Synthesis and characterisation of new porphyrazinato magnesium containing macrobicyclic moieties

Article abstract of DOI:10.1080/10610278.2011.575468

Novel porphyrazinato magnesium (MgPz) containing symmetrically four diaza-tetrathia-macrobicycles on peripheral positions was synthesized by the cyclotetramerisation reaction of 5,8,16,23-tetrathia-1,12-diazabicyclo[9.7. 7Spentacosane-6-en-6,7-dicarbodini

Full text of DOI:10.1080/10610278.2011.575468

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Synthesis and characterisation of new porphyrazinato
magnesium containing macrobicyclic moieties
Nilgün Kabay a & Yaşar Gök a
a Department of Chemistry, Pamukkale University, Kinikli-Denizli, Turkey
Version of record first published: 01 Jun 2011.
To cite this article: Nilgün Kabay & Yaşar Gök (2011): Synthesis and characterisation of new porphyrazinato magnesium
containing macrobicyclic moieties, Supramolecular Chemistry, 23:8, 587-592
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Supramolecular Chemistry
Vol. 23, No. 8, August 2011, 587–592
Synthesis and characterisation of new porphyrazinato magnesium containing
macrobicyclic moieties
¨
Nilgu¨n Kabay and Yas¸ar Gok*
Department of Chemistry, Pamukkale University, Kinikli-Denizli, Turkey
(Received 17 January 2011; final version received 21 March 2011)
Novel porphyrazinato magnesium (MgPz) containing symmetrically four diaza-tetrathia-macrobicycles on peripheral
positions was synthesized by the cyclotetramerisation reaction of 5,8,16,23-tetrathia-1,12-diazabicyclo[9.7.7]pentacosane-
6-en-6,7-dicarbodinitril (9), which was prepared by sequence reaction of N-tosyl-bis[3-bis(tosyloxypropyl)] amine (1) and
disodium cis-1,2-dicyano-1,2-ethylenedithiolate (8). Elemental analysis, IR, NMR, MS and UV–vis data confirmed the
ability of bulky cryptand moieties to induce steric isolation of Pz core in the solid state.
Keywords: cryptand; macrocyclisation; porphyrazine; magnesium complex; template effect
Introduction
azines (11). In addition, the attachment of oxacrown,
azacrown or polyaza–polythia macrocycles to porphyr-
azine has received considerable attention as they are
suitable for enhancing cation selectivity, cation binding
capability and complex stability through changing the
numbers and types of macrocycle donors (12).
Porphyrinic macrocycles are the subject of great interest in
many directions such as industrial dyes and pigments,
growth of micro-organisms (1), electrocatalysts (2),
electrochromic displays (3), photodynamic therapy (4),
chemical sensors, Langmuir–Blodgett films, liquid
crystals and non-linear optics, including their applications
in material science (5). Porphyrazines are similar to
phthalocyanines so they can also be used in similar
applications as phthalocyanines. In contrast, the simi-
larities, prophyrazines and their derivatives such as amino-
porphyrazines, porphyrazinols and porphyrazinethiolates
have been less studied since their first synthesis, which
took place almost 60 years ago (6). Recently, a variety of
porphyrazines have been obtained, which show interesting
and novel physico-chemical properties, including fluor-
escence and inter-system crossing properties (7). Porphyr-
Cryptands are formed by linking two units together
through two bridges and consist of three cavities containing
two lateral circular cavities as in central cavity. A very active
currentresearchactivityinthisarealedtothedevelopmentof
numerousproceduresforeffectingmacrobicylisationsuchas
template effects and high dilution techniques (13). These
kinds of compounds show extraordinary solubility in
common organic solvents and selectivity towards alkali
and alkaline earth metal cations leading to complexation in
aqueous and organic solutions (14).
Our studies on porphyrazine systems carrying
peripherally mixed donor such as sulphur or nitrogen
macrocycles have been extensively directed towards the
synthesis and characterisation of novel porphyrazine
macrocycles (15). Herein, we report the first synthesis of
porphyrazinato magnesium (MgPz) bearing macrobicyclic
substituents in peripheral positions.
¨
azine derivatives, which contain soft S donor atoms, play
an important role in affecting the solid–state interactions.
The first synthesis of crown-fused porphyrazines has been
reported by group Hoffman and Nolte (8). The
coordination chemistry, agregation and electrical proper-
ties of these compounds have been investigated (9). Dithia-
crowned porphyrazine offers an advantage over its
phthalocyanine counterparts in which two S atoms
in each crown moiety are in direct conjugation with 18
p-electron core of the porphyrazine (10).
Experimental
General
A significant disadvantage of porphyrazines is their
low solubility in common organic solvents. This
disadvantage can be abolished by connecting bulky or
long chain groups such as alkyl, alkoxy, sulfo and
macrocyclic units with the peripheral sides of porphyr-
All reactions were performed using oven-dried glassware
1
under argon atmosphere. H and 13C NMR spectra were
determined on a Varian Mercury 200-NMR spectrometer.
Chemical shifts for 1H NMR are reported in parts per million
and calibrated to TMS. Infrared spectra were recorded in
*Corresponding author. Email: gyasar@pau.edu.tr
ISSN 1061-0278 print/ISSN 1029-0478 online
q 2011 Taylor & Francis
DOI: 10.1080/10610278.2011.575468
http://www.informaworld.com

¨
N. Kabay and Y. Gok
588
Perkin–Elmer Spectrum One spectrometer. Mass spectra
were measured on micrOTOF (Bruker, Massachusetts,
USA) and Micromass Quattro Ultima LC-MS/MS spec-
trometers. The elemental analyses were performed on a
Costech ECS 4010 instrument. UV–vis spectra were
measured using Shimadzu UV-1601 spectrophotometer.
Melting points were determined on an electrothermal
apparatus and are uncorrected. N-Tosylbis[3-(tosyloxy)pro-
pyl)]amine (16) and 1,10-diiodo-5,6-dicyano-4,7-dithia-6-
decene (17) were prepared according to the methods
described in the literature. Other reagents were commer-
cially available and were used without further purification
unless otherwise noted. All solvents were dried and purified
according to the standard procedure before use (18).
(50 MHz, CDCl3): d 143.89 (ArCH), 135.98 (ArCH),
130.09 (ArCH), 127.49 (ArCH), 48.16 (Br–CH2), 32.23
(NCH2), 30.54 (CH2), 21.78 (CH3). Elemental anal. calcd:
C, 37.77; H, 4.60; N, 3.39. Found: C, 37.87; H, 4.73; N,
3.21.MS (ES): m/z 414.[M þ 1]þ, 436 [M þ Na]þ.
Synthesis of N-tosylbis(3-thioacetoxypropyl)amine (4)
To a solution of 3 (3.10 g, 8 mmol) in a mixture of
dichloromethane:acetonitrile (100 ml, 1:1) solid potassium
thioacetate (3.66 g, 32 mmol) was added and stirred at
408C for 72 h. The reaction mixture was monitored by
TLC [alumina (chloroform:hexane) (95:5)]. At the end of
this period, the oily product was filtered off, washed with
dichloromethane and then evaporated to dryness under
reduced pressure. Pale brown oily product chromato-
graphed on alumina column [(chloroform:hexane) (95:5)]
gave 4 as a viscous pale brown oil. Yield 68%, 2.2 g. FT-IR
(NaCl disc, cm21): 3038, 2927–2870, 1694, 1598, 1451,
1340, 1158, 959, 816, 727, 922.1H NMR (200 MHz,
CDCl3): d 7.65 (d, 2H, ArCH), 7.35 (d, 2H, ArCH), 3.18
(m, 4H, N–CH2), 2.90 (m, 4H, S–CH2), 2.42 (s, 3H, CH3),
2.18 (s, 6H, CH3), 1.82 (m, 4H, CH2). 13C NMR (50 MHz,
CDCl3): d 195.55 (CvO), 143.47 (ArCH), 135.09
(ArCH), 47.45 (N–CH2), 30.44 (S–CH2), 28.74 (CH2),
26.49 (C–CH3), 21.49 (CH3). Elemental anal. calcd: C,
50.62; H, 6.20; N, 3.47. Found: C, 50.47; H, 6.35; N,
3.67.MS (ES): m/z 404 [M þ 1]þ, 421 [M þ H2O]þ.
Synthesis
Synthesis of N-tosylbis(3-iodopropyl)amine (2)
A solution of 1 (3.93 g, 6.6 mmol) in dry acetone (25 ml)
was added to a solution of dry NaI (6 g, 40 mmol) in dry
acetone (60 ml) in a round-bottom two-necked flask under
argon atmosphere. The reaction mixture was refluxed and
stirred for 3 h. The reaction was monitored by a thin layer
chromatography (TLC) [silica gel (chloroform)]. At the
end of this period, the reaction mixture was filtered off,
washed with dry acetone and then evaporated to dryness
under reduced pressure. The pale yellow crude product
was crystallised from methanol. Yield 81%, 2.74 g; mp
84–858C. FT-IR (KBr disc, cm21): 3033, 2932–2863,
1595, 1455, 1336, 1162, 913, 715, 653, 575.1H NMR
(200 MHz, CDCl3): d 7.71 (d, 2H, ArCH), 7.38 (m, 2H,
Ar–CH), 3.18 (m, 8H, I–CH2, N–CH2), 2.40 (s, 3H,
CH3), 2.10 (m, 4H, CH2). 13C NMR (50 MHz, CDCl3): d
141.32 (ArCH), 133.49 (ArCH), 127.54 (ArCH), 124.90
(ArCH), 47.49 (I–CH2), 30.29 (NCH2), 29.27 (CH2),
19.24 (CH3). Elemental anal. calcd: C, 30.77; H, 3.75, N,
2.76. Found: C, 30.88; H, 3.60; N, 2.84.MS (ES): m/z:508
[M þ 1]þ, 530 [M þ Na]þ.
Synthesis of N-tosylbis(3-mercaptopropyl)amine (5)
Concentrated HCl (7 ml) was added to a solution of 4
(1.6 g, 3.97 mmol) in dry ethanol (70 ml) while refluxed
and stirred under argon atmosphere for 24 h and then
evaporated to dryness under reduced pressure. The yellow
crude product was dissolved in chloroform, washed with
water and dried over MgSO4 and then evaporated to
dryness. The product 5 was obtained as a white crystalline
waxy solid. Yield 90%, 1.1 g. FT-IR (NaCl disc, cm21):
3030, 2929–2866, 2571, 1598, 1457, 1337, 1157, 1090,
1
960, 815; H NMR (200 MHz, CDCl3): d 7.57 (d, 2H,
Synthesis of N-tosylbis(3-bromopropyl)amine (3)
ArCH), 7.24 (d, 2H, ArCH), 3.10 (m, 4H, N–CH2), 2.45
(m, 4H, S–CH2), 2.32 (s, 3H, CH3), 1.74 (m, 4H, CH2),
1.42 (s, 2H, SH); 13C NMR (50 MHz, CDCl3): d 142.95
(ArCH), 135.61 (ArCH), 46.88 (N–CH2), 32.42 (S–CH2),
28.85 (CH2), 21.80 (CH3). Elemental anal. calcd: C, 48.90;
H, 6.58; N, 4.39. Found: C, 49.17; H, 6.42; N, 4.60.MS
(ES): m/z 320 [M þ 1]þ.
Dry NaBr (8.47 g, 82 mmol) was added to a solution of 1
(9.57 g, 16 mmol) in dry DMF(60 ml) under argon
atmosphere. The reaction mixture was stirred in an oil
bath at 1208C for 5.5 h. The viscous product was poured
into a rapidly stirred ice–water mixture (350 ml, 1:1). The
white solid product was filtered off, washed with cold
water and dried in vacuo over P2O5. The white crude
product was crystallised from methanol. Yield 77%,
5.09 g; mp 79–808C. FT-IR (KBr disc, cm21): 3032,
2940–2870, 1596, 1491, 1457, 1337, 1158, 909, 720, 653,
Synthesis of N,N0-bistosyl-4,11-diaza,1,9-
dithiacyclohexadecane (6)
1
571. H NMR (200 MHz, CDCl3): d 7.75 (d, 2H, ArCH),
7.36 (m, 2H, ArCH), 3.42 (q, 4H, Br–CH2), 3.22 (q, 4H,
N–CH2), 2.42 (s, 3H, CH3), 2.14 (m, 4H, CH2). 13C NMR
A solution of 2 (1.27 g, 2.5 mmol) in dry DMF (50 ml) and
5 (0.8 g, 2.5 mmol) in dry DMF (50 ml) was added under

Supramolecular Chemistry
589
argon atmosphere over a period of 20 h to a stirred
suspension of pre-dried Cs2CO3 (2.96 g, 9.1 mmol) in dry
DMF (250 ml) at 308C. The reaction mixture was stirred at
this temperature for 10 h. The DMF was removed under
reduced pressure and the residue dissolved with chloro-
form. The organic phase was washed with water
(30 ml £ 3) and dried over MgSO4 and then evaporated
under reduced pressure to give a white solid product. The
white crude product was crystallised from methanol. Yield
77%, 1.1 g; mp 183–1848C. FT-IR (KBr disc, cm21):
3031, 2948–2871, 1598, 1460, 1332, 1155, 1091, 929,
TLC [hexzane:chloroform (2:3)]. At the end of this period,
the reaction mixture was filtered off, washed with dry
acetonitrile and evaporated to dryness under reduced
pressure. The oily crude product was dissolved in
chloroform and filtered over Celite and then evaporated
to dryness, yielding a dark brown oil that was purified by
column chromatography [silica gel (hexane:chloroform)
(2:3)]. Yield 62%, 1.51 g. FT-IR (NaCl disc, cm21): 2951–
2810, 2206, 1565, 1461, 1439, 1376, 1278, 1235, 1172,
1113, 1044, 813. 1H NMR (200 MHz, CDCl3): d 3.41 (m,
4H, NCH2), 2.80 (m, 4H, NCH2), 2.42 (m, 12H, SCH2),
2.35 (m, 4H, CH2), 1.80 (m, 8H, CH2). 13C NMR (50 MHz,
CDCl3): d 121.70 (CvC), 112.79 (CuN), 56.06 (N–
CH2), 55.17 (N–CH2), 38.71 (SZCv), 30.06 (SCH2),
28.51 (CH2), 27.26 (CH2). Elemental anal. calcd: C, 54.54;
H, 7.44; N, 11.57. Found: C, 54.85; H, 7.09; N, 11.21.MS
(ES): m/z 485 [M þ 1]þ.
1
814, 728. H NMR (200 MHz, CDCl3): d 7.70 (d, 4H,
ArCH), 7.32 (d, 4H, Ar–CH), 3.18 (m, 8H, N–CH2),
2.58–2.45 (m, 8H, S–CH2), 2.41 (s, 6H, CH3), 1.95 (m,
8H, CH2). 13C NMR (50 MHz, CDCl3): d 143.91 (ArCH),
135.72 (ArCH), 130.01 (ArCH), 127.15 (ArCH), 49.45
(N–CH2), 30.18 (S–CH2), 29.10 (CH2), 21.65 (CH3).
Elemental anal. calcd: C, 54.74; H, 6.67; N, 4.91. Found:
C, 54.50; H, 6.52; N, 5.10.MS (ES): m/z: 571 [M þ 1]þ.
Synthesis of MgPz
Magnesium turnings (0.02 g, 0.83 mmol) and a small
crystal of I2 were added to dry n-butanol (10 ml) under
argon atmosphere in a Schlenk tube. The mixture was
refluxed and stirred until the magnesium had completely
reacted to form a suspension of magnesium butoxide within
248C. A solution of 9 (0.63 g, 1.3 mmol) in dry n-butanol
(5 ml) was added to the refluxing suspension. After 24 h, the
reaction mixture was filtered while hot. The dark green
product was purified by column chromatography technique
[silica gel (chloroform:methanol) (95:5)]. Yield 17%,
0.42 g; mp . 3008C. FT-IR (KBr disc, cm21): 2963–2910,
Synthesis of 5,13-diaza-1,9-dithiacyclohexadecane (7)
Compound 6 (2.12 g, 3.68 mmol) was added slowly to a
stirred suspension of LiAlH4 (1.64 g, 43.2 mmol) in dry of
THF (175 ml) under argon atmosphere. After the addition
all the reactants, the mixture was stirred under reflux for
72 h. At the end of this period, the reaction mixture was
cooled to room temperature, the excess LiAlH4 was
destroyed by dropwise addition of 75 ml of THF–H2O
mixture (2:1). The reaction mixture was filtered over
Celite and the precipitate was carefully washed with a little
CH2Cl2. The filtrate was evaporated to dryness under
reduced pressure to give a white crystalline waxy solid.
Yield 71%, 0.69 g. FT-IR (NaCl disc, cm21): 3268, 2925–
2825, 1474, 1448, 1361, 1262, 1094, 1103, 1053, 936, 839,
1
1632, 1251, 1096, 1022, 864, 801. H NMR (200 MHz,
CDCl3): d 3.55 (m, 48H, NCH2), 3.12 (m, 48H, SCH2), 2.55
(m, 24H, CH2), 2.07 (m, 24H, CH2) UV–vis. l (nm) [1025
1 (mol21 cm21)]: 675 (4.39), 616 (4.00), 506 (3.82), 365
(4.49), 344 (4.50), 245 (4.88). Elemental anal. calcd: C,
53.88; H, 7.35; N, 11.43.Found: C, 53.39; H, 6.99; N,
11.05.MS (ES): m/z 2038.4 [M þ 2K]þ.
1
805. H NMR (200 MHz, CDCl3): d 2.80–2.55 (m, 16H,
S–CH2 and N–CH2), 1.82 (q, 8H, ZCH2Z), 1.51 (s, 2H,
NH). 13C NMR (50 MHz, CDCl3): d 46.58 (N–CH2),
29.02 (S–CH2), 28.31 (CH2). Elemental anal. calcd: C,
54.96; H, 9.92; N, 10.69. Found: C, 55.25; H, 9.74; N,
10.96.MS (ES): m/z 263.16 [M þ 1]þ.
Results and discussion
The synthetic routes related to compounds 1–9 and MgPz
are summarised in Scheme 1. In this work, we reported the
synthesis and structural properties of novel MgPz(II).
According to Scheme 1, N-tosylbis(3-iodopropyl)amine 2
and N-tosyl-bis(3-bromo-propyl) amine 3 were syn-
thesized in yields of 81.1 and 77.2%, respectively. Starting
from 3, N-tosylbis(3-thioacetoxypropyl)amine 4 was
prepared in 68.1% yield by the reaction of 3 and
potassiumthioacetate, and then hydrolysed with concen-
trated HCl that afforded compound 5 in 90.12% yield.
These compounds were characterised by their spectro-
Synthesis of 5,8,16,24-tetrathia-1,12-
diazabicyclo[10.7.7]oktakos-6-en-6,7-dicarbodinitrile (9)
A round-bottom two-necked flask (500 ml) containing pre-
dried Cs2CO3 (4.90 g, 15.0 mmol) in dry acetonitrile
(100 ml) and fitted with a condenser was evacuated,
refilled three times with argon and connected to a vacuum
line. Under inert conditions, the flask was charged with
compound 7 (1.31 g, 5.0 mmol) at room temperature. A
solution of 8 (2.38 g, 5.0 mmol) in dry acetonitrile (100 ml)
was added to this mixture and the reaction mixture was
stirred at 358C for 72 h. The reaction was monitored by
1
scopic and analytical data. In the H NMR spectrum of
2–5, characteristic signals concerning I–CH2, Br–CH2,

¨
N. Kabay and Y. Gok
590
OTos
OTos
Br
Br
SCOCH3
SCOCH3
SH
SH
ii
iii
iv
Tos-N
Tos-N
Tos-N
Tos-N
4
1
3
5
i
I
I
SH
SH
S
S
Tos
H
v
vi
N
Tos-N
+
N
Tos-N
N
N
Tos
H
S
S
2
6
5
7
N
S
S
S
N
N
S
S
S
N
N
S
S
S
S
I
N
N
N
N
S
N
CN
CN
CN
CN
vii
viii
Mg
N
N
N
S
7
+
S
N
S
I
S
S
S
N
S
S
S
N
S
N
N
9
8
MgPz
Scheme 1. (i) NaI/aceton; (ii) NaBr/DMF; (iii) KSCOCH3/CH2Cl2:CH3CN; (iv) %37 HCl/ethanol; (v) Cs2CO3/DMF; (vi)
LiAlH4/THF; (vii) Cs2CO3/DMF and (viii) Mg/n–butanol/I2.
S–CH2, CH2, SH, CH3 and tosyl groups were observed at
d ¼ 3.18, 3.42, 2.90–2.45, 2.14–1.74, 1.42 and 2.32 ppm,
respectively, as expected. Proton-decouplet 13C NMR
spectral data of the same compounds indicated the
presence of related carbon atoms. The presence of new
signals at d ¼ 195.55 ppm (4) due to CvO groups also
supported the formation of proposed compound. In the MS
spectra of these compounds, the presence of characteristic
molecular ion peaks confirmed the formation of 2–5.
Treatment of 2 with N-tosylbis(3-thiopropyl)amine (5) in
dry DMF in the presence of Cs2CO3 resulted in the
formation of desired diazadithiamacrocycle 6 in 77%
yield, which was confirmed by IR, NMR, MS spectra and
elemental analysis data. It was found that 1H NMR
spectrum of 6 clearly showed the characteristic emerged
signals for the 16-membered macrocycle at d ¼ 3.18, 2.58,
1.95 and 2.41 ppm concerning N, S connected methylene,
bridging methylene groups and methyl protons, respect-
ively. Compound 6 contained two tosyl moieties and was
substantiated by two characteristic doublets at d ¼ 7.70
and 7.32 ppm as expected. Characteristic signals of the 13
C
NMR spectrum of the same compound were similar to
those of the precursor compounds 2 and 4. In the MS
spectrum of this compound, a peak corresponding to
[M þ 1]þ at m/z ¼ 571 was in good accord with the
suggested structure. Detosylation of 6 performed a
reductive detosylation by using LiAlH4 to minimise the
cleavage of the thioether functional groups (19). The
preparation of 7 was first carried out by Kaden and then by
Lindoy et al. (20). Alternatively, the unsubstituted
macrocycle 7 was synthesized in 71% yield by detosyla-
tion reaction of 6 with excess LiAlH4. After the removal of
the tosyl groups from 6, two terminal NH groups were
1
observed in the H NMR spectrum at d ¼ 1.51 ppm as
expected (20). The other proton-NMR signals of 7 closely
resemble those of the precursor compound (6). The proton-
decoupled 13C NMR spectrum of 7 also clearly indicated
the presence of expected signals. The disappearance of the

Supramolecular Chemistry
characteristic signals concerning tosyl groups, along with
591
the appearance of resonances at d ¼ 46.58, 29.02 and
28.31 ppm corresponding to N–CH2, S–CH2 and CH2
carbons, respectively, was in agreement with the proposed
structure. This was also supported by the presence of the
characteristic peak at m/z ¼ 263.16 [M þ 1]þ in the mass
spectrum using the ES technique.
Treatment of 7 with cis-1,2-dicyano-1,12-ethylene
dithiolate (8) in dry MeCN in the presence of excess
amount of Cs2CO3 resulted in the formation of the desired
macrobicycle 9 in 62.2% yield, which was confirmed by
IR, NMR and MS spectra. Compound 8 contained a
conformation of bicycle skeleton and dicyano subunit was
substantiated by characteristic signals at d ¼ 1.80 and
2.42 ppm for the new bridging methylene and SCH2
protons, respectively, in the 1H NMR spectrum. The
bicycle formation was in the proposed structure as
confirmed by its 13C NMR spectrum, in which the
characteristic signals at d ¼ 112.79 and 121.70 ppm for
the CuN and CvC carbons of the macrobicycle moiety
were present, and the other characteristic signals at
d ¼ 27.26 ppm for the bridging methylene carbons were
also present. A diagnostic feature of macrobicycle
formation from compounds 7 and 8 is the appearance of
the sharp intense CuN vibrational bands at 2206 cm21 in
the IR spectrum. Structure of macrobicycle formation 9
was also confirmed by its MS spectrum at 485, in which
the peak corresponding to [M þ 1]þ was observed.
MgPz was obtained as dark green solids from Linstead
macrocyclisation (21) of compound 9 using magnesium
butoxide in n-butanol in 17.2% yield after purification by
column chromatography on silica gel [chloroform:metha-
nol (95:5)]. In the IR spectrum of this compound, a
diagnostic feature of the formation of MgPz from 9 is the
disappearance of the sharp CuN resonances and the
presence of CvN stretching vibrations at 1632 cm21
confirms the formation of MgPz. In the 1H NMR spectrum
of MgPz, the signals relating to N–CH2, S–CH2 and CH2
groups in the macrobicycle moieties gave significant
resonance characteristics of the proposed structure.
The structure of this compound was also confirmed by
its MS spectrum, in which the peak at m/z ¼ 2038.4
corresponding to [M þ 2K]þ was observed.
Figure 1. Electronic absorption spectrum of MgPz
(1.0 £ 1025 M) in CHCl3.
broad p ! p
transition in the range of B-band
*
corresponds to deep p ! p transition from the a1u, a2u
*
HOMOs to the double degenerate LUMOs (10).
Conclusions
In this study, the new MgPz fused with diazatetrathiama-
crobicycles in peripheral positions have been prepared by
bicyclotetramerisation of the newly synthesized dithioma-
leonitrile derivatives of cryptand in the presence of
magnesium butanolate as template agent. MgPz complex
contains symmetrically four large macrobicyclic cavities,
hence it has the potential to be related to supramolecular
areas.
Electronic spectrum of magnesium porphyrazine
(Figure 1) exhibits a Q band at 675 nm, a less broad
band at 506 nm and a Soret region at 365–344 nm. The two
bands in the UV–vis spectrum of MgPz display maxima at
around 675 and 616 nm caused by a p ! p transition of
*
the Pz ring, which is characteristic of tetrapyrrolic
macrocycle with D4h symmetry (9, 22). In agreement
with other peripherally heterosubstituted porphyrazines,
they tentatively assigned the less intense broad peak at
Acknowledgements
This study was supported by the Research Fund of Pamukkale
University, Project number 2008 FBE 002 (Denizli/Turkey). One
506 nm to the n ! p transition from the lone pairs
*
electron on the peripheral sulphur atoms into a p ring
¨
˙
of the authors (N.K.) also thanks TUBITAK (The Scientific and
Technological Research Council of Turkey-ANKARA) for
financial support.
*
orbital concerning inner core. The second intense and

¨
N. Kabay and Y. Gok
592
Jarrell, W.K.; Sibert, J.W.; Armstrong, N.R.; Saavedra, S.S.;
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