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Benzene Bis(diazocyanides)Чthe First Acceptors of the Inverse Wurster Type for Conductive Organic Materials.

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introduced by syringe and the temperature maintained at 100°C for 2 hours.
After cooling to room temperature, the solvent was removed in vacuo. The
resulting residue was taken up in 3 N HCI (10 mL) and refluxed for 10 hours.
The pH was then carefully adjusted to 12 with NaOH pellets. After extraction
with CHCI, (2 x 50 mL), drying of the combined organic phases, and evaporation of the solvent, the pure mono N-alkylated tetraazamacrocycle was ohtained, generally as an oily residue.
Modified Procedure: direct alkylarion of the phosphonium salt 2
The suspension of 2 in toluene was treated with the required alcohol (1.O mmol)
(Scheme 1). the solvent was removed and replaced by dry DMF (20 mL), an
excess of Na,CO, was added, and the mixture was heated at 100°Cfor 2 hours.
The subsequent work-up was as described above. All the mono N-alkylated
tetramines gave satisfactory IR, MS, and 'H NMR data.
Received: November 12, 1990 [Z 4277 IE]
German version: Angew. Chem. 103 (1990) 563
NY
NCKCN
N,
1
-2.92
CN
I
/N
N'
'N
2
3
4
-2.51
-2.18
-2.30
Scheme 1. Organic electron acceptors and their LUMO energies calculated with
MNDO-AM1 for the parent compounds.
[l] a) K. E. Krakowiak, J. S. Bradshaw, R. M. Izatt, J. Org. Chem. 55 (1990)
3364; b) T. A. Kaden in F. Vogtle, E Weber (Eds.): Hosr Guest Complex
Chemistry Yo/.111, Springer, Berlin 1984, p. 157; c) I. M. Helps, D. Parker,
T. R. Morphy, J. Chapman, Tetrahedron 45 (1989) 219.
[2) a) T. I. Atkins, J. E. Richman, Tetrahedron Letr. 52 (1978) 5149; b) J. E.
Richman, J. J. Kubala, J. Am. Chem. Soc. 105 (1983) 749; c) J. E. Richman,
R. B. Flay, 0. D. Gupta, ACS. Symp. Ser. 171 (1981) 271; d) J. M. Dupart,
A. Grand, J. G. Riess, J. Am. Chem. SOC.108 (1986) 1167; e) F. Bouvier,
J. M. Dupart, A. Grand, J. G. Riess, Inorg. Chem. 26 (1987) 2090.
[3] H. Handel, H. Chaumeil, European patent, 88400839.2. (1988), CNRS.
[4] The P=O derivative of "3434" exhibits a "P NMR signal at 6 = - 18.4;
for other phosphorylated macrocycles, see ref. [Zc].
Benzene Bis(diaz0cyanides)-the First Acceptors
of the Inverse Wurster Type for Conductive Organic
Materials**
By Hartmut Almen, Thomas Bauer, Siegfried Hiinig,*
Vladimir KupEik, Uwe Langohr, Tobias Metzenthin,
Klaus Meyer, Harald Rieder, Jost UIrich von Schiitz,
Ekkehart Tillmanns, and Hans Christoph Worf
Tetracyanoquinodimethane(TCNQ)['] and N,N'-dicyanoquinonediimine(DCNQI)[21 and derivatives thereof (1 and 2
respectively) have proved to be the most important organic
electron acceptors for charge-transfer(CT) complexes or
radical anion salts with electrical conductivity. Both types of
compound form two-stage reversible redox systems and thus
belong to the Wurster type, in which the defined acceptor end
groups are connected to the six membered 7~ ring system in
such a way that the oxidized stage has quinone character.13]
We wondered whether the as yet unused two-stage redox
systems of inverse Wurster type, that is, with aromatic oxidized stagec3](see Scheme 2), is also suitable as acceptor for
conductive organic materials.
The benzene-I ,4-bis(diazocyanides)3 (dicyanazobenzene
[DCNAB]) appeared to be promising candidates, since the
[*I
[**I
Prof. Dr. S. Hiinig, Dipl.-Chem. T. Metzenthin
Institut fur Organische Chemie der Universitat
Am Hubland, W-8700 Wiirzburg (FRG)
Dip].-Phys. U. Langohr, Dip1.-Phys. K. Meyer, Dipl.-Phys. H. Rieder,
Dr. J. U. von Schiitz, Prof. Dr. H. C. Wolf
3. Physikalisches Institut der Universitat Stuttgart
Dip1.-Min. H. Almen, Dipl.-Min. T. Bauer, Prof. Dr. E. Tillmanns
Mineralogisches Institut der Universitat Wiirzburg
Prof. Dr. V. Kuptik
Mineralogisch-KristallographischesInstitut der Universitat Gottingen
This work was supported by the Volkswagen-Stiftung and the Fonds der
Chemischen Industrie. T Mefrenrhin thanks the Fonds der Chemischen
Industrie for a study grant.
Angew. Chem. Int. Ed. Engf.30 (1991) No.5
0 VCH
LUMO energy as calculated by MNDO-AM1 141 (Scheme 1)
of the almost planar structure lies in a similarly favorable
range to the tried and tested compounds 1 and ZtS1It was,
however, doubtful whether the orbital symmetry of 3, which
is vastly different from that of the quinones, would allow the
stacking in the crystal essential for conduction.
We now use the first examples, which also include naphthalene-I ,4-bis(diazocyanide) 4, to show that these compounds, besides having spectroscopically detectable radical
anionst61,not only form fully reversible two stage redox systems of the inverse Wurster type,L3]but are also potent acceptors in conductive CT complexes and radical anion salts.[''
Table 1 shows that the redox potentials of 3 and 4 lie in the
same region as those of TCNQ, l(R = H) and DCNQI, 2
(R = H). The semiquinone formation constants of Ig KSEM
=
Table 1. Redox potentials E, and E, determined by cyclic voltammetry (Pt
electrode vs. Ag/AgCI/CH,CN, electrolyte nBu,NBF,) and semiquinone formation constants Ig KSEMof 1-4 (see also Scheme 2.)
3a
3b
3c
R'
R2
R3
E, [V]
Me
H
CI
H
H
H
Me
H
Cl
- 0.15
4
1 (R = H) 1.51
2 (R = H) [5]
- 0.15
+ 0.07
- 0.01
- 0.28
- 0.25
E,[V]
IgK,,,
+0.20
5.92
6.10
6.82
6.49
11.42
10.75
+ 0.22
+ 0.47
+ 0.32
+ 0.39
+ 0.39
5.92-6.82 are still very large, although a factor of ca. lo4
smaller than in TCNQ and DCNQI. That is predictable,
because the Coulomb repulsion in the longer systems of 3
and 4 (they contain two more atoms) has less effect on the
gain of electrons.IS1Surprisingly, a higher acceptor capacity
(LUMO = 2.30 eV) is calculated for 4 than for 3b, which is
also reflected in a higher reducibility (E2 = 0.32 V). The
opposite is true for the transition from DCNQI to the corresponding naphthalene d e r i ~ a t e . ~ ~ '
Furthermore, the MNDO-AM1 calculations show that
during the reduction (OX + SEM + RED) 3b indeed assumes progressively a quinoid structure. Thus the exocyclic
Car,,-N single bond becomes shorter on gain of electrons
(144 (OX) via 138 (SEM) to 133 pm (RED)); the bond between C2 and C3 also shortens (139 (OX), 137 (SEM),
135 pm (RED)). The corresponding experimentally determined bond lengths in DCNQI are 130 (C-N) and 134 pm
(C =C).'9'
On combining solutions of 3 or 4 with solutions of tetrathiofulvalenes(TTF) or tetramethyltetraselenafulvalenes-
VerfagsgesellschajtmbH, W-6940 Weinheim. 1991
+
0570-08333/91/0505-05618 3.50+ ,2510
561
..~e
..
Yje
C
II
N,
N,N
R'
Ill
CI
N
+
@"+
R3&;
NN
,
R3pR'
kN
R*
N
N--N
ZN
I
I
I1
C
c.
!
C
II
C
Ill
N
II
RED
u = 120 S cm-').[131 A preliminary picture could be obtained by synchrotron-X-ray radiation. Figure 1 shows the
projection onto the y z plane. Although the poor quality of
the crystals, and therefore of the crystal data, has not yet
enabled the determination of the atomic coordinates in the x
direction with satisfactory accuracy, the small lattice constant of 3.76 A allows only one molecular unit per unit cell,
so that the separate arrangement of donor and acceptor
stacks is assured.
The temperature dependence of the conductivity of this
compound (Fig. 2, top) corresponds with that of a metal-like
semiconductor with a small band gap of AE z 40 meV. This
value results from the charge carrier concentration C, which
could be followed in the electron spin resonance experiments
(Fig. 2, bottom) down to very low temperatures. The small
N
I1
CI I
ox
SEM
Scheme 2. Redox systems 3 and 4.
(TMTSF), black CT complexes crystallize, the majority of
which have a high powder conductivity (Table 2), so that
they compare well with the CT complexes of TCNQ['O1 and
DCNQI.["]
I 1
lo'
U
IS crn-'~
ld
Table 2. Powder conductivitiesu of CT complexes with 3 or 4 as acceptor.
[S cm-'1
Acceptor
Donor [a]
m:n [b]
u
3a
3b
3b
3c
3c
3c
3c
4
4
TTF
TTF
TMTTF
DBTTF
TTF
TMTTF
TMTSF
TTF
TMTTF
1:l
1:l
1:l
1:2
1:l
120 [c]
3 x lo-'
3x
[c]
2 10-5
2 10-4
1 x 10-2
1.2
1 :2
1:l
1:l
4x
1
1
[a] TMTTF = tetramethyltetrathiafulvalene, DBTTF = dibenzotetrathiafulvalene.[b] Ratio Acceptor:Donor derived from elemental analysis.[c] Single
crystal conductivities.
lo-'
.
150
175
200
225
TWI
Thus segregated donor and acceptor stacks can also be
assumed for the new CT complexes.*121This characteristic
arrangement for conductive CT complexes was confirmed by
a crystal structure analysis of the 3a/TTF complex (for which
250
275
300
Fig. 2. Top: Temperature dependence of the single crystal conductivity of 3a/
TTF. All crystals break at T < 215 K. Bottom: Normed spin carrierconcentra, x function of the temperature.
tion C = ~ T / 3 0 0 ~ , ,as
ESR signal width of 2 Gauss at 300 K is a strong indication
that the 3a stack is the dominant factor in conductivity,
because when the charge carriers in such complexes come
into contact with sulfur atoms of the TTF stack, the signal
widths are usually at least 6-100 Gauss.['41
Fig. 1 . Structure of 3a/TTF in the crystal; projection along [loo]; space group
P l , a = 3.76, b = 6.54, e = 18.12 A, u = 87.0, p = 85.8, y = 81.7".
562
0 VCH VeriagsgeseiischaflmbH.
W-6940 Weinhelm, 1991
Example 5 shows that conductive radical ion salts can also
be formed from the new acceptor types. This proves that
acceptors of the inverse Wurster type can assume the role of
those of normal Wurster type used till
These results
have prompted us to synthesize further derivatives of 3 and
to test them in conducting materials.
0S70-0833/91JOS05-0562$3.50 + ,2510
Angew. Chem. Inl. Ed. Engl. 30 (1991) No. 5
Experimental Procedure
Reaction of 3a with TTF: 21 mg (100 pmol) 3a in a mixture of 0.5mL dry
dichloromethane and 0.5 mL acetonitrile is treated at room temperature with a
solution of 30 mg (147pmol) TTF in 1 mL acetonitrile. Immediately a dark
precipitate forms. After 45 min at 0°C. filtration and drying over silica gel
yields 36 mg (86%) green-golden needles. M.p. 146°C (dec.). IR(KBr):
v = 2100cm-'. UV/vis (CH,CN): d,.,(lg&) = 226(sh,3.989), 321(4.256),
360(4.416),572 nm(2.739).
have been prepared in this way, especially for the study of
synlanti
Ar-NH2
-
0
Q
CN
ArN,
Received: December 7, 1990 [Z4312IE]
German version: Angew. Chem. 103 (1991)608
CAS Registry numbers:
3a, 132556-13-2;
3 a . TTF, 132566-16-6;
3b, 132619-62-6;
3 b . TTF, 1326193 c . DBTTF, 132566-17-7;
63-7;3 b . TMTTF. 132619-64-8;3c, 132566-14-4;
3~ ' TTF, 132590-84-2;
3 ~TMTTF,
.
132590-85-3;
3 ~TMTSF,
.
132566-18-8;
4, 132566-15-5;
4 . TTF, 132566-19-9;
4 ' TMTTF, 132566-20-2.
~
[I] a) J. Ferraris, D. 0. Cowan, V. Walatka, Jr., J. H. Perlstein, J Am. Chem.
SOC.95 (1973)948; b) D. S. Acker, W. R. Hertler, ibid. 84 (1962)3370;
c) L. B. Coleman, M. J. Cohen, D. J. Sandman, F. G. Yamagishi, A. F.
Garito, A. J. Heeger, Solid State Commun. f2 (1973)1125.
[2]S. Hiinig, Pure Appl. Chem. 62 (1990)395;P. Erk, S.Hiinig, Adv. Muter.,
in press.
[3]K. Deuchert, S. Hiinig, Angew. Chem. 90 (1978)927;Angew. Chem. Int.
Ed. Engf. 17 (1978)875.
[4j a) M. J. S. Dewar, E. G. Zoebisch, H. F. Healy, J. J. P. Stewart, J Am.
Chem. SOC.107 (1985)3902;b) QCPE Program No. 527.
[5]A. Aumiiller, S. Hiinig, Liebigs Ann. Chem. 1986, 165.
[6] I. Ya. Kachkurova, L. D. Ashkinadse, U. Kh. Shamsutdinova, L. A. Kazitsyna, Zh. Org. Khim. 23 (1987)1831.
[7]Presented in part at ICSM '90 ( I n / . Con$ Sci. Teehnol. Synth. Met.), September 1990,Tiibingen.
[8j a) S. Hiinig, D. Scheutzow, P. Carsky, R. Zahradnik, J. Phys. Chem. 75
(1971)335; b) S. Hiinig, H. Berneth, Top. Curr. Chem. 92 (1980)1-44.
[9]G. D. Andreetti, S. Bradamante, P. C. Bizzarri, G. A. Pagani, Mol. Cryst.
Liq. Cryst. 120 (1985)309.
1101 R. C.Wheland, J. L. Gillson, J. Am. Chem. Soe. 98 (1976)3916.
[ll]A. Aumiiller, P. Erk, H. Meixner, S. Hiinig, J. U. von Schiitz, H.-P.
Werner, Liebigs Ann. Chem. 1987, 997.
[12]A CT complex with mixed donor/acceptor stacks was also obtained E.
Tillmanns, S. Hiinig, T. Metzenthin, H. Rieder, J. U. von Schiitz, H. C.
Wolf, Acta Cryslallogr. Sect. C., in press.
[13]S. Hiinig. P. Erk, E. Giinther, H. Meixner, T. Metzenthin, J. U. von Schiitz,
M. Bair, H.-J. GroL3.U. Langohr, S. Soderholm, H.-P. Werner, H. C. Wolf,
E. Tillmanns, Synth. Met., in press.
I141 J. Tomkiewicz, Phys. Rev. B 19 (1979)4038.
[15] In 1,4-bis(tricyanovinyI)benzene a two-stage redox system of the inverse
Wurster type is also present, whose redox potentials are similar to those of
compound 3. Neither stoichiometry nor physical properties are known for
its TTF salt, which exists in at least two phases: F. Wudl, P.-M. Allemand,
P. Delhaes, 2. Soos, H. Hinkelmann, Mot. Cryst. Liq. Cryst. 171 (1989)
179-182.
1
The arene bis(diaz0cyanides) 4 could indeed be synthesized from some p-phenylenediamines 2 via the bis(diazonium) salts 3L51
(Eq. (b)). It was, however, necessary to isolate
the labile and occasionally explosive salts 3 and to extract the
diazocyanides 4, which form in the reaction with cyanide,
continuously into chloroform in order to suppress a further
~ * ~ under
l
addition of cyanide at the nitrile g r ~ u p . L ~Even
these conditions the yields are only 10- 50%. A more serious
disadvantage is that some bis(diazonium) salts (e.g. 3d,
R' = R3 = Me; R2 = R4 = H) can be isolated only in impure state or sometimes not at all.
a3
NH2
N2
I
QN2
2
3
"'*"
NC
I
N
NaCN/H20
CHCl3
ZN
RS
R2
N.
'Y
CN
4
a,R'-RA = H I b,R' =R' =H.R' =R3=CI ;C, R'R'
A New Route to Aromatic Diazocyanides**
By Siedried Hunig* and Tobias Metzenthin
Benzene-I ,4-bis(diazocyanide) and naphthalene-I ,4-bis(diazocyanide) belong, as the previous communication
shows,I'I not only to the reversible two-stage redox systems,
but also to the first acceptors of the inverse Wurster type for
conductive organic materials.L2I We therefore required a flexible synthesis route for this class of compounds.
The problem appeared to be very simple to solve along the
lines of the classical synthesis of arene diazocyanides 1 ac(Eq. (a)). Many compounds
cording to Hantzsch et
I'[ Prof. Dr. S. Hiinig, Dipl.-Chem. T. Metzenthin
Institut fur Organische Chemie der Universitat
Am Hubland, W-8700Wiirzburg (FRG)
[
*
'
I This work was supported by the Volkswagen-Stiftung and the Fonds der
Chemischen Industrie.
Angew. Chem. Int. Ed. Engl. 30 (1991) No. 5
0 VCH
(4
Ar-N=N-CN
syn /anti
I
ICH), ,R3= R4= H
Therefore we searched for a synthesis of 4 in which the
isolation of the bis(diazonium) salts was unnecessary and the
diazocyanide function could be formed without further reaction with excess cyanide. We describe now a general route to
the diazocyanides 1, which can also be applied in the case of
the difunctional derivatives 416] without these difficulties.
This route requires first the nitrosation of N-aryl amides 5
to the N-nitroso derivatives 6 by known methods,"' whose
rearrangement to the 0-aryldiazo esters 7 was studied thoroughly, in particular by Huisgen et al.[*l The thermal rearrangement in the presence of trimethylsilylcyanide in an organic solvent affords the desired diazocyanides 1, in good
yields after their easy separation from the trimethyl esters 8
(e.g., for 4-~hlorobenzenediazocyanide,[4"1
60 % after sublimation; see Scheme 1).
The conversion 7 + 1 is apparently very rapid, because the
competing intramolecular reaction of the methyl group in an
o-substituted arene, which leads smoothly to indazoles, is
not observed. (The same is true for 10 -+ 4.)
Verlagsgesellschajt mbH, W-6940 Weinheim, 1991
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0570-0833/9ll0505-0563 $3.50 .25/0
563
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