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International Conference on Chemical and Environmental Sciences (ICCES'2012) June 16-17, 2012, Bangkok
1
H- NMR, Electronic properties and
conductivity studies of (E)-1,5diphenylcarbazone uranyl acetate (VI)
P
P
P
P
[{(Ar)NNHCONN(Ar) 2}UO2(Ac)(EtOH)]
(Ar = C6H5, acc = CH3COO ) Complex
R
R
R
R
R
R
R
R
R
R
Salem El-t. Ashoor
1B
Different optical conductivity enhancement (OCE) protocols
to eliminate charging during ultra low energy SIMS profiling
of semiconductor and semi-insulating materials using
interaction between the material and the primary ion beam by
some cases (Si1-xGex, phosphorus implanted silicon) was
archived by Morris et al.7 Again conductivity of ZnCoO
diluted magnetic semiconductor was examined in room
temperature ferromagnetic semiconductor, Cu-codoped
ZnCoO film are obtained by sol-gel method. By hall-effect
measurement a p-type conductivity was observed for the Cucodoped films, the hole concentration increases with the
increase in Cu concentraton.8 The conductivity of the glasses
have been studied over ranges of compositions and frequency
by Kanchan in 2009 and his group9 using transport properties
and relaxation studies in BaO substituted Ag 2 O-V 2 O 5 -TeO 2
glass system and how the increases conductivity while
activation energy decreases.
Electronic structure of layered uranium compounds from
photoemission spectroscopy
was showen tetragonal
compounds and anti-ferromagnet and ferromagnet and also
they observed intriguing electronic structure for the
complexes were synthesized by Arko and his group.10
Energetics of intrinsic point defects in uranium dioxide
from electronic structure calculations, the computational
approach integrates high accuracy initio electronic structure
calculation and thermodynamic analysis supported by
experimental data 11
Abstract— A range of new compounds such (E)-1,5diphenylcarbazone
uranyl
acetate
(VI)
[{(Ar)NNHCONN(Ar) 2 }UO 2 (acac)(EtOH)] (Ar = C 6 H 5 , acac =
CH 3 COO ) complex counting the chelating tertaamine and oxygen
has been prepared, and structurally characterized in several cases.
Well-defined
(E)-1,5-diphenylcarbazoneurinailacetate
[{(Ar)NNHCONN(Ar) 2 }UO 2 (acac)(Et 2 OH)] Ar = C 6 H 5 , acac =
CH 3 COO) (Ar)NNHCONN(Ar) 2 }UO 2 (acac)(Et 2 OH)] (Ar = C 6 H 5 ,
acac = CH 3 COO ) was obtained by stoichiometric addition of [(Ar)
NHNHCONN(Ar) 2 } 2 } (Ar = C 6 H 5 ) and {UO 2 (acac) 2 } in ethanol at
reflex temperature. HNMR, IR, CHN, Electronic properties and
conductivity studies have been obtained for this compound.
Electronic Properties by using hyperchem program study has been
improved for this compound such bond distance and then this
compound was defining as electric conductivity also did prove to be
useful use for conductively compound.
P
P
P
P
P
R
Keywords— Acetate, (E)-1,5-Diphenylcarbazone, Conductivity,
Electronic Properties And, Tertaamine Uranyl.
I.
P
INTRODUCTION
T
HE Interest area, Schiff bases ligands have been focused
in the last ten years ago specially with transition metal to
forward complexes, due multiple implication.1-5 Oxygen and
nitrogen as tetra-dentate attached to cobalt acetate has been
reported by Aurel et al.6 and catalytic activity leads to the
obtention of benzoquinone and diphenoquinone products.
Different optical conductivity enhancement (OCE) protocols
to eliminate charging during ultra low energy SIMS profiling
of semiconductor and semi-insulating materials using
interaction between the material and the primary ion beam by
some cases (Si1-xGex, phosphorus implanted silicon) was
archived by Morris et al.7 Again conductivity of ZnCoO
diluted magnetic semiconductor was examined in room
R
R
R
R
R
R
R
P
4B
P
P
II. EXPERIMENTAL
A. Syntheses of (E)-1,5-diphenylcarbazone uranyl acetate
(Ar =
(VI) [{(Ar)NNHCONN(Ar) 2 }UO 2 (acac)(EtOH)]
C 6 H 5 , acac = CH 3 COO ):R
R
R
R
R
R
R
R
R
R
A solution of uranyl acetate (VI) ( 280 mg, 1.179 mmol) in
ethanol
(30
ml)
and
then
(E)-1,5diphenylcarbazoneurinailacetate ( 280 mg, 1.179 mmol mol )
in (40 ml) of ethanol was added drops at room temperature
Salem El-Tuhami ASHOOR, Chemistry department Faculty Science,
Misurata University, Misurat-Libya (corresponding author to provide:
;fax: +218-512623191; e-mail: [email protected] or [email protected]).
133
International Conference on Chemical and Environmental Sciences (ICCES'2012) June 16-17, 2012, Bangkok
and after 15 minutes in room temperature stirring the
temperature was arise to reflux for 5 hours. During that time
the colure was changed from red-brown to pink. The mixture
was filtered and the solution was reduced to volume (20 ml)
and after that was stored at low room temperature for 24
hours.
The
dark
brown-pink
crystal
of
the
[{(Ar)NNHCONN(Ar) 2 }UO 2 (acac)(Et 2 OH)] (Ar = C 6 H 5 ,
acac = CH 3 COO ) in yield ( 550 mg, 0.990 mmol, 83%)
(Scheme 1). Anal calcd for C 14 H 26 N 4 O 5 U, C: 31.8, H: 3.55,
N: 9.89. Found. C: 32.23, H: 3.98, N: 9.57. Mp = 146-147 oC
In solution 3 undergoes dynamic behaviour as shown in its
room temperature 1H NMR spectrum in chloroform-d.
All peaks that we expected were arising from the CH 3 CH 2 OH
group is resolvable 3.7 ppm (q, 2H, CH 2 ), 1.1 ppm (t,
suggesting that is
3H,CH 3 ), 2.2 ppm (S, H, OH)
uncoordinated to the urinal centre. Again the peak of H ( NHCO-R) is celery appear at 
( = 8.10 p pm) that come across
with our experimental just one acetyl acetate was eliminated
from the metal centre. Also disappear the singlet peak that
especially for (s, H, ArNHN) which suggesting that is one
mole of acetyl acetate was eliminate from metal centre. Other
peaks such aromatics system were appear at (δ = 6.90, ppm)
(m, 6H, C 6 H 5 ) and (δ = 7.15 ppm) (m, 6H, C 6 H 5 ). This
complex 3 comparable to other published dioxouranium (VI)
and uranyl ion with aminoalcoholbis(phenolate) complexs.12,
Scheme 1
(E)-1,5-diphenylcarbazone uranyl acetate (VI)
H
N
N
H3COO
U
O O
O
N
13
N
B. UV- Visible Study :
3
Ref. 5h
EtOH
The electronic spectrum of 3 shows four picks. Strong pick
at 229 nm which in frequency 43668 cm-1, madam pick at 293
nm which is in 34129 cm-1, these are due to intraligand
π →π* and n→ π* and with other picks at 472 and 648 nm in
frequency 21186 cm-1 and 15432 cm-1 these are consists for
complex exhibit a pair of bands appearing in publication the
region 20000 – 14300 cm-1. 14, 15
O
HN
HN
N
N
[UO2(CH3COO)2]
1
2
(E)-1,5-diphenylcarbazone
Fig. 1 Scheme 1
B. Spectroscopic Techniques:
C. Electronic and structural properties
Electronic spectra were recorded at room temperature on
UV-Vis spectrophotometer mini 1240- Shimadzu.
The convergence is set to 0.001 kcal molK1. The electronic
properties of (E)-1,5-diphenylcarbazone uranyl acetate (VI)
[{(Ar)NNHCONN(Ar) 2 }UO 2 (acac)(Et 2 OH)] (Ar = C 6 H 5 ,
acac = CH 3 COO ) 3 showen in table 1.
1
H NMR spectra of 3 was acquired at El-fatah universityLibya on a Bruker Spectrospin AG 300DPX and operating at
300.13 MHz for 1H measurements. Chemical shifts are
reported in ppm and referenced to the solvent peaks. Coupling
constants are quoted in Hertz (Hz).
TABLE 1 : ELECTRONIC PROPERTIES OF 3 :
Geometry optimization of the studied molecules was done by
performing the semi-empirical molecular orbital theory at the
level PM3 using the restricted Hartree–Fock (RHF) procedure
bye using Hyperchem program version 7.5 running on a
Windows XP workstation with a Pentium IV PC. The Polak–
Ribier algorithm was used for the optimization.
Conductivity measurement was carryout in glass device and
photometer measurements. Elemental analyses for 3 were
carried out by Asuete University- Egypt.
Total Energy
-29351.70313 (kcal/mol)
Total Dipole Moment
78.92D
Energy Symmetry (CS)
-29351.702203 (kcal/mol
Orbital (HOMO) Energy
Symmetry
25.66085 er
Symmetry
38A`
C. Reagents and Materials:
UO 2 (acac) 2 and (E)-1,5-diphenylcarbazone were
purchased from Aldrich . Ethanol was order from from Acros.
The structural properties of 3 to conform optimized
structure shown in fig. 2
III. RESULTS AND DISCUSSIONS
A. 1H NMR Study :
134
International Conference on Chemical and Environmental Sciences (ICCES'2012) June 16-17, 2012, Bangkok
even after reflex 5 hour. They did prove to be useful
metathesis reagents for introducing the chelating amides of the
ligand to uranyl metal centre. Also one mole of the solvent
was not co-ordinate with ion metal of the complexes unusual
saturation state as shown by NMR as free.
Also the geometry optimization of the studied molecules were
done by performing the semi-empirical molecular orbital
theory at the level PM3 using the restricted Hartree–Fock
(RHF) procedure and showed the high energy of this
compound. Conductivity behavior of the 3 was found within
the range of semiconductors.
Fig. 2 The optimized structure
Appendix 1
D. Conductivity study :
Conductivity behavior of the 3 was followed the Arrhenius
behavior and the activation energy can be calculated using
different temperatures. The conductivity of this compound 3
has been explaind in term of the following Eq.
σ = 1/ρ = Ω cm-1 were
ρ = R A/L and A = π r2
A = 3.14 x (0.25)2 = zz → R = V/I = 0.9998v/ 1.08717
x 10-7 A = dd
P = dd zz/0.1
Were: ρ = specific resistance & A = surface area & R =
resistance &
V = voltage & I = current intensity
The value of conductivity was shown to be writhen the
range of semiconductors values (1.5 x 106 ) Ω cm.
The following graph explains the relation between current
and voltage (Appendix 1). The slope equal to resistance, from
the obtained the resistance the resistively was calculated
according to the above mentioned equations
A(X)
B(Y)
A(X)
B(Y)
1
2.7 E-6
5.5
1.42 E-5
1.5
3.8 E-6
6
1.56 E-5
2
5.2 E-6
6.5
1.68 E-5
2.5
6.4 E-6
7
1.80 E-5
3
7.8 E-6
7.5
1.93 E-5
3.5
9.0 E-6
8
2.03 E-5
4
1.04 E-5
8.5
2.19 E-5
4.5
1.15 E-5
9
2.32 E-5
5
1.29 E-5
9.5
2.46 E-5
10
2.59 E-5
ACKNOWLEDGMENT
This study was done in chemistry department science faculty
Misurata university witch we are extremely grateful to the
department and university for to given the chance.
0.000030
SEAII. 5
Data1B (SEAII. 5)
0.000025
Current A
0.000020
REFERENCES
0.000015
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0.000010
0.000005
0.000000
0
2
4
6
8
10
Voltage V
Fig. 3 Graph between current and voltage
Conductivity arises mainly while the activation energy
increase, the conductivity is due the electronic transfer
between the aromatic system and nitrogen attached the
aromatic and then to metal centre (delocalization electron).
The conductivity of 3 has been measured in the voltage range
1 to 10 V. It is found to follow the Jonscher`s power law.
IV. CONCLUSIONS
The chemistry presented in this paper shows that not only
chelating with one amides of with U(VI) are accessible, but
that simple acetylacetate still co-ordinate with metal centre
[15]
135
A. T. Mubarak, Spectrochimica Acta Part A 65 (2006) 1197-1207.