OCH2 and SCH2 groups
at d = 4.40–4.29 and 4.24–4.16 ppm, respectively, which
were assigned to the equivalent protons of the O2S2-
1
macrocyclic moieties. The H NMR spectrum of MgPz
compound gave rather broad peaks. This situation could
be attributed to aggregation of this compound [44].
The 13C NMR spectra of metalloporphyrazines clearly
indicate the cyclotetramerization of dicyano derivative
(6), with the disappearance of the C≡N carbon resonances
at d = 113.20 ppm and appearance of C=N resonances at
d = 145.96 and 144.61 ppm concerning the inner core.
The other chemical shifts belong to the aromatic, thio
ether and oxa crown ether carbons, and are similar to
those of the precursor compound as expected (Figs S14,
S17). Corresponding B3LYP/6-31G (d, p) calculated
values are 104.14 ppm in gas phase and 105.52 ppm
in solution chloroform (Table 1). The C≡N stretching
vibrations of precursor dicyano groups at 2204 cm-1
According to Koopmans’ theorem [49], ionization
potential and electron affinity of a species can be defined
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Y. BAYGU ET AL.
Fig. 3. The correlation graphs between the experimental and calculated 13C and 1H chemical shifts for compound 6 calculated by
using B3LYP/6-31G(d, p) level in gas phase and chloroform
(a)
(b)
(c)
Fig. 4. The molecular electrostatic potential surface map calculated at B3LYP/6-31G (d, p) level of the compounds: (a) Compound
6. (b) MgPz and (c) ZnPz
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SYNTHESIS, CHARACTERIZATION AND COMPUTATIONAL INVESTIGATION OF NOVEL METALLOPORPHYRAZINES
9
HOMO
LUMO
Fig. 5. The HOMO and LUMO energies for compound 6 with B3LYP/6-31G (d, p) basis set in gas phase
with respect to frontier molecular orbital energies. These
are as in the following respectively: I = -EHOMO and A =
-ELUMO. Physical and/or chemical characteristics such as
the global hardness m = (I–A)/2, the global softness S =
1/(2h), the electronic chemical potential m = -(I + A)/2 =
-c (c is electronegativity) and the global electrophilicity
index w = m2/(2h) measuring the affinity of species to
attract electrons could be commonly defined with these
quantities [25].
One of the electronic characteristics reflecting the
ability for electrons to jump from the highest occupied to
the lowest unoccupied molecular orbital and the ability
for the species to participate in the chemical reactions to
some extent is the HOMO–LUMO gap. A high chemical
stability is characterized by a large gap value. The
electronic gap values calculated at B3LYP/6-31G (d, p)
level are 3.86 eV for compound 6, 2.20 eV for MgPz
and 2.22 eV for ZnPz as seen in Table 2. The optic gap
values for compound 6, MgPz and ZnPz are 3.79, 1.87
and 1.88 eV, respectively. At the same time, these energy
Fig.6. The UV-vis spectra of MgPz and ZnPz (1 × 10-5 M in
chloroform)
gap values are indicators of the existence of charge
transfer in the molecules.
The high electron density is mostly localized on the N
atom as can be seen in Figs 5 and 7. Also, the calculated
self-consistent field (SCF) energies of compound 6, MgPz
and ZnPz are calculated to be -1867.355, -7669.8215
and -9248.8154 a.u., respectively. Associated with partial
charge and electronegativity plots, the electrostatic
potential map demonstrates the distribution of charge of
compounds in terms of the difference between positive
and negative charge [33]. The shape and electrostatic
potential values are shown by the electrostatic potential
map of the surface presented in molecular size. Different
colors on the surfaces represent different values of
electrostatic potentials. While the regions carrying the
most electronegative potentials. i.e. electron rich regions
are represented by the color red, regions of most positive
potentials. i.e. electron-poor regions are represented by
the color blue. Moreover, zero potential is represented by
the color green. The following order shows the increase
of the aforementioned potentials: red < orange < yellow <
green < blue. The darkest blue region means the strongest
attraction whereas the darkest red means the strongest
repulsion. However, the negative (red) regions represent
the electrophilic reactivity and the positive (blue) regions
represent nucleophilic reactivity.
The electrostatic potential map of compound 6,
MgPz and ZnPz changes are reported in Fig. 4. In the
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Y. BAYGU ET AL.
Fig. 7. The HOMO and LUMO energies for MgPz and ZnPz with B3LYP/6-31G (d, p) basis set in gas phase
Table 2. Electronic parameters calculated at B3LYP/6-31 G (d, p) level of the compounds
Electronic parameters
Gas Phase
MgPz
Chloroform
MgPz
Compound 6
ZnPz
Compound 6
ZnPz
HOMO (eV)
LUMO (eV)
DELUMO–HOMO (eV)
TD (DELUMO–HOMO) (eV)
I (eV)
-6.26
-2.40
3.86
-5.77
-3.57
2.20
-5.78
-3.55
2.22
-6.27
-2.56
3.72
-5.71
-3.47
2.24
-5.72
-3.47
2.26
3.79
1.87
1.88
3.60
1.91
1.92
6.26
5.77
5.78
6.27
5.71
5.72
A (eV)
2.40
3.57
3.55
2.56
3.47
3.47
c (eV)
4.33
4.67
4.67
4.41
4.59
4.60
Hardness (h) (eV)
1.93
1.10
1.11
1.86
1.12
1.13
-1
Softness (S) (eV )
0.52
0.91
0.90
0.54
0.89
0.89
m (eV)
-4.33
4.85
-4.67
9.90
-4.67
9.80
-4.41
5.24
-4.59
9.41
-4.60
9.35
w (eV)
Wave length (nm)
Oscillator strength (fos)
350.97
0.1522
661.32
0.051
660.21
0.028
344.8
0.3213
647.84
0.2009
646.96
0.1201
electrostatic potential map of MgPz, the electrophilic
reactivities at -4.0e–2a.u. and nucleophilic reactivities at
8.0e–2a.u. are starting to become active. Similarly, for
the ZnPz is starting to become active the nucleophilic
reactivitiesat-4.135e–2a.u.andelectrophilicreactivitiesat
4.135e–2a.u. The MgPz complex is seen to be planar and
more stable than ZnPz complex. The energy optic gaps of
MgPz(DELUMO–HOMO = 1.88 eV) andZnPz(DELUMO–HOMO
=
1.88 eV) have been calculated to be significantly
smaller than compound 6 (DELUMO–HOMO = 3.79 eV),
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SYNTHESIS, CHARACTERIZATION AND COMPUTATIONAL INVESTIGATION OF NOVEL METALLOPORPHYRAZINES
11
Fig. 8. NBO. (a) MgPz, (b) ZnPz
Fig. 9. ORTEP-3 [3] drawing of the title compound with the atom-numbering Scheme- (Displacement ellipsoids are drawn at the
50% probability level)
which could be attributed to the introduction of electron–
donating sulfur atoms at the positions of porphyrazine.
The HOMO–LUMO value could become smaller than
compound 6, especially when sulfur moieties at the
positions in porphyrazine destabilize the HOMO energy
[50]. LUMO electrons are mostly localized on double-
and triple-bonded groups like C=C and C≡N as shown
in Fig. 5 for compound 6. In addition, it is seen that the
HOMO electrons are mostly localized on the aromatic
and thia ether groups whereas the LUMO electrons of
MgPz (Fig. 7) are mostly localized on C–N moieties,
but the HOMO electrons are mostly localized on carbon
and sulfur atoms which are linked with pyrrole units.
The other electronic properties of the molecules are also
given in Table 2.
For the MgPz compound as seen from Fig. 8a, the
electron–donations from LP1 (N9), LP1 (N10), LP1
(N36) and LP1 (N52) to the antibonding acceptor
s*(C8–N57), s*(N54–C58), s*(C5–N54), s*(C34–
N56), s*(C35–N56), s*(N55–C59), s*(N55–C60)
and s*(N57–C173), respectively, have 14.79 kcal/mol
and give the structure a strong stabilization. In the
s*(C8–N57), s*(N54–C58), s*(C5–N54), s*(C34–
N56), s*(C35–N56), s*(N55–C59), s*(N55–C60) and
s*(N57–C173) bonds, hybrids of the C and N atoms and
bonds, gain 23.91% in s character 76.02% in p character
(with hybrid orbital sp3.18). Similarly, for the ZnPz
compound (Fig. 8b), LP1 (N9), LP1 (N10), LP1 (N36)
and LP1 (N52) to the antibonding acceptor s*(C8–
N56), s*(N53–C57), s*(C5–N53), s*(C34–N55),
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Y. BAYGU ET AL.
Table 3. Crystallographic data
X-ray structure
Empirical formula
Color/shape
Formula weight
T (K)
C21H18N2 O2S2
colorless/plate
349.649
X-ray structural determination of the title compound
confirms the assignments of its structure from spectro-
scopic data (Table 3). The molecular structure, along with
the atom-numbering scheme, is depicted in Fig. 9, and
the bond lengths and angles are within normal ranges.
The selected bond lengths, bond angles and torsion
angles and the hydrogen-bond geometry are given in
Table S5. The average C–S bond lengths and C–S–C
bond angles are 1.782 (6) Å and 102.6 (3)° (Fig. S5),
respectively. The ligand cavities may play important
roles in the complexations and metal-ion selectivities.
173 (2)
Radiation used. graphite monochr. Mo Ka (l = 0.71073 Å)
Crystal system
monoclinic
P 21
Space group
a (Å)
4.8060 (5)
20.026 (3)
9.9467 (12)
90
b (Å)
…
…
The intramolecular S1 O2 (5.180 (3) Å). S1 C12
c (Å)
…
…
(5.899 (3) Å). S1 C11 (5.712 (3) Å). S1 C13 (5.707
a (°)
…
…
(3) Å). S1 C18 (5.534 (3) Å). C4 C18 (6.184 (3) Å)
b (°)
96.773 (7)
90
…
…
C9 C18 (6.161 (4) Å) and C9 C19 (6.051 (4) Å
distances may indicate the hole sizes of the rings. The
planar rings A (C4–C9) and B (C13–C18) are oriented
at a dihedral angle of A/B = 78.69 (22)°. In the crystal
structure, the molecules are stacked along the a-axis and
elongated along the b-axis (Table S5, Fig. S19).
g (°)
V (Å3)
4062.07 (14)
8
Z
Absorption coefficient (mm-1)
0.299
r
calc (mg mm-3)
1.378
Table S1 reports for the first time the selected X-ray
data and the theoretical bond lengths, bond angles and
torsion angles belonging to the compound 6 and MgPz
computed via B3LYP/6-31G (d, p). These computed
values help to understand the molecular structure of
compound 6 and MgPz. For instance, the mean bond
length of the N–C is measured as 1.141 Å, while it is
computed as 1.165 Å for compound 6, and 1.336 Å for
MgPz at the B3LYP/6-31G (d) level. Additionally, the
mean length value of the S–C is measured as 1.742 Å
while it is computed as 1.84 Å for compound 6, 1.82 Å
for MgPz and 1.82 Å for ZnPz at B3LYP/6-31G (d, p)
level. The mean bond angle of the C–S–C is measured
as 102.6°, it is 102.2° for compound 6, 104.4° for MgPz
and 104.5° for ZnPz at B3LYP/6-31G (d, p) level. The
mean bond angle of the C–C–C is measured to be 115.4°,
while it is calculated to be 114.9° for compound 6, 105.3°
for ZnPz and 105.3° for MgPz. The mean bond angle of
the N–C–C is measured to be 177.7° whereas it is 177.9°
for compound 6, 124.9° for pyrrolic (aromatic) in MgPz
and 123.9° for pyrrolic in ZnPz. As a result, it is seen
that there is compatibility between experimental and
theoretical results for characterizing the compounds.
Crystal dimensions (mm)
q (Max.) (o)
q (Min.) (o)
0.09 × 0.19 × 0.24
26.73
2.03
Reflections measured
7667
Range of h. k. l
-6 < h < 6
-16 < k < 25
-10 < l < 12
No. of reflections with I > 2s (I)
Corrections applied
Structure solution
2541
Lorentz-polarization
Direct methods
Geometric calculations
245
Treatment of H atoms
No. of parameters var
Goodness-of-fit S
1.120
R = ||F | – |Fc|||/|F |
0.0862
o
o
Rw
0.2356
Rint
0.0890
(D/r)max (e Å-3)
(D/r)min (e Å-3)
1.016
-1.235
CONCLUSIONS
s*(N54–C58), s*(N54–C59) and s*(N56–C172)
respectively, have 14,96 kcal/mol and 14.97 kcal/mol
strong stabilization energies. Also, in the s*(C8–N56),
s*(N53–C57), s*(C5–N53), s*(C34–N55), s*(N54–
C58), s*(N54–C59) and s*(N56–C172) bonds hybrid
of the C and N atoms and bonds gain 23.96% in s
character 75.94% in p character (with hybrid orbital
sp3.17). These strong stabilization energies indicate the
larger delocalization over the C–N antibonds (see in the
Supplementary information, Tables S3–S4).
In summary, the substituted porphyrazine derivatives
containing 15-membered dioxa-dithia macrocyclic
moieties have been synthesized in good yields.
7.8-dihydro-6H.14H.19H-dibenzo[bj] [1.12.5.8]dioxa-
dithiacyclopentadecine-16.17-dicarbonitrile was used
for the cyclotetramerization reaction in the presence
of M(BuO)2 to obtain metalloporphyrazines. The
porphyrazino-zinc complex has been achieved through a
one-step reaction by using Zn(BuO)2 as template agent
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SYNTHESIS, CHARACTERIZATION AND COMPUTATIONAL INVESTIGATION OF NOVEL METALLOPORPHYRAZINES
13
in this study. Attempts to obtain a metal-free derivative of
ZnPz could not be achieved. This result could be ascribed
as due to zinc(II) porphyrazine complex being more
stable than its magnesium analogs. In addition, the
optimized conditions for the same reaction steps such
as reduction (2) and iodination (4) reactions have
been significantly achieved. 15-membered dioxa-thia
macrocycle (6) was synthesized, and the X-ray structure
of this compound showed that it crystallizes in the
monoclinic system with a P21 space group.
The geometry optimization of dioxa-dithia macro-
cycle (6), magnesium and zinc porphyrazines were
also examined by means of the B3LYP method with a
the 6-31G (d, p) basis set. Figure 9 demonstrates the
comparison of such X-ray data as bond lengths, bond
angles and structure concerning macrocyclic compounds
with theoretical results. For the first time, the theoretical
calculation of compound 6, MgPz and ZnPz compounds
obtained at B3LYP/6-31G (d, p) level are reported in
this study. The compatibility between experimental and
theoretical results was identified to characterize the
compounds in question. The HOMO and LUMO orbitals
of compound 6, MgPz and ZnPz were also predicted as
theoretical.
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Acknowledgments
The numerical calculations reported in this paper
were partially performed at TUBITAK ULAKBIM.
High Performance and Grid Computing Center (TRUBA
resources).
Supplementary information
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