Synthesis and spectral study of tetra(2,3-thianaphtheno)-porphyrazine, its tetra-tert-butyl derivative and their Mg(II), Al(III), Ga(III) and In(III) complexes

Article abstract of DOI:10.1142/S1088424611002969

Starting from easily available thiophenols (PhSH (1a), 4-tert-butyl-PhSH (1b)) and oxalylchloride we have prepared 2,3-thianaphtenequinones 2a,b which were then successively converted to thianaphthene-2,3-dicarboxylic acids 4a,b their imides 10a,b, diamides 9a,b and finally to thianaphthene-2,3- dicarbonitriles 11a,b the key precursors for the series of novel porphyrazines bearing four 2,3-annulated thianaphthene moieties. The free-bases 12a,b were obtained by cyclotetramerization of the dinitrile 11a,b in the presence of lithium in n-pentanol, while the reaction with magnesium(II) butoxide in n-butanol leads to the Mg(II) complex 13a. Complexes with Al(III) (14a,b), Ga(III) (14a,b) and In(III) (14a,b) were obtained by the template cyclotetramerization of the dinitriles 11a,b in a melt with the corresponding (hydroxy)acetates. Tetra(2,3-thianaphtheno)porphyrazine 12a and its metal complexes 13a15a are only sparingly soluble in common organic solvents, the solubility is enhanced for their tert-butyl substituted derivatives 12b, 14b16b. The study of the electronic absorbtion spectra has revealed that the extension of the porphyrazine π-chromophore by fusion of four thianaphthene fragments due to the angular type of their annulation (similar to that found in 1,2-naphthalocyanines) and negative inductive effect of the sulfur atoms has an effect on its spectral properties which is less than in the case of the isoelectronic naphthalene rings fusion and is comparable with the influence of four benzene rings in phthalocyanines.

Full text of DOI:10.1142/S1088424611002969

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2011; 15: 54–65
DOI: 10.1142/S1088424611002969
Published at http://www.worldscinet.com/jpp/
Synthesis and spectral study of tetra(2,3-thianaphtheno)-
porphyrazine, its tetra-tert-butyl derivative and their Mg(II),
Al(III), Ga(III) and In(III) complexes
Ekaterina S. Taraymovich*a, Andrey B. Korzhenevskiia,†, Yulia V. Mitasovaa,
Roman S. Kumeevb, Oscar I. Koifmana and Pavel A. Stuzhin*a
a Department of Chemistry and Technology of Macromolecular Compounds, Ivanovo State University of Chemistry
and Technology, Ivanovo 153000, Russia
b Institute of Solution Chemistry, Russian Academy of Science, Ivanovo 153000, Russia
Received 19 October 2010
Accepted 17 December 2010
ABSTRACT: Starting from easily available thiophenols (PhSH (1a), 4-tert-butyl-PhSH (1b)) and
oxalylchloride we have prepared 2,3-thianaphtenequinones 2a,b which were then successively converted
tothianaphthene-2,3-dicarboxylicacids4a,btheirimides10a,b,diamides9a,bandfinallytothianaphthene-
2,3-dicarbonitriles 11a,b — the key precursors for the series of novel porphyrazines bearing four 2,3-
annulated thianaphthene moieties. The free-bases 12a,b were obtained by cyclotetramerization of the
dinitrile 11a,b in the presence of lithium in n-pentanol, while the reaction with magnesium(II) butoxide
in n-butanol leads to the Mg(II) complex 13a. Complexes withAl(III) (14a,b), Ga(III) (14a,b) and In(III)
(14a,b) were obtained by the template cyclotetramerization of the dinitriles 11a,b in a melt with the
corresponding (hydroxy)acetates. Tetra(2,3-thianaphtheno)porphyrazine 12a and its metal complexes
13a–15a are only sparingly soluble in common organic solvents, the solubility is enhanced for their tert-
butyl substituted derivatives 12b, 14b–16b. The study of the electronic absorbtion spectra has revealed
that the extension of the porphyrazine π-chromophore by fusion of four thianaphthene fragments due
to the angular type of their annulation (similar to that found in 1,2-naphthalocyanines) and negative
inductive effect of the sulfur atoms has an effect on its spectral properties which is less than in the case
of the isoelectronic naphthalene rings fusion and is comparable with the influence of four benzene rings
in phthalocyanines.
KEYWORDS: 2,3-thianaphthene derivatives, porphyrazines, tetra(2,3-thianaphtheno)porphyrazines,
magnesium(II), aluminium(III), gallium(III), indium(III), electronic absorbtion spectra.
optical data storage, electrodes in fuel cell, photoelectric
INTRODUCTION
conversion materials and others [4–8]. A great number of
Initially observed as unexpected byproducts [1, 2], now
promising applications of phthalocyanines arise from the
phthalocyanines, [MPc], are produced in million tons per
year [3]. They are one of the major types of tetra-pyrrole
presence of the unique 18π-electron conjugated aromatic
porphyrazine (PA) core which determines their remark-
derivatives showing a wide range of practical applications
able optic and coordination properties and endows them
in various high technology fields such as nonlinear optics,
with high thermal and chemical stability. Useful proper-
photosensitizers, gas sensors, catalysis, liquid crystals,
ties of phthalocyanine materials can be tuned by struc-
tural modification of the periphery of the macrocyclic
*Correspondence to: Ekaterina S. Taraymovich, email:
taraimoviches@bk.ru and Pavel A. Stuzhin, email: stuzhin@
isuct.ru, tel/fax: +7 4932-416693
ligand. Along with introduction of different appendages
in benzene rings of phthalocyanine, the growing attention
is now given to heterocyclic phthalocyanine analogues
containing aromatic heterocycles instead of the benzene
†Deceased.
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SyntheSIS anD SPeCtral StuDy Of tetra(2,3-thIanaPhthenO)POrPhyrazIne
55
Chart 1. Molecular structures of metal phthalocyanines and its heterocyclic and π-extended analogues
rings [9, 10]. Azaanalogues of phthalocyanine containing
6-membered N-heterocycle (pyridine or pyrazine) fused
to the porphyrazine core instead of benzene rings (i.e.
tetrapyrido- and tetrapyrazinoporphyrazines, [MPyPA] and
[MPyzPA]) and their benzohomologues containing qui-
noline and quinoxaline fragments are mostly well studied
[9–13]. In the recent decade considerable advances have
been also achieved in the synthesis and study of the chalco-
gen analogues of pyrazinoporphyrazines containing S or Se
atom instead of the pyrazine C=C bond, i.e. porphyrazines
with annulated 1,2,5-thiadiazole or 1,2,5-selenadiazole
rings [14]. Thiaanalogues of phthalocyanine — porphyra-
zines with fused thiophene rings, [MThPA], which were
first reported by Linstead in 1937 [15], since then have
been only scarcerely studied [16–18]. Linstead and cowork-
ers [15] have also observed formation of thiaanalogues of
naphthalocyanine — upon melting of 2,3-thianaphthenedi-
carbonitrile with metallic reagents (CuCl, Cu, AlCl3, Mg)
green products were obtained. However, these species
were not characterized and, to the best of our knowledge,
since then no reports appeared on tetra(2,3-thianaphtheno)
porphyrazine complexes [MSNc]. In our opinion, such
porphyrazine macrocycles containing “mild” peripheral
S-atoms with accessable d-sublevel might exhibit inter-
esting and unusual properties and deserve more detailed
investigation.
and on the synthesis and characterization of Mg(II),
Al(III), Ga(III) and In(III) complexes. The latter might
be especially interesting for investigation of their non-
linear optical properties, since In(III) complexes of
phthalocyanine and its analogues (porphyrazines, naph-
thalocyanines) often exhibit enhanced performance as
optical limiting materials [19–22].
EXPERIMENTAL
General
All chemicals were commercially available reagent
grade species (Aldrich, Merck, Reakhim, Vecton, Tech-
nolog) and used without further purification otherwise
specified. Solvents such as n-butanol, DMF and pyridine
were distilled before use. Infrared spectra were measured
on IR-spectrometer AVATAR 360 FT-IR in KBr pellets,
UV-vis spectra were recorded with Perkin Elmer spec-
trometer Lambda 20, elemental analyses were performed
on a CHN analyser Flash EA 1112. Mass-spectrometric
measurents were carried out by mass-spectrometer Saturn
2000R (Varian Chrompack) for porphyrazine precursors
and MALDI-TOF Bruker Ultraflex spectrometer for por-
phyrazines. The melting points for porphyrazine precur-
sors were determined using Buchi Melting Point B-540
apparatus.
In this work, we report on the improved preparation of
the precursors for tetra(2,3-thionaphtheno)porphyrazines
Copyright © 2011 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2011; 15: 55–65

56
e.S. taraymOvICh et al.
Preparation of precursors
7.6 g (63%), mp 103–105 °C. Anal. calcd. for C12H12SO2
(%): C, 65.43; H, 5.49; S, 14.56; O, 14.53. Found (%):
C, 64.78; H, 4.88; S, 13.69; O, 13.98. IR (KBr): ν, cm-1
3409s (ν(COOH)), 3072m (ν(CH)Ar), 2964s, 2871m
(ν(CH)tBu), 1708vs (ν(C=O)), 1596s, 1562m, 1477s,
1365m, 1288m, 1257m, 1201m, 1110m, 1004m, 919m,
850m. 1H NMR (CDCl3): δ, ppm 7.84 (1H, m, ArH), 7.69
(1H, m, ArH), 7.39 (1H, m, ArH), 1.33 (9H, s, tBu).
2-oxalylphenylthioglycolic acid [2-(2-carboxy-
methylsulfanylphenyl)-2-oxoacetic acid] (3a). It was
prepared by modification of the earlier reported proce-
dure [25]. Solutions of 2,3-thionaphthenequinone 2a
(5g, 30.5mmol)andchloroaceticacid(2.88g, 30.5mmol)
each in 20 mL of 10% aqueous NaHCO3 were mixed
together, heated for 10–15 min and cooled to 5 °C. Addi-
tion of conc. aqueous HCl leads to precipitation of 3a
as yellow product, which was filtered and dried. Yield
6.95 g (95%), mp 164–168 °C. Anal. calcd. for C10H8SO5
(%): C, 50.00; H, 3.33; S, 13.33; O, 33.3. Found (%):
C, 48.31; H, 3.15; S, 13.65; O, 30.94. IR (KBr): ν, cm-1
3414m (ν(OH)), 1711s (ν(COOH)), 1676s (ν(C=O)),
1612s (ν(C=O)), 1591m, 1554vs, 1522vs, 1493vs,
1458s, 1412s, 1373m, 1333m, 1290s, 1271vs, 1244s,
1142m, 1107s, 1014w, 974m, 891w, 802m, 789s, 762vs,
4-tert-butylbenzenesulfonyl chloride. It was syn-
thesized as described elsewhere [23]. Yield ca. 80%,
mp 78–80 °C (lit. data 79–80 °C [24]). Anal. calcd.
for C10H13SO2Cl (%): C, 51.61; H, 5.63; S, 13.78; O,
13.76. Found (%): C, 49.94; H, 6.10; S, 13.58; O, 13.95.
IR (KBr): ν, cm-1 3070w and 3030w (ν(CH)Ar), 2970s
and 2872m (ν(CH)tBu), 1926w, 1793w, 1664w, 1589s,
1477m, 1462m, 1402s, 1373vs (ν(SO2Cl)), 1298m,
1269m, 1236m, 1201s, 1176vs (ν(SO2Cl)), 1111s,
1080s, 1012m, 835m, 752m, 615s, 575s, 534s. MS: m/z
1
217 (100%, [M]+). H NMR (CDCl3): δ, ppm 8.00 (2H,
m, ArH), 7.60 (2H, m, ArH), 1.36 (9H, s, tBu).
4-tert-butylbenzenethiol (1b). Zinc dust (22 g, 0.336
mol) was added to a mixture of chopped ice (125 g) and
concentrated sulfuric acid (35 mL) under intensive stir-
ring in a three-neck flask. Then 4-tert-butylbenzenesul-
fonyl chloride (15 g, 0.06 mol) was immersed in small
portions. Reaction mixture was stirred for 3 h and then
refluxed 2 h on the water bath. The resulting suspension
was cooled and the product was extracted in chloroform
or ether. Extract was purged with water to neutrality, dried
with CaCl2 and after evaporation of the solvent 4-tert-
butylbenzenethiol was obtained as yellow oil. Yield 9.1 g
(85%), bp 120–122 °C at 20 mmHg (lit. data 112–114 °C
at 15 mmHg [24]).Anal. calcd. for C10H14S (%): C, 72.23;
H, 8.49; S, 19.28. Found (%): C, 71.54; H, 7.99; S, 19.18.
IR (KBr): ν, cm-1 3080w and 3030w (ν(CH)Ar), 2962vs,
2904m and 2868m (ν(CH)tBu), 2550w (ν(SH)), 1492s,
1398m, 1362m, 1267m, 1117s, 990s, 823s, 551m. MS:
1
723s, 689s, 638m, 575m, 480m, 446vs, 426s. H NMR
(DMSO-d6): δ, ppm 3.89 (2H, s, -S-CH2-COOH), 7.36
(1H, t, ArH), 7.49 (1H, d, ArH), 7.67 (1H, t, ArH), 7.79
(1H, dd, ArH).
5-tert-butyl-2-oxalylphenylthioglycolic acid {5-tert-
butyl-2-[(carboxymethyl)thio]phenyl}(oxo)acetic
acid (3b). It was prepared from quinone 2b similarly to
unsubstituted acid 3a. After acidification of the reaction
mixture with aqueous HCl, the product was extracted
with chloroform to give 3b as a ductile yellow liquid.
Yield 8.5 g (83%). Anal. calcd. for C14H16SO5 (%):
C, 56.74; H, 5.44; S, 10.81. Found (%): C, 50.64; H, 5.71;
S,8.85.IR(KBr):ν,cm-1 2964s,2906m,2868w(ν(CH)tBu),
1708vs (ν(C=O)), 1596s, 1477m, 1468m, 1396m,
1363m, 1288m, 1263m, 1207m, 1169m, 1004m, 921m,
1
m/z 166 (45%, [M]+). H NMR (CDCl3): δ, ppm 7.54
(2H, m, ArH), 7.37 (2H, m, ArH), 3.37 (1H, s, -SH), 1.29
(9H, s, tBu).
2,3-thianaphthenequinone
[2,3-dihydrobenzo[b]
thiophene-2,3-dione] (2a). Oxalyl chloride (14.6 mL,
0.144 mol) was added to thiophenol (1a) (15.0 mL, 0.144
mol) under vigorous stirring which was continued till solid-
ification of the reaction mixture. Then carbon disulfide (45
mL) was added, solution was cooled to 0–5 °C and anhy-
drous AlCl3 (38.5 g, 0.288 mol) was immersed in portions
to regulate acylation reaction. Stirring was continued for
further 10 min and then the solvent was evaporated by
heating on a water-bath at 42–45 °C. Dark residue was
mixed with ice and kept overnight. The orange precipitate
was filtered and treated with saturated aqueous NaHCO3
solution. Filtrate was collected and carefully acidified by
concentrated HCl solution until complete precipitation of
the bright orange product (yield 53%), mp 119–121°C.
Anal. calcd. for C8H4SO2 (%): C, 58.54; H, 2.41; S, 19.51;
O, 19.51. Found (%): C, 58.03; H, 2.27; S, 19.95; O,
19.81. IR (KBr): ν, cm-1 1726m, 1714s (ν(C=O)), 1589m,
1468s, 1452m, 1360s, 1342s, 1282s, 1242m, 1147s, 1108s,
1060m, 962m, 843s, 748m, 449m.
1
851m, 585m. H NMR (CDCl3): δ, ppm 8.56 (1H, m,
Ar-H), 8.10 (1H, m, ArH), 7.72–7.54 (1H, m, ArH), 3.73
(2H, s, -S-CH2-COOH), 1.33 (9H, s, tBu).
Thianaphthene-2,3-dicarboxylic acid [benzo[b]
thiophene-2,3-dicarboxylic acid] (4a). It was prepared
by modification of the earlier reported procedure [25].
Acid 3a (6.95 g, 0.029 mol) was dissolved in 30% aque-
ous NaOH solution (30 mL) with heating. After transfor-
mation of the red solution to dense gruel of beige color,
distillated water (40 mL) was added to dissolve the pre-
cipitate. Then the solution was cooled and acidified with
conc. aqueous HCl to precipite the acid 4a which was
filtered and dried. Yield 5.21 g (81%), mp 248–252 °C.
Anal. calcd. for C10H6O4S (222.21) (%): C, 54.05; H,
2.7; S, 14.41; O, 28.83. Found (%): C, 53.21; H, 2.41; S,
13.92; O, 27.45. IR (KBr): ν, cm-1 1675m (ν(COOH)),
1554m, 1492s, 1263s, 1243m, 1106m, 802s, 761m.
5-tert-butyl-2,3-thianaphthenquinone [5-tert-butyl-
2,3-dihydrobenzo[b]thiophene-2,3-dione] (2b). It was
prepared similarly to unsubstituted quinone 2a. Yield
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SyntheSIS anD SPeCtral StuDy Of tetra(2,3-thIanaPhthenO)POrPhyrazIne
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1H NMR (DMSO-d6): δ, ppm 7.45–7.60 (2H, m, ArH),
dinitrile 11a (see characterization details below). Sub-
limation of the insoluble residue gave the imide 10a as
yellow crystals. Yield 2.1 g (39.5%), mp 235–240 °C.
Anal. calcd. for C10H5NO2S (203.21) (%): (C 59.10% H
2.48% N 6.89% O 15.75% S 15.78%). Found (%): (C,
59.73; H, 2.56; N, 7.42, O, 13.11; S, 16.34). IR (KBr):
ν, cm-1 3242s (ν(NH)), 3066m (ν(CH)Ar); 1834m, 1768s
1730s and 1709s (ν(imide), 1597w, 1520m, 1473m,
1429m, 1392m, 1329s, 1306s, 1259m, 1194m, 1173w,
1063m, 1047s, 995s, 947w, 899w, 856w, 841m, 787m,
752s, 721, 665m, 644m, 565m, 519m, 496m, 428s. MS:
m/z 203 (100%, [M]+). 1H NMR (CDCl3): δ, ppm 7.5–7.6
(2H, m, ArH), 7.95–8.00 (1H, m, ArH), 8.2–8.3 (1H, m,
ArH). Remark. The residue obtained after the reaction
of dicarboxylic acid 4a with thionyl chloride is a mix-
ture consisting from anhydride 6a (m/z = 204) and easily
hydrolizable dichloroanhydride 7a (m/z = 259). mp 64
(partly) and 156–159 °C (completely). IR (KBr): ν, cm-1
3579m (ν(OH)), 3082m (ν(CH)Ar), 2093m, 1837vs and
1756vs (ν(-CO-O-CO-)), 1662s, 1633w, 1597s, 1562m,
1522vs, 1470vs, 1419s, 1394s, 1325s, 1267vs, 1218w,
1203w, 1171s, 1149vs, 1118vs, 1049m, 1005s, 960m,
891vs, 831vs, 785vs, 756vs, 731s, 719s, 700s, 661s,
633m, 563m, 513m, 487m, 484m, 426s. Anal. found
(%): C, 53.24; H, 1.77; S, 15.00; O, 17.49. Calcd. (%) for
C10H4SO3 (204.19): C, 58.82; H, 1.96; S, 15.69; O, 23.53;
for C10H4ClSO2 (259.10) C, 46.36; H, 1.56; S, 12.37; O,
12.35. Separation of this mixture is wasteful and it was
used as obtained in further ammonolysis.
5-tert-butylthianaphthene-2,3-dicarboximide [2,3-
dihydro-7-tert-butyl-1H-benzothieno[2,3-c]pyrrole-
1,3(2H)-dione (10b). The synthetic method of substituted
imide is the same as described above for 10a (method
B). Yield 1.5 g (31%), mp 179–181 °C. Anal. calcd. for
C14H13SNO2 (%): C, 64.84; H, 5.05; S, 12.36; N, 5.40;
O, 12.34. Found (%): C, 64.30; H, 5.09; S, 12.13; N,
5.46. IR (KBr): ν, cm-1 3444m, 3211m (ν(NH)), 3058m
(ν(CH)At), 2964m (ν(CH)tBu), 2904m, 2865m, 1765s,
1734vs (ν(C=O)imide), 1637m, 1545w, 1519m, 1459m,
1433m, 1394m, 1357m, 1331m, 1294s, 1255m, 1184m,
1103m, 1068m, 1039m, 997m, 883m, 819m, 740m,
725m, 704m, 681m, 640m, 519m, 451w, 428w. 1H NMR
(CDCl3): δ, ppm 8.20 (1H, s, Ar-H), 8.01 (1H, m, -CO-
NH-CO-), 7.89 (1H, d, ArH), 7.65 (1H, m, ArH), 1.43
(9H, s, tBu).
8.00–8.15 (2H, m, ArH).
5-tert-butylthianaphthene-2,3-dicarboxylic acid [5-
tert-butylbenzo[b]thiophene-2,3-dicarboxylic acid] (4b).
It was prepared similarly to the unsubstituted acid
4a, but the reaction time was increased to 1 h. Yield
5.2 g (65%), mp 132–137 °C with decomposition. Anal.
calcd. for C14H14SO4 (%): C, 60.43; H, 5.07; S, 11.51; O,
22.99. Found (%): C, 58.50; H, 4.87; S, 11.25; O, 20.11.
IR (KBr): ν, cm-1 2965s, 2927m, 2871m (ν(CH)tBu),
2366w, 1841w, 1708vs (ν(COOH)), 1596s, 1562m,
1477s, 1467m, 1413m, 1398m, 1365m, 1299m, 1288m,
1259m, 1207m, 1110m, 1089m, 1047m, 1004m, 921m,
906w, 879w, 850w, 836w, 775w, 755w, 730w, 709w,
690w, 667w, 588w, 543w, 497w, 449w, 418vw. MS: m/z
277 (40%, [M]+). 1H NMR (CDCl3): δ, ppm 7.89 (2H, m,
COOH), 7.70 (1H, m, Ar-H), 7.46 (1H, m, Ar-H), 7.39
(1H, m, Ar-H), 1.33 (9H, s, tBu).
Thianaphthene-2,3-dicarboxylic acid anhydride
[1,3-dihydrobenzo[4,5]thieno[2,3-c]furan-1,3-dione]
(6a). It was obtained following the procedure of Linstead
[15] by refluxing of acid 3a in acetic anhydride for 1 h
with yield ca. 95%, mp 171–173 °C. IR (KBr): ν, cm-1
3088w (ν(CH)arom), 1832vs and 1762vs (ν(-CO-O-CO-)),
1597m, 1563m, 1522s, 1470s, 1419m, 1394m, 1324m,
1267s, 1170m, 1151s, 1119s, 1050m, 1006m, 961w,
890s, 830s, 785s, 757s, 719s, 700m, 661m, 632m, 563m,
492m, 425m. Anal. calcd. for C10H5O3S (204.19) (%):
C, 58.82; H, 1.96; S, 15.69; O, 23.53. Found (%): C,
57.91; H, 1.68; S, 14.18; O, 21.82.
Thianaphthene-2,3-dicarboximide
[2,3-dihydro-
1H-benzo[4,5]thieno[2,3-c]pyrrole-1,3-dione] (10a).
Method A. Dry NH3 was bubbled through a stirred solu-
tion of the anhydride 6a (2 g, 0.01 mol) in CHCl3 for
2–3 h at room temperature. This leads to precipitation of
amidoacids 8a, which were filtered, dried, dissolved in
DMF (10 mL) and treated with POCl3 (2.6 mL, 0.03 mol)
in an ice bath overnight. The precipitate formed after
pouring of the reaction mixture into water was filtered,
dried and sublimed to give 0.98 g of the imide 10a
(yield ca. 50%). Method B. Dicarboxylic acid 4b (5.79 g,
0.0261 mol) was refluxed with thionyl chloride (40 mL,
0.56 mol) for 6 h. Excess SOCl2 was removed under
reduced pressure, the residue (see remark below) was
dissolved in chloroform (40 mL) and dry ammonia gas
was bubbled through the solution for 2–3 h. The obtained
suspension was kept in a closed flask overnight. The
precipitate containing a mixture of amidoacids 8a and
diamide 9a (mp 178–192 °C, yield 3.1 g, 54%) was fil-
tered, dried and dissolved in DMF (20 mL). The solu-
tion was cooled in an ice bath to 0–5 °C and POCl3
(5.14 mL, 0.056 mol) was added in portions to keep the
temperature at 5–7 °C. The stirring of the reaction mix-
ture was continued for another 3 h and then it was left
overnight. Precipitate formed upon pouring of the reac-
tion mixture on ice was filtered, dried and washed with
CHCl3. Evaporation of the extract gave 0.48 g (10%) of
Thianaphthene-2,3-dicarboxylic acid diamides (9).
[Benzo[b]thiophene-2,3-dicarboxamides] (9a). Imide
10a or 10b (3.69 mmol) was suspended in the saturated
ammonia solution (0.88 g/cm3, 30–40 mL). On the next
day, the white precipitate of diamides 9a or 9b was fil-
tered and dried. Diamide 9a. Yield 0.68 g (84%), mp
221–225 °C (lit. mp 204–205 °C [15]). Anal. calcd. for
C10H8N2O2S (220.24) (%): C, 54.54; H, 3.64; S, 14.55;
N, 12.73. Found (%): C, 54.84; H, 3.35; S, 14.61; N,
11.65. IR (KBr): ν, cm-1 3381s and 3269m (ν(NH2)),
3059w (ν(CH)Ar), 1668vs and 1616s (ν(C=O)amide), 1567s,
1519m, 1456w, 1404s, 1381w, 1313m, 1252w, 1147m,
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58
e.S. taraymOvICh et al.
1117m, 1103m, 1051m, 937m, 881m, 800m, 733s, 704s,
667s,648s,636s,471m,434m,407m.1HNMR(DMSO-d6):
δ, ppm 8.37 (2H, s, CONH2), 8.18 (2H, s, CONH2), 8.0–
8.1 (1H, m, ArH), 7.9–8.0 (1H, m, ArH), 7.45–7.55 (2H,
m, ArH). Diamide 9b. Yield 1.3 g (81%), mp 221–225 °C
with decomposition. Anal. calcd. for C14H16SN2O2 (%): C,
60.85; H, 5.84; S, 11.60; N, 10.14. Found (%): C, 60.93; H,
5.63; S, 11.78; N, 9.35. IR (KBr): ν, cm-1 3332s and 3197s
(ν(NH2)), 2963s and 2869m (ν(CH)), 1764m, 1722m,
1658vs and 1612s (ν(C=O)amide), 1525m, 1442s, 1398m,
1363m, 1325m, 1292m, 1259m, 1201m, 1160m, 1105m,
(pyridine): λmax, nm (A/Amax) 319 (2.87), 370sh (1.73),
631 (1.05), 649 (1.02), 696 (1). [H2SNctBu4] (12b).
The product was purified by column chromatogra-
phy on alumina (eluent: CHCl3). Yield 0.26 g (52%).
Anal. calcd. for C56H50SN8 (963.30) (%): C, 69.82;
H, 5.23; N, 11.63; S, 13.31. Found (%): C, 68.01; H,
5.86; N, 10.98; S, 12.98. UV-vis (CHCl3): λmax, nm
(log ε) 329 (4.56), 636 (4.22), 653 (4.24), 702 (4.42).
UV-vis (pyridine): λmax, nm (log ε) 328 (4.44), 640sh
(4.12), 659 (4.28), 705 (4.42). IR (KBr): ν, cm-1 3288w
(ν(NH)); 2956s, 2927s and 2858m (ν(CH3)); 1602m,
1571m, 1525m, 1456m, 1417s, 1373s, 1317m, 1297m,
1257m, 1155vs, 1072m, 1016s, 925m, 833m, 809w,
798w, 730w, 690m, 580w, 516w, 487w.
1
979w, 914w, 879w, 810w, 646m, 586m, 526w, 441w. H
NMR (DMSO-d6): δ, ppm 8.42 (1H, s, Ar-H), 8.15–8.12
(2H, s, CONH2), 7.98 (1H, d, ArH), 7.87 (2H, s, CONH2),
7.63 (1H, m, ArH), 1.35 (9H, s, tBu).
MgII complex [MgSNc] (13a). To a solution of mag-
nesium chips (15 mg, 0.62 mmol) in dry butanol (15 mL)
(dissolution was initiated by iodine crystal) dinitrile 11a
(80 mg, 0.435 mmol) was added and the mixture was
refluxed for 20 h. After evaporation of the solvent the
residue was stirred with aqueous acetic acid (50% v/v,
30 mL) at room temperature for 30 min. The precipitate
was centrifugated and washed thoroughly with water and
methanol. After purification by column chromatography
(silica, CHCl3) the MgII complex 13a was obtained .Yield
34 mg (42%). UV-vis (CHCl3): λmax, nm (A/Amax) 337
(1.96), 611 (0.43), 659 (1), 669 (1). UV-vis (pyridine):
2,3-dicyanothianaphthenes
[benzo[b]thiophene-
2,3-dicarbonitriles] (11). POCl3 (2.5 mL, 0.028 mol)
was added in portions to a solution of diamide 9a or 9b
(3.09 mmol) in DMF (10–15 mL) at 0–5 °C. The reac-
tion mixture was stirred further for 2 h, kept overnight
and then poured on ice. The precipitate was filtered,
washed with water, dried and sublimed. Dinitrile 11a.
Yield 0.5 g (88%), mp 151–153 °C (lit. 148 °C [15]).
Anal. calcd. for C10H4N2S (184.21) (%): C, 65.22; H,
2.17; S, 17.39; N, 15.22. Found (%): C, 64.43; H, 2.16;
S, 17.03; N, 14.00. IR (KBr): ν, cm-1 2229vs (ν(C≡N)),
1982w, 1940w, 1817w, 1726m, 1589m, 1498s, 1460m,
1423m, 1348m, 1321w, 1267m, 1182m, 1157s, 1134m,
1020w, 993w, 955m, 864m, 764vs, 729s, 661w, 642m,
518m, 488m, 438s, 413m. MS: m/z 184 (100%, [M]+).
1H NMR (CDCl3): δ, ppm 7.69 (2H, m, ArH), 7.96 (1H,
d, ArH), 8.08 (1H, d, ArH). Dinitrile 11b. Yield 0.95 g
(84%), mp 96–98 °C. Anal. calcd. for C14H12SN2 (%): C,
69.97; H, 5.03; S, 13.34; N, 11.66. Found (%): C, 68.71;
H, 5.01; S, 12.98; N, 10.98. IR (KBr): ν, cm-1 3086m and
3064m (ν(CH)Ar), 2964vs, 2837s and 2871s (ν(CH)tBu),
2229s (ν(C≡N)), 1934m, 1795vs, 1754m, 1653m,
1544m, 1510s, 1467s, 1440s, 1417s, 1367vs, 1317m,
1297m, 1253s, 1203m, 1159vs, 1105m, 1054m, 1016s,
925m, 916m, 879m, 831s, 777w, 755w, 734m, 690m,
λ
max, nm (A/Amax) 326 (1.34), 381 (1.19), 601 (0.34), 658
(0.98), 670 (1). IR (KBr): ν, cm-1 1654s, 1596s, 1523m,
1457s, 1407s, 1317m, 1267m, 1122s, 1095m, 1079m,
1043m, 917w, 858m, 750m, 725m.
Complexes with AlIII (14), GaIII (15) and InIII (16),
[(HO)MSNc] and [(HO)SNctBu4]. General method of
preparation. Mixture of the dinitrile 11a (0.5 g, 2.7 mmol)
or 11b (0.5 g, 2.1 mmol) with the corresponding metal
acetate ([Al(OAc)3] [26]), or hydroxodiacetate ([M(OH)
(OAc)2] M = GaIII or InIII produced by “Reakhim”) in a
2:1 molar ratio was placed in a glass test tube and rapidly
heated to 250 ºC in a metallic bath till complete solidi-
fication (1–3 min). Unreacted dinitriles were extracted
with diethyl ether and the residue purified by column
chromatography on Al2O3 (eluent: chloroform).
1
669m, 592m, 517w, 499m, 441m. H NMR (CDCl3): δ,
ppm 8.02 (1H, m, ArH), 7.91–7.88 (1H, m, ArH), 7.81
(1H, m, ArH), 1.45 (9H, s, tBu).
[(HO)AlSNc] (14a). Yield 26%. UV-vis (CHCl3):
λ
max, nm (A/Amax) 331 (1.12), 383 (0.98), 468 (0.37), 611
(0.38) 665 (0.97), 673 (1). UV-vis (pyridine): λmax, nm
(A/Amax) 387 (0.84), 470 (0.28) 609 (0.33), 670 (1.01),
678 (1). IR (KBr): ν, cm-1 1498m, 1462m, 1417s, 1402m,
1373m, 1319m, 1261m, 1155s, 1107m, 1076m, 1016m,
923m, 762m, 728m, 690w.
Preparation of tetra(2,3-thianaphtheno)porphyrazines
Free-bases [H2SNc] (12a) and [H2SNctBu4] (12b).
Dinitrile 11a (0.5 g, 2.7 mmol) or 11b (0.5 g, 2.1 mmol)
were added to a solution of lithium (0.05 g, 7 mmol)
in freshly distilled n-amyl alcohol (15 mL), and the
reaction mixture was refluxed until dark green color
was achieved (4–6 h). The solvent was evaporated, the
residue was washed with ethanol, 50% aqueous acetic
acid, water, and dried. [H2SNc] (12a). Low solubil-
ity prevents further purification. Yield 0.15 g (30%).
UV-vis (CHCl3): λmax, nm (A/Amax) 325 (2.11), 365sh
(1.64), 440sh, 629 (1.01), 642 (0.97), 694 (1). UV-vis
[(HO)AlSNctBu4] (14b). Yield 19%. Anal. calcd. for
C56H49S4N8OAl + 2H2O (1041.31) (%): C, 64.59; H, 5.13;
N, 10.76; S, 12.32. Found (%): C, 65.21; H, 5.04; N,
10.55; S, 12.08. UV-vis (CHCl3): λmax, nm (A/Amax) 335
(3.24), 628 (0.56), 684 (1). IR (KBr): ν, cm-1 2958vs and
2863m (ν(CH)tBu); 1636m, 1509m, 1463s, 1411s, 1384m,
1360s, 1296s, 1253s, 1222s, 1185s, 1099s, 1015m, 921m,
915s, 883m, 809s, 740s, 701m, 572m, 447m.
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SyntheSIS anD SPeCtral StuDy Of tetra(2,3-thIanaPhthenO)POrPhyrazIne
59
[(HO)GaSNc] (15a). Yield 65%. UV-
vis (CHCl3): λmax, nm (log ε) 334 (3.99),
378sh (3.88), 470sh, 616sh (3.66), 677
(4.08), 684 (4.08). UV-vis (pyridine): λmax
,
nm (A/Amax) 385 (0.73), 469sh, 611 (0.32),
678 (1). IR (KBr): ν, cm-1 3644m ν(OH),
3058m ν(CH)Ar, 1598s, 1498s, 1465s,
1421s, 1400s, 1309s, 1257s, 1228s, 1201s,
1189s, 1157s, 1128s, 1093s, 1060s, 1014s,
921m, 885s, 856m, 819m, 765s, 734s,
686s, 557s. MS (MALDI-TOF): m/z 805
[M - OH]+, 822 [M]+, 840 [M + H2O]+.
[(HO)GaSNctBu4] (15b). Yield 58%.
Anal. calcd. for C56H49S4N8OGa + 2H2O
(1084.04) (%): C, 62.05; H, 4.93; N, 10.34;
S, 11.83. Found (%): C, 62.51; H, 4.84; N,
9.68; S, 11.68. UV-vis (CHCl3): λmax, nm
(log ε) 341 (4.82), 369sh, 433 (4.49), 483
(4.49), 621 (4.27), 688 (4.92). IR (KBr): ν,
cm-1 2960vs and 2865m (ν(CH)tBu), 1639s,
1506s, 1463s, 1407s, 1394s, 1361s, 1296s, 1255s, 1222s,
1197vs, 1180vs, 1105s, 1016m, 937m, 916s, 890m, 809s,
757m, 740s, 701m, 632m, 570m, 559m, 457m. 1H NMR
(DMSO-d6): δ, ppm 8.22–8.06 (8H, m, ArH), 7.89–7.75
(4H, m, ArH), 1.39 (36H, s, tBu).
Scheme 1. Synthesis of 2,3-thianaphthendicarboxylic acid 4
prepared according to Friedlaender [25] from 2,3-thia-
naphtenequinone 2a which in turn was synthesised star-
ting from thioindoxyl (benzo[b]thiophen-3-ol, 5) using
the 3-stage Mayer�s procedure [29] (Scheme 1). In our
work we have prepared 2,3-thianaphthenquinone 2a in
one stage from more easily available thiophenol (1a)
[(HO)InSNc] (16a). Yield 73%. UV-vis (CHCl3):
λ
max, nm (log ε) 333 (4.23), 382 (4.01), 483sh, 618
and oxalyl chloride following the approach suggested by
(3.74), 684 (4.35). UV-vis (pyridine): λmax, nm (A/Amax
330sh, 391(0.68), 616sh (0.22), 683 (1). IR (KBr): ν,
cm-1 3616m ν(OH), 3060w and 3023w ν(CH)Ar, 1558m,
1519m, 1492m, 1454m, 1398m, 1309m, 1255m, 1224m,
1195m, 1182m, 1157m, 1124s, 1106s, 1095s, 1064s,
1037m, 914w, 875w, 811vw, 763w, 730w, 698w. MS
(MALDI-TOF): m/z 851 [M - OH]+, 868 [M]+.
)
Dutta [30] for thiophene-fused phenanthrene. Taking into
account the peculiarities of intramolecular acylation pro-
cesses [31] we have optimized the conditions and carried
out the reaction at 0–5 °C under vigorous stirring and
short reaction time. As a result, the yield of the quinone
2a was increased from 13% to 53%.
[(HO)InSNctBu4] (16b). Yield 61%. Anal. calcd. for
C56H49S4N8OIn + 3H2O (1147.16) (%): C, 58.63; H, 4.83;
N, 9.77; S, 11.18. Found (%): C, 58.71; H, 5.04; N, 9.38;
S, 10.98. UV-vis (CHCl3): λmax, nm (log ε) 347 (4.63),
386 (4.51), 420sh, 489 (4.24), 625 (4.26), 693 (4.94). IR
(KBr): ν, cm-1 2962s, 2925s and 2867s (ν(CH)tBu); 1633s,
1514s, 1463s, 1415s, 1363s, 1296s, 1257s, 1222s, 1155s,
1088s, 1049s, 1016s, 917s, 885m, 809m, 740m, 701m,
597m, 574m, 435m. 1H NMR (CDCl3): δ, ppm 7.98–7.87
(8H, m, ArH), 7.68 (4H, m, ArH), 1.44 (36H, s, tBu).
While the dinitrile 11a could be easily obtained by
dehydration of the diamide 9a (e.g. upon refluxing with
acetic anhydride, 80–90% yield [15]), the conversion
of the diacid 4a to its diamide 9a implicates some diffi-
culties (Scheme 2). According to the procedure used in
[15] the diacid 4a upon treatment with acetic anhydride
was dehydrated to the anhydride 6a, which on heating
with PCl5 was converted to the dichloroanhydride 7a
with high overall yield (ca. 90%). However, ammonoly-
sis of the dichloroanhydride 7a gave after recrystalliza-
tion from water only 13% of the diamide 9a along with
ca. 13% of amidoacids 8a from the mother liquid. The
disadvantage of this synthetic approach and low overall
yield of the dinitrile 11a (ca. 9% on the used diacid 4a),
is evidently connected with high sensitivity of the dichlo-
roanhydride 7a to hydrolysis. This leads to formation
of considerable amounts of amidoacids 8a which were
mainly lost during recrystallization. We have elaborated
the improved synthetic procedure taken into account that
the diamide 9a can be prepared by ammonolysis of the
imide 10a with almost quantitative yield. According to
Linstead�s report [15] the imide 10a is formed upon dis-
tillation of amidoacids 8a with P2O5, but the attempts of
RESULTS AND DISCUSSION
Synthesis of the precursors
Template cyclotetramerization of dinitriles of ortho-
dicarboxylic acids in the presence of metals or metal salts
is the most convenient methodology for the preparation
of porphyrazines with various annulated heterocycles [9,
27, 28]. In the original Linstead�s work [15] 2,3-thia-
naphthenedicarboxylic acid 4a, the key intermediate
in the synthesis of the corresponding dinitrile 11a, was
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60
e.S. taraymOvICh et al.
So the overall combined yield of the dinitrile 11a from
the diacid 4a in the “one-pot” procedure (B) (ca. 45%)
was larger than that in the procedure (A) (30–35%), and
much higher than in the original Linstead�s procedure
(9–10%).
A similar strategy has being used for the synthesis
of the tert-butyl substituted dinitrile 11b from tert-
butylthophenol 1b which was prepared by reduction of
tert-butylbenzenesulfochloride with zinc dust in concen-
trated sulfuric acid.
Synthesis of porphyrazines
The dinitriles 11 afford tetra(2,3-thianaphtheno)por-
phyrazines upon cyclotetramerization. Refluxing of the
dinitriles 11 in n-amyl alcohol in the presence of lithium
amylate leads to the dilithium complexes which upon
isolation are demetalated to give the corresponding free-
base macrocycles [H2SNc] (12a) or [H2SNctBu4] (12b).
Cyclotetramerization of 11a in n-butanol in the presence
of magnesium butylate gives the MgII complex [MgSNc]
(13a). Complexes with GaIII (15a, 15b) and InIII (16a, 16b)
were very easily produced with 65–75% yields by tem-
plate cyclotetramerization of the dinitriles 11 when melt-
ing with the corresponding hydroxydiacetate [M(OH)
(OAc)2] in a metallic bath for 3–5 min at 170–250 °C.
The AlIII complexes (14a, 14b) could be obtained from
AlIII acetate only with 20–25% yield. Purification were
troublesome for the free-base 12a and AlIII complex 14a
due to their extremely low solubility in organic solvents,
but complexes of GaIII (15a, 15b) and InIII (15a, 15b) as
well as tert-butyl substituted species 12b, 14b–16b could
be purified by column chromatography. Thianaphthene
rings can be 2,3-annulated to four pyrrole rings of the
porphyrazine macrocycle in a different manner and we
obtained tetra(2,3-thionaphtheno)porphyrazines as a
mixture of four randomers having different symmetry
(2,3:2,3:2,3:2,3 – C4h, shown in Chart 1; 2,3:2,3:2,3:3,2
– Cs; 2,3:2,3:3,2:3,2 – C2v and 2,3:3,2:2,3:3,2 – D2h, see
Chart 2). Unfortunately, our column chromatographic
procedure was not effective enough for isolation of the
individual randomers. The presence of the mixture of
randomers leads to complex multiplets in the aromatic
region of the 1H NMR spectra and to broadening or split-
ting of the Q-band in the UV-vis spectra (see below).Ana-
lytical data indicate that metal complexes 14b–16b were
obtained as hydrated materials. All new porphyrazines
have been characterised by UV-vis and IR spectroscopy,
and some of them by MALDI-TOF mass-spectrometry
and 1H NMR spectra.
Scheme 2. Conversion of 2,3-thianaphthenedicarboxylic acid
4 to dinitrile 11
its direct preparation from the anhydride 6a by its melting
with urea or ammonium carbonate gave unsatisfactory
results. We have synthesized the imide 10a in two dif-
ferent ways. (A) Ammonolysis of the anhydride 6a with
dry NH3 in chloroform solution leads to precipitation of
the mixture of aminoacids 8a, which upon dehydration
with POCl3 in DMF gave the imide 10a (50% yield after
sublimation) along with some amount of mononitrile. (B)
In another procedure, the imide 10a was obtained from
the diacid 4a in three stages by consecutive treatment
with SOCl2, dry NH3, POCl3 in DMF and sublimation
with 39–40% overall yield. In line with observations
made in [15] we have found that treatment of the diacid
4a with SOCl2 leads to a mixture of the dichloroanhy-
dride 7a with the anhydride 6a. It was partly melted at
58–65 °C and completely at 155–165°C. Melting points
for the dichloroanhydride 7a and the anhydride 6a repor-
ted in [15] are 72°C and 173°C, respectively. We could
not find conditions for complete conversion of the diacid
4a to the dichloroanhydride 7a under action of SOCl2 and
separation of the anhydride 6a and the dichloroanhydride
7a was a wasteful procedure. Instead we have directly
treated their mixture of with dry NH3 to obtain mixture
of amidoacids 8a and the diamide 9a which were then
dehydrated with POCl3 to the imide 10a and the dinitrile
11a. The latter is soluble in CHCl3 and could be isolated
with ca. 10% yield (on the used diacid 4a). The reaction
of the insoluble imide 10a with conc. aqueous NH3 solu-
tion yielded the diamide 9a (84%) which upon treatment
with POCl3 in DMF gave the target dinitrile 11a (88%).
As is usual for MgII complexes of phthalocyanine [32]
and its heterocyclic analogues (see e.g. [33]) for the MgII
complex 13a one water molecule is assumed to be coor-
dinated [(H2O)MgSNc]. Complexes of AlIII, GaIII and
InIII were obtained as hydroxo complexes [(HO)MSNc]
(M = AlIII, GaIII, InIII). In the MALDI-TOF spectra
recorded for 15a and 16a the intense peaks of [MSNc+]
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SyntheSIS anD SPeCtral StuDy Of tetra(2,3-thIanaPhthenO)POrPhyrazIne
61
Chart 2. Structural formulae of four possible randomers of tetra(2,3-thianaphtheno)porphyrazines [MSNc] (12a–16a) and
[MSNcBu4] (12b,14b–16a). M = 2H (12a,b), (H2O)Mg (13a), (HO)Al (14a,b), (HO)Ga (15a,b), (HO)In (16a,b). R = H (a),
R = tert-Bu (b)
(100%) are accompanied by lower intensity peaks of
hydroxocomplexes [(HO)MSNc+] (30% for 15a and
10% for 16a), and in the case of the GaIII complex 15a
an additional peak of the aquahydroxo complex [(HO)
(H2O)GaSNc+] is also seen in Fig. 1. In the IR spectra,
the bands of the stretching OH vibrations ν(OH) can
be seen at 3644 cm-1 for 15a and at 3616 cm-1 for 16a.
Elemental analysis data obtained for 14b–16b provide
evidence that these species were isolated as hydrated
materials.
spectral characteristics of tetra(thianaphtheno)porphyra-
zines 12-16 with the data for the related porphyrazines,
phthalocyanines and naphthalocyanines taken from the
literature.
UV-vis spectra obtained for the metal complexes of
the present tetra(thianaphtheno)porphyrazines, [MSNc]
and [MSNcBu4] (13–16) (see Fig. 2), are typical for
porphyrazine and phthalocyanine metal complexes (see
[9, 34, 35]) and contain the intense absorption bands in
the far-red visible and in the UV-region. For the tert-
butyl substituted species the absorption maxima are
shifted slightly to the longer wavelength as compared
to the unsubstituted tetra(thianaphtheno)porphyrazines.
The low-lying HOMO→LUMO π-π* transitions of
the porphyrazine π-chomophore are responsible for
the appearance of the intense Q-band absorption at
665–695 nm, which is accompanied by vibronic sat-
ellites on the blue side. It should be noted that unlike
metal complexes of symmetrically substituted por-
phyrazines and phthalocyanines which have a strict
D4h symmetry of the π-chromophore and hence the
degenerated eg* type LUMO, the present metal com-
plexes of tetra(thionaphtheno)porphyrazines 13–16
have lower symmetry due to “angular” 2,3-annulation of
UV-vis spectra
Due to essentially planar structure of the macrocycle
[H2SNc] (12a) and its metal complexes [MSNc] 13a–16a
have low solubility and exhibit some tendency to aggre-
gate. They are relatively well soluble in pyridine, DMF,
α-chloronaphthalene and partly aggregated in CHCl3.
The corresponding tert-butyl substituted derivatives
[H2SNcBu4] (12b) and [MSNcBu4] (14b–16b) have better
solubility and are less aggregated. The electronic absorp-
tion spectra (UV-vis spectra) recorded for the free-bases
12a,b and for their metal complexes 13–16 in CHCl3 and/
or in pyridine are shown in Fig. 2. Table 1 compares some
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62
e.S. taraymOvICh et al.
(12a) and [H2SNctBu4] (12b) which, due
to the presence of the inequivalent pyrrole
and pyrrolenine units, have effective sym-
metry of the π-chromophore close to D2h
and, as can be seen from Fig. 2, exhibit
considerable splitting of the Q-band into
two components (629 and 694 nm for 12a
and 653 and 702 nm for 12b in CHCl3).
As can be seen from the data presented
in Table 1, the Q-band maxima for the free-
bases of the thianaphthene annulated por-
phyrazines 12a,b and their metal complexes
13–16 is shifted bathochromically by ca.
80 nm as compared to the corresponding
β-unsubstituted or tert-butyl-substituted
of porphyrazines ([MPA] and [MPAtBu4],
M = 2H, MgII) and by 30–40 nm as com-
pared to the octaphenyl substituted species
([MPAPh8] M = 2H, Mg, ClAlIII, ClGaIII
and ClInIII [38, 39]). Such bathochromic
shift is a typical consequence of the exten-
sion of π-chromophore by annulation of
peripheral aromatic fragments [34]. The
bathochromic shift of the Q-band (∆λQ)
caused by 2,3-fusion of four 10π-electron
thianaphthene moieties (∆λQ = 79 nm for
[H2SNc]) is larger than the effect of four
6π-electron thiophene rings (∆λQ = 59 nm
for [H22,3ThPA] [17]), but comparable with
annulation of benzene rings in phthalocy-
Fig. 1. MALDI-TOF mass-spectrum of the GaIII complex 15a and comparison
of the experimental and calculated isotopic distribution for the molecular ion
peaks
anines (∆λQ ca. 80 nm for [H2Pc] [35, 40]. The spectral
data available for the MgII complexes indicate that the
bathochromic shift upon 2,3-fusion of four thianaph-
thene fragments (∆λQ = 86 nm for [MgSNc]) is slightly
less that the effect of isoelectronic 1,2-fusion of the
naphthalene rings (∆λQ = 96-107 nm for [Mg1,2Nc]
[36]), but much less that the effect of 2,3-nahthalene
annulation (∆λQ = 190 nm for [Mg2,3Nc] [41]). These
facts show that benzene rings of the thionaphthene
units are not effectively involved in conjugation with
the central porphyrazine π-chromophore. This is due
to the “angular” type of annulation also observed in
1,2-naphthalocyanines. Smaller bathochromic shift for
[MSNc] as compared to [M1,2Nc] species is consist-
ent with the electron-withdrawing effect of the more
electronegative S-atom as compared to the ethylene
CH=CH unit.
thionaphthene moieties. The symmetry of four possible
randomers is C4h, C2v, Cs or D2h (see Chart 2) and there-
fore two LUMO is not degenerated. Indeed, the Q-band
for the metal complexes [MSNcBu4] and [MSNcBu4]
(13–16) is broader than for the symmetrical metal por-
phyrazines [MPA] and phthalocyanines [MPc], and the
splitting of the Q-band is definitely seen for the MgII
complex 13a (658 and 670 nm in pyridine), for the AlIII
complex 14a [(HO)AlSNc] (670 and 678 nm in pyrid-
ine) and for the GaIII complex 15a [(HO)GaSNc] (677
and 684 nm in chloroform). A similar situation was
observed [36] for the MgII complex of 1,2-naphthalo-
cyanine [Mg1,2Nc] containing “angularly” fused naph-
thalene units. Four randomers of this latter species were
separated chromatographically and distinguished by
slight differences in the Q-band maximum position and
its splitting (up to 4 nm) taking into account the theo-
retical prediction of the Q-band splitting values [37]. In
our case, although we have observed some spectral dif-
ferences in the successively eluted fractions of the broad
band during column chromatography, the effective sep-
aration of the individual randomers was not achieved.
The observed splitting of the Q-band for [MSNc] does
not exceed 12 nm, indicating that effective symmetry of
the π-chromophore in metal complexes is only slightly
lower than D4h. This is unlike the free-bases [H2SNc]
The maximum of the Q-band for the InIII complexes
is shifted slightly bathochromically as compared with
the MgII, AlIII and GaIII complexes. This is typical for
complexes of porphyrazines [MPAPh8] [38, 39] and
phthalocyanines [MPc] [35, 42] (see Table 1) and can
be explained by larger ionic radius of InIII which causes
doming of the macrocyclic ligand and destabilization of
its HOMO.
The broad absorption band in the UV-region has
maximum at 320–340 nm and maximum or shoulder
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SyntheSIS anD SPeCtral StuDy Of tetra(2,3-thIanaPhthenO)POrPhyrazIne
63
appear near 330 nm (326 nm in [MgPA] [43]), but
shifted bathochromically upon introduction of substit-
uents in pyrrole rings (376 nm for [MgPAPh8] [44])
and/or extention of the conjugated π-system by annu-
lation (377–381 nm for [Mg1,2Nc] [36]). In the spec-
tra of metal porphyrazines and phthalocyanines only
single maximum is present in the 300–400 nm region.
The second UV maximum observed for [MSNc] at
320–340 nm can be therefore assigned to the π-π*
transitions localized on the thionaphthene fragments.
The broad lower intensity absorption at 450–500 nm
can be tentatively assigned to the charge transfer
from thionaphthene units to the central porphyrazine
macrocycle.
CONCLUSION
We have modified and improved the procedure for the
preparation of thianaphthene-2,3-dicarbonitriles — the
key intermediates for template synthesis of thianaph-
thene annulated porphyrazines. This allows us to prepare
the symmetrical tetra(2,3-thianaptheno)porphyrazine, its
tetra-tert-butyl substituted derivative and their complexes
with MgII, AlIII, GaIII and InIII, which were spectroscopi-
cally chasracterized. It is shown that the extension of
the porphyrazine π-chromophore by annulation of four
thianaphthene fragments have only a moderate effect on
its spectral properties which is comparable with fusion
of four benzene rings in phthalocyanines. This is due to
the angular type of their annulation (similar to that found
in 1,2-naphthalocyanines) and negative inductive effect
of the sulfur atoms. The effect of thianaphthene annula-
tion on the acid-base properties of porphyrazine macro-
cycle and on the non-linear spectral properties (optical
limiting) is currently under investigation. Our interest on
new classes of annulated porphyrazines is also related
to possibilities of further structural modification of
thianaphthene fragments.
Fig. 2. UV-vis spectra of tetra(2,3-thianaphtheno)porphyrazines
12a–16a (solid and dotted lines) and 12b, 15b, 16b (dashed
lines) in pyridine (solid lines) and in chloroform (dotted and
dashed lines). Absorption maxima for tert-butyl substituted
porphyrazines 12b, 15b, 16b are given in italics
at 380–390 nm. The latter can be assigned to the por-
phyrazine Soret band due to strongly mixed transitions
from the lower lying occupied π-MOs to LUMO.
Indeed for unsubstituted porphyrazines the Soret band
Table 1. Position of the Q-band (λmax, nm) in the UV-vis spectra of tetra(2,3-thianaphtheno)porphyrazines
[MSNc] and related porphyrazine, phthalocyanine and naphthalocyanine analogues
Porphyrazine
2H
MgII
AlIII
GaIII
InIII
Reference
[MPA]
545, 617a
547, 620c
599, 664d
665, 698a
668, 703g
780g
584b
591c
637d
675f
678h
[43]
[35]
[MPAtBu4]
[MPAPh8]
[MPc]
[MPctBu4]
[M2,3Nc]
[M1,2Nc]
[MSNc]
636e
691g
683i
815g
694l
670, 678f
684d
636e
700g
689j
815g
703l
678f
688d
642e
690d
697d
823d
[38, 40, 44]
[35, 40, 42]
[35, 42]
[19, 42]
[35, 36]
this work
this work
[17]
776g
678, 691i,k
658, 670f
629, 642, 694d
636, 653, 702d
632, 676m
683f
693d
[MSNctBu4]
[M2,3ThPA]
b
c
d
e
f
g
g
i
aChlorobenzene. MeOH. Hexane. CHCl3. CH2Cl2. Pyridine. 1-Chloronaphthalene. iso-AmOH. DMSO.
jMethyl methacrylate. kD2h randomer. lo-Dichlorobenzene. mTetrahydrofurane.
Copyright © 2011 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2011; 15: 63–65

64
e.S. taraymOvICh et al.
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This work was supported by the state grants of the
President of Russian Federation for leading scientific
schools (NSh-2642.2008.3) and young candidates of
sciences (MK-4752.2009.3), as well by the Federal Pro-
gram “Scientific and Educational Personnel of Innovative
Russia” (state contracts 02.740.11.0116, P-1105, P-2077).
TheauthorsarethankfultoDr.Y.EnakievafromtheInstitute
of Physical Chemistry Russian Academy of Sciences
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