Full Paper
2,5-Bis(4-bromophenyl)thaizolo[5,4-d]thiazole (BPTzTz)
Single-crystal X-ray diffraction
The compound was synthesized using a modification of literature
Diffraction data for 2 were collected on a Bruker-Nonius FR951
Kappa APEX II equipped with a MoKa (l=0.71073 ꢁ) radiation
[21]
procedures. A solution of dithiooxamide (1.2 g, 10 mmol) and 4-
bromobenzaldehyde (4.0 g, 22 mmol) in DMF (40 mL) was refluxed
for 3 h. The mixture was filtered, washed with water, and the resi-
source. For 2·I , data were collected on an Agilent Technologies Su-
2
perNova diffractometer, employing CuKa (l=1.5406 ꢁ) radiation.
due recrystallized from cyclohexanone to afford BPTzTz as a yellow
An Oxford Cryosystems 700 Plus cryostream attachment produced
1
solid (1.2 g, 27%, m.p.>2608C); H NMR (300 MHz, d -pyridine):
a continuous stream of N at 150 K in both cases. Following har-
5
2
13
d=7.98 (d, J=8.7 Hz, 4H), 7.69 ppm (d, J=8.6 Hz, 4H); C NMR
vest, crystals were coated in a thin film of paratone-N oil and
(
1
75 MHz, d5-pyridine): d=176.7, 141.5, 140.7, 132.5, 128.1,
mounted on a mohair fiber affixed to a goniometer head. Data re-
ꢀ
1
25.1 ppm; IR (KBr): ~n =1442, 1068, 1004, 840, 811 cm ; LR-APCI-
duction, integration and absorption corrections were performed
+
[22]
MS m/z 453 [M] . HR-APCI-MS m/z calcd for C H Br N S :
4
C H Br N S : C 42.50, H 1.78, N 6.20; found: C 41.92, H, 1.90; N,
6
using the Agilent Technologies CrysAlisPro
software (version
16
9
2
2 2
+
52.85534 [M] ; found: 452.76054; elemental analysis calcd (%) for
1.171.35.8) for the SuperNova collection, while the APEX II collec-
[
23]
tion was processed using SAINT+
within the APEX2 software
1
6
8
2
2 2
[24]
.15.
suite. Crystal structures were solved using SUPERFLIP and refined
[25]
2
within SHELXL-97
method.
using the full-matrix least-squares on F
N,N’-(Thiazolo[5,4-d]thiazole-2,5-diylbis(4,1-phenylene))-
bis(N-(pyridine-4-yl)pyridin-4-amine (1)
CCDC-1012472(2) and CCDC-1012473(2·I ) contain the supplemen-
2
tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
4
,4’-Dpa (430 mg, 2.5 mmol), BPTzTz (450 mg, 1.0 mmol), anhy-
drous potassium carbonate (690 mg, 5.0 mmol), anhydrous copper
sulfate (150 mg, 0.90 mmol), 18-crown-6 (36 mg, 0.15 mmol), and
diphenyl ether (10 mL) were heated at 2008C for 6 days. After the
reaction had cooled, water (20 mL) was added. The aqueous layer
was extracted with CH Cl (3ꢂ100 mL), and the organic layer dried
Crystal data for C H N O S Zn (2, M=822.14): monoclinic, space
36 24 10
6 2
group P2/n (no. 13), a=7.4144(6) ꢁ, b=10.0591(8) ꢁ, c=
3
2
6.668(2) ꢁ, b=93.175(3)8, V=1985.9(3) ꢁ , Z=2, T=150(2) K,
ꢀ
1
ꢀ1
3
m(Mo )=0.780 mm , Dcalc =1.375 gm m , 95334 reflections
Ka
2
2
measured (5.62ꢁ2Vꢁ65.74), 7409 unique (R =0.0441, Rsigma
=
over NaSO . The solvent was removed under reduced pressure and
int
4
0
.0237), which were used in all calculations. The final R was 0.0708
1
the residue purified by silica gel column chromatography (using an
elution gradient of 20:1 CH Cl :Et N to 20:1:1 CH Cl :Et N:MeOH)
(
I>2s(I)) and wR was 0.1952 (all data).
2
2
2
3
2
2
3
to afford the title compound as a dark yellow solid (510 mg, 81%,
Crystal data for C H I N O S Zn (2·I , M=855.14): monoclinic,
36 24 0.26 10 6 2 2
1
m.p.>2608C); H NMR (300 MHz, [D ]DMSO): d=8.46 (dd, J=4.8,
space group P2m (no. 10), a=7.3967(13) ꢁ, b=10.0457(13) ꢁ, c=
6
3
1
4
.5 Hz, 8H), 8.12 (dd, J=6.7, 2.0 Hz, 4H), 7.37 (dd, J=6.7, 2.0 Hz,
13.636(2) ꢁ, b=102.788(17)8, V=988.1(3) ꢁ , Z=1, T=150(2) K,
13
ꢀ1
ꢀ1
3
H), 7.06 ppm (dd, J=4.8, 1.5 Hz, 8H);
C NMR (75 MHz,
m(Cu )=3.929 mm , D =1.437 gm m , 7437 reflections mea-
Ka calc
[
1
7
D ]DMSO): d=167.7, 151.3, 151.0, 150.5, 146.2, 130.6, 128.1, 127.2,
sured (12.28ꢁ2Vꢁ153.06), 2169 unique (R =0.0407, Rsigma
=
6
int
17.0 ppm; IR (KBr): ~n =3038, 1577, 1494, 1339, 1287, 1217, 818,
0.0262), which were used in all calculations. The final R was 0.1303
1
ꢀ
1
+
35, 625, 535 cm ; LR-ESI-MS m/z 633 [M] . HR-ESI-MS m/z calcd
(I>2s(I)) and wR was 0.4070 (all data).
2
+
for C H N S : 633.15989 [M] ; found: 633.16412; elemental analy-
3
6
25
8 2
sis calcd (%) for C H N S ·4H O: C 61.15, H 4.32, N 15.75; found: C
3
6
24
8
2
2
Electrochemistry
6
1.36, H, 4.57; N, 15.90.
Cyclic voltammetry (CV) was performed using a BASi Epsilon Elec-
trochemical Analyzer with ferrocene (Fc) as an internal reference.
Measurements were conducted under an inert Ar atmosphere
using a conventional three-electrode cell: a glassy carbon working
[
Zn(NO ) (1)] (2)
3 2
Single crystals were grown by heating Zn(NO ) ·6H O (10 mg,
+
3
2
2
electrode, a Pt wire auxiliary electrode, and a Ag/Ag quasi-refer-
0
(
.03 mmol) and 1 (1 mg, 2 mmol) in a 1:1 MeCN:DMF solution
5 mL) at 1208C for 72 h, followed by cooling to room temperature
over 12 h. Heating 1 (40 mg, 0.063 mmol) and Zn(NO ) ·6H O
ence electrode. A [nBu N]PF /MeCN electrolyte (0.1m) was em-
4
6
ployed. Solution-state samples were measured with scan rates in
3
2
2
ꢀ1
the range 25–250 mVs . Solid-state samples were mounted on
(
40 mg, 0.15 mmol) in the same solvent system (15 mL) at 1208C
the glassy-carbon working electrode by dipping the electrode into
a paste made of the powder sample in MeCN, and measured with
for 48 h with stirring yielded a yellow powder of 2 (34 mg, 66%).
ꢀ
1
scan rates in the range 100–1000 mVs .
Oxidation of the ligand by NOPF : 1 was dissolved in dry MeCN
6
ꢀ
(
6 mL) and oxidized using a stoichiometric amount (1, 2, and 4e
ꢀ
3
Solution state UV/Vis-NIR SEC
equivalents) of 5ꢂ10 m NOPF /MeCN solution, through which N2
6
was bubbled for 10 min, facilitating the removal of NO.
ꢀ1
Spectroelectrochemistry over the range of 4000–35000 cm was
performed using a CARY 5000 spectrophotometer interfaced to
Varian WinUV software. In the solution state, the absorption spec-
tra of the electrogenerated species were obtained in situ by the
use of an Optically Semi-Transparent Thin-Layer Electrosynthetic
(OSTLE) cell, path length 0.65 mm, mounted in the path of the
spectrophotometer. Solutions for the spectroelectrochemical ex-
periment contained [nBu N]PF /MeCN supporting electrolyte
Reduction of the ligand by LiNp: 1 was suspended in THF (2 mL)
ꢀ
and reduced with a 4e equivalent of LiNp/THF solution (0.1m).
H O (1 mL) was subsequently added to oxidize any remaining
2
naphthalenide radical and the solution was stirred under Ar for
one hour.
4
6
Impregnation of the framework by I : A small 2 mL glass vial con-
(0.1m) and approximately 1 mm of the compound. Appropriate
potentials were applied by using an eDAQ e-corder 410 potentio-
stat and the current was carefully monitored throughout the elec-
trolysis. By this method, the electrogenerated species were ob-
2
taining the neutral crystal coated in paratone-N oil was placed
inside a larger 21 mL glass vial containing solid iodine, which was
allowed to diffuse throughout the chamber.
Chem. Eur. J. 2014, 20, 1 – 10
7
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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