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Synthesis and Electronic Communication in Dumbbell-shaped

Phenothiazine Dyads Bridged by Heterocycles
Full Name,a Full Namea,b and Thomas J. J. Müllera*
Received (in XXX, XXX) 1st January 2007, Accepted 1st January 2007
5 First published on the web 1st January 2007
DOI: 10.1039/b000000x

The symmetrical dumbbell-shaped phenothiazine dyads 9, 12 and 13 show intense electronical

coupling between the redox-active phenothiazine units revealed from the cyclovoltammetric
spectra and DFT calculations. Futhermore, we have shown that the fluorescence emmision of
10 derivatives 9 and 10 can be switched off by the addition of TFA and on by neutralization.

Introduction 3 mol% of Pd2(dba)3.dba as palladium source, 5 mol% of

PHtBu3BF4 as ligand, NaOtBu as base and 1,4-dioxane as
Phenothiazines belong to an important class of tricyclic
solvent.16 After refluxing the reaction mixture over night, the
nitrogen-sulfur heterocycles,1 with a broad spectrum of
syntheses furnished in the desired coupling products 8-13 in
pharmacological activity.2 Most interestingly, phenothiazines
55 moderate to good yields (Scheme 1).
15 are also able to cleave DNA upon photochemical induction. 3
As a consequence of a low oxidation potential, they readily
Br Br
form stable radical cations and some of their physiological n n
he x hex
activity can be attributed to this circumstance. 4 Furthermore, 2
S
N N
S
the radical cations give rise to a fingerprint of characteristic, cond., 73 % n n
hex hex
20 deep-colored absorptions.5 Thus, phenothiazine derivatives 8
have become important spectroscopic probes in molecular and
supramolecular arrangements for photoinduced electron
transfer (PET) studies6 and as motifs in organic materials. 7 Br N Br N N N
The prospect of integrating strongly coupled redox fragments 3 S S

25 like phenothiazines into conjugated chains could constitute a cond., 59 %

9
so far unknown class of redox addressable molecular wires, in
particular, for a redox manipulation of single molecules with
nanoscopic scanning techniques.8,9 As part of our program to Br S
N
synthesize and investigate phenothiazinyl based molecular Br N
30 wires,10-12 we have communicated syntheses, structures, and 4 N N
first cyclic voltammetry measurements of directly linked cond., 50 % S
10
S
phenothiazinyl dyads, triads and up to heptades11 that can be
regarded as models for polymer-based coupled electrophores. N
Recently, we reported studies on the correlation of the folding H S
35 angle of phenothiazines and the electronic properties by 1
Br N
introducing several sterically demanding aromatic substituents
N N
in the 10-position. 12 Here, we present the synthesis and Br N
N N
5
electronic studies on heterocyclic bridged, dumbbell-shaped S 11
con d., 35 %
phenothiazine dyads with tunable redox and in some cases,
40 fluorescence properties.

Results and discussion Br O

6
Br N O N
S S
Syntheses cond., 30 %

Generally, there are two well-described methods in literature 12

for the amination of (hetero)arenes: The Ullmann-coupling, 13

45 where overstoichiometric amounts of a copper-salt as Br S Br
N S N
mediator are needed and the palladium-catalyzed Buchwald- 7
S S
Hartwig reaction.14 Recently, Buchwald also described a Scheme 1 Synthesiscond.,of 52dumbbell-shaped
% phenothiazine dyads 8-13
catalytical, palladium-free protocol of the Ullmann-coupling. 15 (reaction conditions: dibromoarene 2-7 (1 eq.), 10H-phenothiazine
13 1
In our synthetic approach, the coupling of 10H-phenothiazine (2.2 eq), 0.03 eq Pd2(dba)3.dba, 0.05 eq PHtBu3BF4, 2.3 eq NaOtBu, dry
60 1,4-dioxane, reflux, 19 h).
50 (1) with dibromo (hetero)arenes (2-7) was accomplished using

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The structures of N,N´-bridged phenothiazine dyads 8-13 were symmetrical structure as the energy minimum. The tilt angles
unambiguously assigned by 1H and 13C NMR, UV/vis, and IR 35 of both phenothiazine units valued 32.1° in our calculation
spectroscopy, by mass spectrometry and by correct and were signifficantly different to the ones of the thiophene
combustion analyses. (Eigentlich war es das schon zu den derivative 13. We assume this smaller tilt angle of 11 to the
5 Synthesen, falls Du einen Vorschlag bzgl. eines wichtiges electron-deficient character of the pyridazine bridge. Here, we
Aspekts oder zum Füllen hast, dann kann ich dies gerne also found the intra-configuration of both phenothiazines to
ausführen). 40 be the most stable one. However, looking at the calculated
frontier orbitals of 11 we found a completely diffrent electron
DFT-Caculations
distribution (Figure 2) in comparison with the thiophene
To determine the structure-properties relationship we carried derivative 13. While the LUMO (Figure 2, top) of 11 is
10 out calculations on the DFT level of theory (B3LYP/6- located mostly at the pyrazidine moiety, the HOMO (Figure 2,
31+G(d,p)). Herein, we used the gaussian software package. 17 45 bottom) is distributed over the whole molecule; in the case of
After the optimization of the structures of 3,6-pyridazine- (11) 13 one could observe a distict seperation between HOMO and
and 2,5-thiophene- (13) bridged phenothiazine dyads we LUMO due to electron-rich and electron-deficient units in the
focussed on the electron density distribution in the frontier molecule.
15 orbitals HOMO and LUMO.
In case of the thiophene bridged phenothiazine dyad 13 we
obtained an almost C2v-symmetrical structure in the geometry
optimization (Figure 1). The phenothiazine moieties both
show a tilt angle in its butterfly structure of 43.0°.
20 Futhermore, the one can see in both phenothiazine units an
intra-configuration, which is typical for N-aryl
phenothiazines.18 Due to this symmetry, the calculated HOMO
(Figure 1, bottom) is localized on both phenothiazine
moieties, while the LUMO (Figure 1, middle) is localized on
25 the central thiophene. This gives a realistic distribution, since
the phenothiazine units are regarded as strong electron donors
while the thiophene moiety serves as an acceptor.

50
Fig. 2 DFT calculated HOMO (bottom) and LUMO (top) of the
phenothiazine dyad 11 containing a pyridazine spacer.

Electronic properties
The electronical properties of the dumbbell-shaped
55 phenothiazine dyads 8-13 were determined by absorption and
emission spectroscopy and by cyclic voltammetry (Table 1).
Optical spectroscopy studies (UV/vis and fluorescence
spectra) of systems 8-10 and 11-12 display weak fluorescence
with emission of blue-green light and large Stokes shifts
60 (9600–10600 cm-1). The pyridazine bridged phenothiazine
derivative 11 does not display any emission properties.
As shown by comparison with the spectra of 10H-
30 Fig. 1 DFT calculated frontier orbitals, HOMO (bottom) and LUMO (top)
of the N,N´-thiophene bridged phenothiazine 13. phenothiazine (1) the same absorbtion spectra maxima appear
in the spectra of the dyads indicating that the donor
We also performed calculations with 10,10’- 65 (phenothiazine) and acceptor (pyridine, pyridazine, furane,
biphenothiazinyl-3,6-pyridazine (11) and also obtained a C2v- thiophene or fluorene) π-systems are essentially electronically

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decoupled in the electronic ground state. The absorption
spectra of dyads 8-13 are very similar and show a significant
band at around 303-333 nm, a second intense absorption at
around 252- 259 nm and in the case of 8, 9 and 10 a third
5 intense absorption at 280 nm, 288 nm, and 283 nm,
respectively.
The great difference of both oxidation processes (∆E= 396
mV) is assumed to be caused by an electronic coupling of
both phenothiazine units in the stage of the in-situ formed
mono radical cation of 10, which is widely delocalized.
2

Table 1 Selected (absorption and emission spectra, cyclic voltammetry)

electronic properties of dumbbell-shaped phenothiazine dyads 8-13 0

Compound Absorption Emission Stokes shift E00/+1 E0+1/+2

I [µA]
-2
λmax,abs λmax,abs [cm-1] [mV]b [mV]b
[nm]a [nm]a
8 259, 280, 477, 506 11500 761 - -4

308 (sh.)
9 288, 251, 516, 552 10600 891 1276 -6
333 (sh.) 1,6 1,4 1,2 1,0 0,8 0,6 0,4 0,2 0,0

10 253, 283, 517, 556 13000 736 1132 U [V]

309 (sh.) U [V]

11 253, 303 - - 851 1155c 50
Fig. 3 Cyclic voltommogram of 13, recorded in CH2Cl2.
12 252, 304 443, 503 10300 608 954
(sh.)
13 256, 311 444, 512 9600 640 1072
Most remarkable is cyclovoltammogram of 11 (Figure 4)
(sh.) which shows a separation of two anodic oxidations by more
a
then 300 mV and just a single reversible process. This
Recorded in CH2Cl2. b Recorded in CH2Cl2, 20 °C, v = 100 mV/s,
10 electrolyte: nBu4N+ PF6-, Pt working electrode, Pt counter electrode, 55 behavior can be explained through the simultaneous one
Ag/AgCl reference electrode. c Irreversible oxidation. electron oxidation each at both phenothiazine units at the frist
redox potential of E00/+1 = 851 mV. The second oxidation can
The emission spectra of the dyads 8-13 are broad at range
be assigned to the irreversible formation of the diradical
from 443-517 nm. The dyads with pyridinyl acceptor show the
phenothiazinyl species, presumably in both phenothiazine
lowest energy emission and very similar maxima either at 517
60 units. The voltammogram of 8 with a 2,7-fluorene spacer
15 nm (10) or at 516 nm (9). The compounds with a electron rich
reveals only one single reversible oxidation potential with
spacer (furane derivative 12, thiophene derivative 13) present
perfect Nernstian behavior. In comparison to the symmetric
a very similar maximum of emission at 443 and 444 nm, and
phenothiazine dyads 9, 12 and 13, the phenothiazine units in
reveal an increase in energy emission comparative with the
the symmetric pyridazine bridged (11) and the 2,7-fluorene
electron poor–spacer (pyridine). Concomitantly, the Stokes
65 bridged (8) derivatives seem to be electronically decoupled.
20 shift is significantly increased from dyad 13 (9600 cm-1) to the
This is in good agreement with the presented data obtained
dyad 10 (13000 cm-1) and can be attributed to significant
from the DFT calculations, where no separation of the frontier
geometrical changes upon excitation from a highly nonplanar
orbitals could be observed in case of 11. On the other hand, a
ground state to a largely planarized excited state. 19 Hence, an
clearly separation of HOMO and LUMO was found while
electronic communication could be responsible for the
70 calculating the symmetrical, thiophene bridged phenothiazine
25 coupling of donor and acceptor in the exited state.
dyad 13.
According with cyclic voltametry two reversible anodic
oxidations can be found for the dyads 9, 10, 12 and 13 (Figure
3). In comparison with 10H-phenothiazine (E00/+1= 624 mV) 1,0

the first reversible one electron oxidations are shifted

0,5
30 annodically, except for the furane bridged derivative 12 which
is shifted slightly cathodically (E00/+1 = 608 mV). The anodical 0,0

shift values up to 270 mV in case of the 2,6-pyridine bridged

I [µA]

-0,5

9 (E00/+1 = 891 mV). The second oxidation occurs at a higher -1,0

potential, where the highest oxidation potential was observed
35 for the second redox step of 9 (E0+1/+2= 1276 mV). This can be -1,5

interpreted as a strong electronic coupling between the -2,0

phenothiazinyl units as a consequence of an extended -2,5

delocalization of the initially formed radical cation. Since the
1,4 1,2 1,0 0,8 0,6 0,4 0,2 0,0
2,5-pyridine bridged dyad 10 is not symmetrical at all, it is not
U [V]
40 surprisingly that two reversible oxidation processes are
observed. The first one (E00/+1= 736 mV) can be assigned to
Fig. 4 Cyclic voltommogram of 11, recorded in CH2Cl2.
the more electron-rich phenothiazine moiety located at the 2-
position of the central pyridine unit. The other phenothiazine, Since the phenothazine dyads 9 and 10 contain of a basic
connected at the electron-deficient 5-position of pyridine is 75 pyridine moiety, titration studies monitored by fluorescence
45 oxidized in a second redox step, occuring at E00/+1 = 1132 mV. spectroscopy were performed with trifluoroacetic acid (TFA)

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in methylene chloride (Figure 5). Generally, the protonation

of phenothiazine derivatives leads to the formation of radical 1,0
cations.1,20 As we recently reported, 10d titration studies of
phenothiazines with TFA in methylene chloride are possible 0,8

PL Int. at 517 nm [a.u.]

5 and reproducable. Both compounds 9 and 10 show similar
behaviour after the addition of increasing amounts of TFA.
0,6
The neutral compounds 9 and 10 display an emission at 517
nm and 516 nm, respectively. After the addition of 0.1 eq – 5
eq of TFA the emission is quenched in both cases. We assume 0,4

10 that first the pyridine units are protonated, leading to a species

with a very low band gap, as the LUMO is stabilized by 0,2

protonation. This species are nonfluorescent as there

apparently are effective paths available for non-radiative 0,0
excited-state deactivation, in line with energy gap law.21 Upon 0 1 2 3 4 5

15 further addition of TFA, the phenothiazine units are likewise Eq. of TFA

protonated, stabilizing the HOMO.

Fig. 6 Fluorescence signal of 9 at 517 nm plotted vs. the added
equivalents of TFA.
350

300
35 Conclusions
0 eq
0.1eq
0.2eq
In conclusion, we have presented the synthesis and electronic
250
properties of dumbbell-shaped phenothiazine dyads. The
PL intensity [a.u.]

0.3eq
0.5eq
200 1eq introduction of the heterocyclic bridge was easy accomplished
2eq
3eq by the Buchwald-Hartwig aryl amination. The symmetrical
5eq
150 40 systems 9, 12 and 13 show intense electronical coupling
between the redox-active phenothiazine units as shown from
100
the cyclovoltammetric spectra and DFT calculations.
50 Futhermore, we have shown that the fluorescence emmision of
derivatives 9 and 10 in CH 2Cl2 can be switched off by the
0 45 addition of TFA and on by neutralizing the sample solution.
350 400 450 500 550 600

Wavelength [nm]
Fig. 5 Emission spectra of 9 in presence of increasing amounts of TFA.
However, this process is reversible, since the neutralization
20 of the acidic sample with a base led back to the original
fluorescence signal .This marks out that both pyridine bridged
phenothiazines 9 and 10 possess tuneable fluorescence
properties upon protonation/deprotonation besides the
observed electronic communication between the phenothazine
25 moieties.
While plotting the intensity of the fluorescence signal at
517 nm of 9 versus the added equivalents of TFA one obtains
a exponential graph (Figure 6). (Hier könnte man dieses
Phänomen noch etwas diskutieren, wenn man eine log
30 Auftragung wählt, bekommt man eine recht gute Gerade mit
einem fir von r² = 0.98211).
The presented phenothiazine derivatives represent a new class
of tunable molecules, switchable by redox processes and by
the pH value in case of 9 and 10. Futher studies with more
emission harvesting phenothiazine derivatives are currently
50 underway.
Experimantal
General considerations
Reagents, catalysts and ligands were purchased reagent grade
and used without further purification. The used solvents were
55 dried and distilled according to standard procedures. 22 2,5-
Dibromofurane23 (6) and 9,9’-dihexyl-2,7-dibromofluorene24
(2) were prepared according to literature. Column
chromatography: silica gel 60, mesh 70-230. TLC: silica gel
plates. 1H and 13C NMR spectra: CD2Cl2, (locked to Me4Si).
60 The assignments of quaternary C, CH, CH 2 and CH3 have been
made by using DEPT spectra. Elemental analyses were carried
out in the Microanalytical Laboratories, Institut für
Pharmazeutische Chemie, Heinrich-Heine University,
Düsseldorf, Germany.
65 Fluorescence measurements (Perkin-Elmer LS-55) were
performed in dry and degassed CH 2Cl2 at room temperature.
To avoid re-absorption and re-emission effects the
concentrations were strictly kept below 1 µM. The solutions
were irradiated at approximately 10 nm less in energy than the
70 longest wave length absorption maximum.
Electrochemistry: Cyclic voltammetry experiments (EG &

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G potentiostatic instrumentation) were performed under argon
in dry and degassed CH 2Cl2 at room temperature and at scan
rates of 100, 250, 500, and 1000 mVs –1. The electrolyte was
Bu4NPF6 (0.025 M). The working electrode was a 1 mm
5 platinum disk, the counter-electrode was a platinum wire, and
the reference electrode was a Ag/AgCl electrode. The
potentials were corrected to the internal standard of Fc/Fc + in
CH2Cl2 (E00/+1 = 450 mV).25
General procedure (GP)
10 Under inert conditions anhydrous 10H-phenothiazine 1 (2.2
eq), bromo derivatives 2-7 (1 eq), Pd 2(dba)3.dba (0.03eq.),
PHtBuF4 (0.05 eq.), NaO tBu (2.3 eq.) and anhydrous 1,4-
dioxane were placed in a pressure tube. The reaction mixture
was stirred at 101 ºC for 19 h. After cooling to r.t., the
15 solution was diluted with deionized water, saturated Na 2SO3
solution and methylene chloride. The aqueous phase was
extracted with small portions of methylene chloride, the
combined organic phases were dried with anhydrous MgSO 4
and the solvents were removed in vacuo. The residue was
20 chromatographed on silica gel (hexane) to furnish the
products 8-13 as solids or resins.
3,6-[10,10’]Biphenothiazinyl-9,9-dihexyl-9H-fluorene (8)
This compound was synthesized according to GP and after
purification by flash-chromatography on silica gel (hexane) 8
25 (800 mg, 73 %) was obtained as a colourless resin. Mp. 227
°C. Rf (hexane/acetone 10:1): 0.51 1H NMR (CD2Cl2, 500
MHz): δ 0.76 (t, J = 7.0 Hz, 6H), 1.07 (m, 16H), 2.04 (t, J =
8.3 Hz, 4H), 6.27 (dd, J = 1.5 Hz, J = 8.0 Hz, 4H), 6.84 (m,
8H), 7.03 (dd, J = 2.0 Hz, J = 7.3 Hz, 4H), 7.39 (dd, J = 1.5
30 Hz, J = 8.0 Hz, 2H), 7.44 (d, J = 1.5 Hz, 2H), 8.02 (d, J = 8
Hz, 2H). 13C NMR (CD2Cl2, 125 MHz): δ 13.4 (CH3), 22.0
(CH2), 23.6 (CH2), 29.1 (CH2), 31.2 (CH2), 39.8 (CH2), 55.5
(Cquat.), 115.4 (CH), 119.3 (Cquat. ), 121.8 (CH), 122.1 (CH.),
125.6 (CH), 126.2 (CH), 126.5 (CH), 129.4 (CH), 139.7
35 (Cquat.), 140.0 (C quat.), 144.1 (C quat.), 153.7 (C quat.). IR (KBr) ν =
2953, 2925, 2853, 1592, 1483, 1461, 1442, 1305, 1259, 1237,
1121, 1043, 924, 825, 744, 673, 613, 546 cm-1. UV/Vis: λ max
(ε ) = 259 (164700), 280 (49600), 308 (35200). MS (MALDI)
m/z: 728.234 (M+ ). Anal. calcd. f. C 49H48N2S2: C 80.72, H
40 6.64, N 3.84, found: C 80.72, H 6.79, N 3.82.
10, 10’-Biphenothiazinyl-2,6-pyridine (9)
This compound was synthesized according to GP and after
purification by flash-chromatography on silica gel (hexane) 9
(1.72 g, 59 %) was obtained as a colorless solid. Mp.138 °C.
45 Rf (hexane/acetone 5:1): 0.45. 1H NMR (CD 2Cl2, 500 MHz):
δ 6.33 (d, J = 8.0 Hz, 2H), 7.21 (m, 9H), 7.39 (dd, J = 1.5
Hz, J = 7.5 Hz, 4H), 7.46 (dd, J = 2.0 Hz, J = 8.0 Hz, 4H). 13C
NMR (CD2Cl2, 125 MHz): δ 100.9 (CH), 125.2 (CH), 126.7
(CH), 127.6 (CH), 127.7 (CH), 133.1 (Cquat.), 138.5 (CH),
50 141.0 (Cquat. ), 155.2 (Cquat.). IR (KBr) ν = 1594, 1575, 1476,
1429, 1345, 1301, 1254, 1194, 1169,1124, 1087, 1033, 940,
861, 778, 752, 731, 695, 659, 635, 612, 546, 523 cm -1.
UV/Vis: λ max (ε ) = 251 (39000),288 (10900), 333 (17600).
MS (EI+ ) m/z (%): 475 (5, Mn+2 ), 474 (15, M n+1), 473.0 (30,
55 M+), 274 (20), 242 (35), 198 (100), 154 (23), 127 (8). Anal.
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calcd. f. C29H19N3S2: C 73.54, H 4.04, N 8.87, found: C 73.31,
H 3.86, N 8.82.
10, 10’-Biphenothiazinyl-2,5-pyridine (10)
This compound was synthesized according to GP and after
60 purification by flash-chromatography on silica gel (hexane) 10
(1.07g, 50 %) was obtained as a colourless solid. Mp. 220 °C.
Rf (hexane/acetone 5:1): 0.50. 1H NMR (CD 2Cl2, 500 MHz):
δ 6.29 (dd, J = 1.5 Hz, J = 8.0 Hz, 2H), 6.82 (dt, dJ = 1.5 Hz,
t
J = 7.5 Hz, 2H), 6.88 (dt, dJ = 1.5 Hz, tJ = 7.5 Hz, 2H), 7.01
65 (dd, J = 1.5 Hz, J = 7.5 Hz, 2H), 7.09 (m, 1H), 7.23 (dt, dJ =
1.0 Hz, J = 7.5 Hz, 2H), 7.37 (dt, dJ = 1.5 Hz, tJ = 7.5 Hz,
2H), 7.48 (m, 3H), 7.75 (dd, J = 1.0 Hz, J = 8.0 Hz 2H), 8.18
(m, 1H). 13C NMR (CD2Cl2, 125 MHz): δ 109.8 (CH), 115.7
(CH), 120.1 (Cquat. ), 122.3 (CH.), 125.8 (CH), 126.4 (CH),
70 126.6 (CH), 126.7 (CH), 127.4 (CH), 127.9 (CH), 130.0
(Cquat), 133.3 (Cquat), 140.0 (CH), 140.4 (Cquat), 144.0 (Cquat),
149.5 (CH), 155.1 (Cquat). IR (KBr) ν = 1602, 1584,
1551,1475, 1460, 1440, 1385, 1307, 1259, 1233, 1127, 1082,
1044, 824, 746, 621, 540 cm -1. UV/Vis: λ max (ε ) = 253
75 (107800), 283 (26400), 309 (26900).MS (MALDI) m/z:
472.941 (M+ ).Anal. calcd. f. C29H19N3S2.0.2 CH2Cl2: C 71.49,
H 3.99, N 8.57, found: C 71.47, H 4.30, N 8.38.
10, 10’-Biphenothiazinyl-3,6-pyridazine (11)
This compound was synthesized according to GP and after
80 purification by flash-chromatography on silica gel (hexane) 11
(346 mg, 35 %) was obtained as a yellow resin. Mp. 231 °C.
Rf (hexane/acetone 5:1): 0.32 1H NMR (CD2Cl2, 500 MHz): δ
7.04 (s, 2H), 7.16 (dt, dJ = 1.0 Hz, tJ = 7.5 Hz, 4H), 7.27 (dt,
d
J = 1.0 Hz, J = 7.5 Hz, 4H), 7.37 (dd, J = 1.5 Hz, J = 7.5 Hz,
85 4H), 7.52 (dd, J = 1.0 Hz, J = 7.5 Hz, 4H). 13C NMR (CD 2Cl2,
125 MHz): δ 120.1 (CH), 124.8 (CH), 125.3 (CH), 126.8
(CH), 127.5 (CH), 130.8 (C quat.), 140.8 (C quat.), 154.9 (C quat.).
IR (KBr) ν = 2967, 2371, 2345, 1774, 1725, 1655, 1627, 1578,
1533, 1509,1478, 1460, 1417, 1364, 1314, 1259, 1233, 1084,
90 1027, 947, 825, 803, 754, 695, 665, 623, 546 cm -1. UV/Vis:
λ max (ε ) = 253 (25600), 303 (10400). MS (MALDI) m/z:
474.9 (M+ ).Anal. calcd. f. C28H18N4S2.0.3 CH2Cl2: C 69.45, H
3.79, N 11.51, found: C 69.40, H 4.22, N 11.24.
10, 10’-Biphenothiazinyl-2,5-furane (12)
95 This compound was synthesized according to GP and after
purification by flash-chromatography on silica gel (hexane) 12
(800 mg, 30 %) was obtained as an orange resin. Mp. 200 °C.
Rf (hexane/acetone 5:1): 0.48 1H NMR (CD2Cl2, 500 MHz): δ
6.59 (s, 2H), 6.78 (d, J= 8 Hz, 4H), 6.95 (t, J = 7.5 Hz, 4H),
100 7.09 (t, J = 7.5 Hz, 4H), 7.13 (d, J = 8.0 Hz, 4H). 13C NMR
(CD2Cl2, 125 MHz): δ 108.2 (CH), 116.3 (CH), 122.1 (Cquat. ),
123.4 (CH.), 126.5 (CH), 126.8 (CH), 142.7 (C quat.), 144.8
(Cquat.). IR (KBr) ν = 1615, 1589, 1568, 1462, 1443, 1300,
1253, 1234, 1169, 1126, 1085, 1039, 986, 916, 825, 746, 718,
105 677, 661 cm-1. UV/Vis: λ max (ε ) = 252 (80700), 304 (8200).
MS (EI+ ) m/z (%): 464 (10, M n+2), 463 (21, Mn+1 ) 462.0 (48,
M), 236 (100), 198 (100), 154 (21). Anal. calcd. f.
C28H18N2OS2.0.1CH2Cl2: C 71.64, H 3.89, N 5.95, found: C
71.63, H 3.83, N 5.79.
110 10, 10’-Biphenothiazinyl-2,5-thiophene (13)
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ARTICLE TYPE
This compound was synthesized according to GP and after
purification by flash-chromatography on silica gel (hexane) 13
(250 mg, 52 %) was obtained as a yellow solid. Mp. 215 °C.
Rf (hexane/acetone 5:1): 0.45 1H NMR (CD2Cl2, 500 MHz): δ
5 6.91 (d, J = 8.5 Hz, 4H), 6.95 (d, J = 7.5 Hz, 4H), 7.06 (m,
2H), 7.10 (m, 8H). 13C NMR (CD2Cl2, 125 MHz): δ 116.9
(CH), 121.8 (Cquat.), 123.3 (CH.), 126.4 (CH), 126.5 (CH),
126.9 (CH), 141.7 (Cquat.), 143.3 (Cquat. ). IR (KBr) ν = 3439,
3067, 1589, 1556, 1461, 1442, 1302, 1251, 1234, 1198, 1168,
10 1128, 1042, 915, 814, 750, 712, 659, 631, 562 cm-1. UV/Vis:
λ max (ε ) = 256 (46300), 311 (5100). MS (EI+) m/z (%): 480
(17, Mn+2), 479 (20, Mn+1 ),478.0 (50, M), 279 (3), 247 (10),
198 ( M-278, 100), 154 (3), 127 (4). Anal. calcd. f.
C28H18N2S3.0.25 CH2Cl2: C 67.88, H 3.73, N 5.60, found: C
15 67.78, H 3.87, N 5.43.
Acknowlegments
The support of this work by the Deutsche
Forschungsgemeinschaft DFG (Priority program 1181), the
Deutscher Akademischer Austauschdienst DAAD (scholarship
20 for L. N. P.), and by the Fonds der Chemischen Industrie is
gratefully acknowledged. The authors also cordially thank
Dr. Stefan Beutner for valuable discussions and the
BASF AG for the generous donation of chemicals.
Notes and references
a
25 Institut für Organische Chemie und Makromolekulare Chemie,
Heinrich-Heine-Universität Düsseldorf, Universitätsstr. 1, 40225
Düsseldorf, Germany. Fax: +4902118114324; E-mail:
ThomasJJ.Mueller@uni-duesseldorf.de
b
Babes-Bolyai University Cluj-Napoca, Faculty of Chemistry and
30 Chemical Engineering, Arany Janos Str. no.11, Cluj-Napoca, 400428
Romania
† Electronic Supplementary Information (ESI) available: Detailed
experimental procedures, and copies of 1H and 13C NMR spectra of
compounds 8–13; cyclovoltammetric and flourescence spectra of 8-13;
35 atomic coordinates of the calculated structures of 11 and 13.See
DOI: 10.1039/b000000x/
‡ Footnotes should appear here. These might include comments relevant
to but not central to the matter under discussion, limited experimental and
spectral data, and crystallographic data.
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