Synthesis Characterization and Study of some electrical properties of compound of Octaphenylporphyrazin Cobalt (III) complexes

 

Hasan Sabeeh Jabur

Chemistry Department College of Science. University of Al-Muthana. Al-Muthana. Iraq.

 

ABSTRACT:

The present study the preparation of complexes octaphenalporphyrazin Cobalt (III), the prepared compounds are characterized by elemental analysis, infrared, uv-visible, and ¹H-NMR. The elemental analysis results showed a good agreement with the calculated results. The IR-spectra show a strong band at the range (2235-2240cm^-1 ). which are attributed to the stretching vibrations of the (C≡N) band and hidden in the complexes.The UV-Visible spectra are characterized by the appearance of the two main absorption bands. The first at the range (600-675)nm which is called Q-band and the second at the range (305-350)nm which is called B or sort band. The ¹H-NMR spectra data of all prepared compounds are similar, in general, and consist of aromatic protons signals within the range (735-793) ppm which is attributed to the meta, para and Ortho protons. Electrical conductivity of the polymer was measured by using the iodine doping. lt was found that the electrical conductivity increased up to (10^-4 ohm^-1. Cm^-1).

 

 

INTRODUCTION:

Porphyrazines and porphyrines are considered as two main divisions from tetrapyrrolic macro cycles compounds which have a large cycle, but they differ essentially. Porphyrazine is of a large tetrapyrrolic cycle which differs from porphyrine in figure(1-1a) in the existence of Nitrogen instead of CH group figure (1-1b).^[1] porphyrazinare the second most important class of colorant and iron porphyrazin is the largest volume colorant sold. porphyrazin have also found extensive use in many modern high technologies⁽²⁾ for intence they are used as catalyst in the merox process and photoconductor xerographic doubic layers of laser printers and copy machines.

 

The Metallophthalocyanines and porphyrazine were prepared by many methods.

 

The synthesis of Phthalocyanine is usually at a high temperature cyclotetramerisation of phthalonitrile or phthalic anhydride^(3,4).

 

The cyclotetramerisation of phthalocyanines is a clear reaction and using phthalic anhydride or phthalonitrile is favored method in industry . Both reactions are assisted by temperature and with a suitable metal ion such as (Fe, Al, Cu, Ni, Co and Mn… etc). It is know that Pc marcocyclic can be derived from over (70) different elements. However metal free phthalocyanine (Pc H₂) can be prepared by the removal of metal ions such as (Li^± or Mg⁺²) after cyclotetramerization Metallophthocyanine compounds containing different peripheral substituted on the aromatic rings such as substituted phthalonitrilephthalic acid or phthalic anhydride where prepared^(5,6). For example metallophthalocymine polymer is prepared as dihydroxy silicon phthlocyaninetetrasulfonic acid as shown in structure(1)^[5] and the converted to oligo-µ-oxo silicon  phthalocyanine tetra sulfonic acid methods Also some infrared absorbing porphyrazin cover many important high technical application including the porphyrazin therapy if cancer⁽⁷⁾, optical data storage and reverse storable absorbs⁽⁸⁾ porphyrazinrings may either be separate units, such as metal free or copper porphyrazin, or linked with other porphyrazin rings in the form of dimer, oligomers or polymers⁽⁹⁾.

 

MATERIALS AND METHODS:

Synthesis Materials:

1- The synthesis of Benzil (Bz):

A (5g, 23×10^-3Mol) of benzoin was placed into a conical flask. (12.5ml) of concentrated nitric acid then added and the mixture was heated on the steam bath for 15min the appearance of brown nitrogen oxide fumes. The heating was continuing till all the nitrogen oxides are removed of A 75 ml of water was added to the reaction flask. The mixture then left to be cooled to the room temperature to the precipitated product. The yellow solid was collected on a Buchner funnel. The wet product was then recrystallized by dissolving it in 10 ml of ethanol and heating it on a steam bath. The solid product was then filtered and dried. The product pale yellow solid yield (3.8g, 76%) M.P (93-95C).^[10]

 

 

Figure 1: Synthesis of Benzil

 

2-Synthesis of 2,3-dicyano-5,6-diphenyl pyrazine (PN):

A(1g,4.7×10^-3mol) of Benzil was dissolved in 25 ml ethanol and 28 drop of acetic acid then added into conical flask containing (0.5g, 4.6×10^-3mol) of diaminomalonetrile (DAMN) dissolved in 25ml ethanol and refluxed for 4 hours. The reaction product was then left for two days and filtered and the solid product was recrycstallized from a mixture of hexanol and acetone (1:1) ratio. The product is yellow microcrystal. The Yield is (0.7g, 52%) m.p(253-255). ^[11]

 

 

Figure 2: Synthesis of PN

 

3- The synthesis of octa phenyl tetra pyrazinoporphyrazineCobalt(III) (OPPzCo). ^[12]

A mixture of iron chloride anhydrous(0.133g, 1×10^-3mol), PN(1.12g, 4×10^-3mol) , urea (1.5g, 2.5× 10^-2 mol), and 8ml quinoline was refluxed for 4 hours, the reaction mixture was  then cooled and then the solvent was evaporated. The crude reaction products were purified by dissolving it in chloroform and then added to abeaker containing ethanol. The solid product was then filtered and dried at 110C° .the product is dark brown powder. The yield is (0.36g, 30%).

 

 

 

 

Figure 3: Synthesis of a.OPPZCo

 

RESULT AND DISSECTION:  

Table 1: The condition for the preparation of Octa phenyl tetra pyrazineporphyrazino‎Cobalt complexes

Compounds used	Wt. of  Compounds used	Reaction time	Product colour	Yield	Product name
Co Cl3 Anhydrous	0.162g 1×10-3mol	4 hours	Dark brown powder	0.8g 66%	Octa phenyl tetra pyrazineporpyrazine Cobalt(III) OPPzCo

 

1- The CHN Analysis:

The C.H.N analysis is shown in Table (2). It shows that the calculated values are nearly similar. The little difference may be attributed to the general difficulty of the phthalocyanine purification and Tetea Pyrazinoporphrazino (T.P porphyrazino) compounds which is due to the difficult solubility in common organic solvents.

 

 

Table(2): The elemental analysis data of the studied compounds

Compounds	Calculated			Found %
	C	H	N	C	H	N
PN C18H10N4	48.40	1.34	37.64	48.90	1.68	37.08
Complexes (opCoPz) (C72H40N16Co)	71.82	3.32	18.62	71.00	3.35	18.06

 

 

 

2- Infra-red Absorption spectra:

Figures (4) and (5) show the IR Spectra of the prepared compounds taken on KBr disc.

 

Table 3 shows the main IR absorption frequencies for the prepared compounds.

 

The IR spectra show a strong band in the range(1400-1520)cm^-1 due to (c=c) stretching, while (C=N) appears in the range of (1591-1683)cm^-1 , and the(C-N) appears in the range of (1230-1379)cm^-1 .

 

The aromatic C-H stretching band appeared in range(3018-3055)cm^-1 . In all spectra of the prepared complexes, there are several bands ranged(700-1230)cm^-1  assigned to the compounds skeletal vibrations, and the appearance in the range of (2235-2240)cm^-1 which are attributed to the stretching vibration of the (C≡N) band. The (N-H) appears in the range of (3295)cm^-1.⁽¹³⁾

 

 

 

Table (3): The IR absorption data for compounds

Compounds	V(C=C) cm-1	V(C-H) cm-1	V(C=N) cm-1	V(C-N) cm-1	V(C≡N) cm-1
PN	(1410-1530)s	(3020-3030)w	(1590-1680)s	(1230-1379)s	(2235-2240)s
Complexes opPzCo	(1400-1520)s	(3018-3055)w	(1591-1383)s	(1235-1380)s	-

 

 

Figure 4: IR-Spectra of(PN)

 

 

Figure5: IR-Spectra of complexes (op PzCo)

 

3-Electronic spectra:

The UV-Visible data of all prepared complexes were measured in the range of (200-800nm) used DMSO as solvent.

 

Figure (6) and (7) and tables (4) show electronic spectra and the data taken from the spectra for compounds.

 

All of the spectra give the general features of spectra of Schiff Base complexes with two main peaks.^[14]

 

The first transition was observed in the range of (345-654nm) which can be attributed to a Q-band to (π-π^*).

The second band observed in the range (245-300nm) can be attributed to a B-band, assigned to (π-π^*).

 

Table 4: The uv-visible date for compounds

Compounds	B band (λmax nm)	Q band (λmax nm)
PN	245,275	345
OpPzCo	300	654

 

 

Figure6:UV-visible Spectra of (PN)

 

 

Figure 7: UV-visible of complexes (opPzCo)

4-¹H-NMR Spectra:

The ¹H-NMR Spectra data of the prepared compounds, Schiff Base complexes are shown in figures (8). In general, the spectra are similar and consist of aromatic protons signals within the range (7.35-7.93) ppm which is attributed to the Meta, para and ortho protons.

 

The ¹H-NMR Spectra show the deuterated DMSO with tetramethyl saline as an internal standard. All spectra showed a signal at 2.5-3.25 ppm for the DMSO solvent and showed a sharp signal at 3.33ppm for water in DMSO^.[15]

 

The ¹H-NMR Spectra of (opCoPz) , figure(8), show bands at (735,738,793)which could be related to aromatic proton in the position Meta,Bara and Ortho.

 

 

Figure 8:¹H-NMR Spectra of complexes(opPzCo)

 

Electrical conductivity:

The electrical properties of Porphyrazines and related compounds defend verymuch up on the Morphology of the Macro cyclic systems, Toachieve goodsemiconducting or even conducting properties.

 

Doping of the polymer Iodine was achieved by the dissolved of polymer in CCI₄and stirrer at (79C) for t(72h), after that the polymer doping was filtered and driedin vacuum oven at(50C) the maximum conductivity of the doped polymer samples is 3-52 X10^-4 ohm^-1. It increases conductivity by the overlap of the Ʌ Porphyrazinesorbitals of rings , A high electrical conductivity has been reported by Wohrle⁽¹⁶⁾for iodine - doped Complex was explained by assuming that the eclipsed ring structure persists in the partially oxidized Material .

 

Table 5: Shown the values ΔE and σº

sample	ΔEev	σº (ohm-1(cm-1)
complex	0.57	1.2x10-4
Iodine-doped complex	0.54	8.30x10-4

 

 

Figure 9: The dc conductivity of Complex and doped Complex

 

CONCLUSIONS:

In this work figure(3) we have reports of complexes derives from of Schiff Base ligand , obtained from the reaction of Benzil and diaminomalonetrile (DAMN) to give Schiff Base ligand that reaction with salt metals such as CoCL₃(III) . the structures of the compounds and complexes characterization by C.H.N, uv-visible , IR and ¹H-NMR –spectroscopy . Also measurement electrical (Dc) for Complex and dopd Complex 

 

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Accepted on 20.09.2018        © RJPT All right reserved

Research J. Pharm. and Tech 2019; 12(2):495-498.