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’Jawaharlal Nehru Centre, Indian Institute of Science Campus, Bangalore, India, ’Department of Physics,
Indian Institute of Science, Bangalore 560 012, India, and ’Department of Inorganic
and Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India
SYNOPSIS
140/90 scanning model, using Co K,( X = 1.791 A) ylene chloride, until the washings are colorless, to
radiation and a 2 deg/min scanning rate. The pow- remove the unreacted starting materials. The final
dered complex is made into pellets ( 8mm dia, 2 mm product is dried at 40°C in a vacuum oven for 15 h.
thick), under 4 kbar pressure, and the electrical re-
sistivity data are taken using a conventional four
Platinum (II)/ 1,4-Diaminoanthraquinone
probe (Vanderpauw) DC technique, with increas-
ing and decreasing temperatures, in the range Recrystallized 1,4-diaminoanthraquinone(0.26 gm)
300-30 K. is dissolved in dimethylformamide (25 mL) .To this,
High pressure studies have been performed, using platinum (11)chloride (0.36) is added and is left for
a 4 mm tip Bridgman anvil setup. Pressure is gen- 1 h. The precipitate of the complex is washed with
erated by a hydraulic press, supplied by AIMIL India acetone, water, and methylene chloride, until the
Ltd., Bombay. For the precision control of the oil washings are colorless, and is dried under vacuum
flow, a needle valve is provided. The oil pressure is at 40°C overnight. The palladium complex is pre-
measured by a Heise gauge (0-1000 psi), with a res- pared in a similar manner, using palladium dichlo-
olution of 1psi (pounds per square inch). The room ride. Since the yield is poor, the data on these com-
temperature calibration of the generated pressure plexes could not be obtained.
has been performed using the phase transitions of Nickel, silver complexes, and complexes of cop-
bismuth and ytterbium. per, starting with copper ( I ) chloride and copper
(11) chloride, are prepared using the method re-
ported earlier.”
Synthesis of Copper (II)/ 1,4-
Diaminoanthraquinone Complex
1,4-diaminoanthraquinone(1.00 gm) is added to a RESULTS AND DISCUSSION
solution of copper (11)nitrate trihydrate (0.769 gm),
dissolved in dimethyl formamide (25 mL). The The solubility of these complexes is extremely low,
black precipitate formed is filtered and is washed even in solvents such as DMSO, making the char-
successively with water, acetone, and methylene acterization difficult. The molecular weight could not
chloride several times, until the washings are col- be obtained for the same reason.
orless, to remove unreacted starting materials. The The elemental analysis and the corresponding
product is dried a t 40°C in a vacuum oven for about empirical formulae of the complexes are obtained
15 h. from C,H,N, and metal percentages. The percentage
of oxygen is calculated to be the remainder after the
percentages of the other elements are determined.
Complex of Cobalt (II)/ 1,4-
The details are shown in Table I.
Diaminoanthraquinone
The X-ray powder diffraction pattern of these
Cobalt (11) chloride hexahydrate (0.5 gm) and tri- complexes shows them to be polycrystalline with two
ethylamine (0.84 gm) are added to a solution of 1,4- major d-spacings common in all complexes (Figs. 1
diaminoanthraquinone (0.5 gm) , dissolved in di- and 2). The most intense diffraction peak corre-
methylformamide (25 mL) . The black precipitate sponds to a d-spacing of 11 8, and of 3.2 A. The
formed is washed with acetone, water, and meth- crystallite sizes, computed for these complexes using
Table I Elemental Assay and Empirical Formula for the 1,4-DAAQ Metal Complexes
Metal C H N
Salt % % % 0“ Metal % Emperical Formula
a Calculated to be the remainder after the percentages of the other elements are determined.
PROPERTIES OF METAL-ANTHRAQUINONES 2 173
1
Figure 1 X-ray powder diffraction of Copper complex
( a ) Cu(I1) nitrate, ( b ) Cu(1) chloride, and ( c ) Cu(I1)
chloride.
0
the Scherrer formula,'' are presented in Table 11.
This allows for computation of the average number N
of repeating units per crystallite, obtained using the H
crystallite size and d -spacing."
Figure 3 Ln p vs. ( T )-”* plots of copper complexes prepared from ( a ) copper ( I ) chloride,
( b ) copper (11) nitrate, and ( c ) copper (11) chloride.
has gone into the system in obtaining the complex. of absolute temperature (Fig. 4).For semiconduct-
It is clear from Table I1 and Figure 3 that the com- ing materials, these plots should yield straight lines
plexes containing more copper have greater con- over the given temperature range, obeying the equa-
ductivity. Surprisingly, complexes prepared with tion p = poexp( E / 2 k T ) , where p is the resistivity
copper chloride show a complete absence of chlorine, at absolute temperature T, po is a constant, and E
as confirmed by several tests for chlorine. is the energy gap. In this case, it was found that such
For silver and cobalt complexes, measurements a simple relationship does not hold good.
are performed down to 77 K. In these complexes, Several models have been proposed to account
the resistance is of the order of Mega ohms or larger for the electronic properties of the various groups
below 77 K. For other complexes, the measurements of polycrystalline materials.22However, the concept
are carried out until 30 K. In order to interpret the of localized states at the Fermi level is common to
data, In ( p ) has been plotted against the reciprocal all models; the electronic charge transport critically
I4t
21 I I I I I I I I I I I I I I I I I
0.24 0.28 0 -32 0.36 0.40
+( K-lk)
Figure 5 Ln p vs. ( T ) of nickel and copper complexes.
depends on it. The semiconducting behavior is near the mobility edges and ( 2 ) tunneling conduc-
driven by the minimal activation energy for free tion near the Fermi level (when tunneling is re-
charge carrier to go through the mobility gap. A large stricted to seek centers, which lie energetically closer
enough thermal agitation is necessary for this pro- and within the range kT).This is the Variable-
cess to hold, and at low temperatures, other mech- Range-Hopping process, described by Mott and
anisms become important. The dc conductivity does Davis, 23 and this process has the following relation
not follow a simple exponential law. As the temper- for dc conductivity
ature decreases, it is postulated that conduction c = Const. [ ( T o /T ) l’l+n]
proceeds through two kinds of hopping among lo-
calized states near the Fermi level: (1) thermally- where n = 3, 2, or 1,depending on the dimensionality
assisted tunneling between the localized gap states of the conducting system. T o is a constant, which
c
C
b > +*++
++++ + +++-r
++ +++
++ +++ ++
s+ ++
+++ +++++++
+ ++++ ++
+
,++++ ++
** *
% **
**
I I I I I I I
0.24 0.26 0.28 0.30 0.32
+
+
-2.0/ + + + + +
+ + + + + + + +
-2.d I I I I I
0 1 2 3 1 5
Pressure (GPal
Figure 7 Normalized resistivity as a function of pressure. (0)
copper complex and ( + )
cobalt complex.
depends on the details of the model, is always in- carriers excited fully to the extended states, but by
versely proportional to the density of states at the the hopping of carriers excited to the localized states
Fermi level, and is assumed to be energy indepen- near the mobility edge.
dent. Pressures up to 6 GPa have been applied to study
We find that the data is in general agreement the variation of resistivity of the sample with pres-
with the above model. The conductivity measure- sure. The resistivity of the complexes generally de-
ments of these complexes show that the temperature creases with pressure in the beginning and later re-
dependence satisfies the relation l n ( p ) K mains constant. This behavior of resistivity varia-
(Figs. 5 and 6 ) . Thus, the carrier transport process, tion with pressure has been observed in many
studied by the temperature dependence of conduc- organic conductor^,^^ and has been explained on the
tivity, shows that conduction is not governed by basis of the molecular orbital overlap picture, where
01 +
1
t
+o
-0.6
-
Q
\
a
+ OOoo
-
t
+ O 00
+ 0
+
-C -Oa8
L5 + OO n
+
-l.L
0
I 1
2
+
++ , + + + + + ++ 1
L
I
6
I
Pressure ( GPa l
Figure 8 Normalized resistivity as a function of pressure. ( 0 )silver complex and ( + )
nickel complex.
PROPERTIES OF METAL-ANTHRAQUINONES 2 177
with increasing pressure, the overlap between ad- 6. L. W. Shacklette, R. L. Elsenbaumer, R. R. Chance,
jacent molecules increases, resulting in enhanced H. Eckharot, J. E. Frommer and R. H. Baughman, J .
conductivity. As the pressure is further increased, Chem. Phys., 75,1919 ( 1981).
the coulomb repulsive forces result in the levelling 7. K. K. Kanazawa, A. T. Daiz, W. D. Gill, P. M. Grant,
G. B. Street, G. P. Gardini and J. F. Kwak, Synth.
off of the overlapping. If the steric hinderances and
Met., 1,329 (1980).
structural distortion become important, the resis-
8. D. Wohrle, Adu. Polym. Sci., 4 7 , 50 (1983).
tivity may slightly increase at high pressures. This 9. R. S. Norh, P. M. Kuznesof, K. J. Wynne, M. E. Ken-
is the general behavior observed in the cobalt com- ney, a n d P . G. Srebenmann, J . Am. Chem. SOC.,1 0 3 ,
plex (Fig. 7 ) , the silver complex (Fig. 8 ) , and the 4371 ( 1981).
nickel complex (Fig. 8).For the copper complex also, 10. K. F. Schoch, B. R. Kundalkar, and T. J. Marks, J .
somewhat similar behavior is observed, except that Am. Chem. SOC.,101,7071 (1979).
the steric hinderances start dominating a t much 11. Oh-Kilmin, T. H. Yoon, and D. Mcdermitt, J . Chem.
lower pressures. Similar behavior of resistivity with SOC.Chem. Commun., 1 1 , 740 (1989).
pressure at high pressures is observed by Bentley 12. Wegner and G. Angew, Chem. Int. Ed. Engl., 20,361
and D r i k a m e ~in
- ~many
~ alkaline metals and organic (1981).
13. J. E. Frommer, Acc. Chem. Res., 2 , 19 (1986).
semiconductors.
14. G. E. Holdcroft and A. E. Underhill, Synth. Met., 1 0 ,
In conclusion, the complexes of 1,4-diaminon-
427 (1985).
athraquinone, formed with cobalt, nickel, copper, 15. S. Minomura, Ed., Solid State Physics under Pressure,
and silver, are semiconducting, and exhibit variable D. Reidel, Tokyo, 1985.
range hopping transport a t low temperatures (30 K 16. H. A. Pohl, A. Rembaum, and A. Henry, J . Am. Chem.
to 300 K ) and upon the application of hydrostatic SOC., 84, 2699 ( 1962).
pressure, conductivity increases and reaches a sat- 17. Y. Harada, Y. Maruyama, and I. Shirotani, Bull. Chem.
uration value. SOC.Jpn., 37,1378 (1964).
18. R. S. Bradly, J. C. Grace, and D. C. Monro, Trans
The authors are grateful to the Department of Science Farady SOC.,46, 776 (1962).
and Technology, Government of India, New Delhi, India, 19. G. K. Rickel, Macromolecules, 2 2 , 1517 (1989).
for financial assistance. 20. B. D. Cullity, in E. Reading, Elements of X-Ray Dif-
fraction, 2nd Ed, Addison-Wesley, Massachusetts
(1978).
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