CC BY
25
UDC 547:1:3'
SYNTHESIS OF MONO-, BI- AND TRINUCLEAR CARBINOL DERIVATIVES OF FERROCENE, DEVELOPMENT OF TECHNOLOGIES OBTAINING OF THIN COVERINGS OF PHOTOCOMPOSITES WITH POLYMER MATRIXES AND STUDY OF
SOME ELECTROPHYSICAL PROPERTIES
G.Z.Suleymanov, M.A.Gurbanov*, A.Kh.Akbarov**, Z.M.Mammadova, A.F.Gochuyeva*
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan * H.Abdullayev Institute of Physics, NAS of Azerbaijan **M.Rasulzade Baku State University
Synthesis technology of mono-, bi-, trinuclear carbinol derivatives of ferrocene [C5H5FeC5H4]nC-OH (n=1, 2, 3) was developed and thin coverings of photocomposite materials with polymer matrixes were produced. Considering the dependence of photo quenching efficiency of photocomposite ferrocene-polymer depends on the amount of ferrocene, in the work the experimental results of the dependence in composition samples on a number of nuclei of ferrocene were presented, as well as the reasons of elec-troconductivity of photo quenching in samples based on mono- and multinuclear carbinols of polymer-ferrocene were determined and the mechanism of photo quenching effect was proposed.
Keywords: mono-, bi-, trinuclear ferrocenylcarbinols [C5H5FeC5H4]nC-OH (n=1, 2, 3), polymer photocomposite materials, photo quenching effect.
At present, in connection with the creation of photosensitive materials which convert light energy to electric energy scientific-practical research works are being carried out. They are the followings:
using semi-conductors the creation of new photosensitive materials, obtaining of new materials of photoelectrics based on different functional group materials, obtaining of organic matrix multi-functional photosensitive semicon-ductive photosensitive composite materials, and obtaining of negative electric conductive composite materials based on inotganic, metalcomp-lex and metal-organic compounds [1, 2].
Among the abovementioned directions we observed photo inhibition effect of electric conductivity in thin film polymer dielectric composites based on different metalcomplexes. Such type photocomposite materials are used as memory elements for schemes which keep na-nosize magnetics and information for photoe-lectronic industry [3].
Considering the above-mentioned advantages obtaining and studying thin film photocomposite matrix materials using metal-organic compound (MOC), development and study of technologies using MOC can be the most urgent problems of photoelectronics.
Experimental part
All experiments were conducted at nitrogen medium. Solvents used in the experiment were purified and made absolute according to relevant methods.
1. Synthesis of ferrocenyl mononuclear dimethyl carbinol derivative C5H5FeC5H4C(CH3)2OH (Ia). For this purpose firstly, according to method [4] lithium metal-organic compound C5H5FeC5H4Li [1] is produced by mixing 12 ml (1.14 N) n-C4H4Li - 50 ml of heptane solvent with 0.1 mol 1.76 g of ferrocene 3 hours in the range of 30-400C. Considering that this compound is easily hydrolyzed in an open air, it should be used directly for the next stage. Thus, 6 ml of acetone is added into solution (I) and mixed and after an hour mixing is stopped. Then the reaction mixture is processed with 5% HCl. In this case the reaction solution rises above water. Humid reaction product is assembled on paper filter and dried in an open air. The yield of synthesized by this way and dried light yellow (Ia) compound is 2.05 g or for ferrocene it is 79.5%. Light yellow compound has a melting temperature (Tmelt) 67-680C and a decomposition temperature (Tdecomp) 2070C. According to the results of element analysis C13H16FeO conforms to chemical formula. IR
spectrum of this compound: Voh 2750-2830 cm-1, two multiplet type OH groups were detected according to the results of a device provided with thermometer and in four-camera furnace heated with DP-2 electric.
2. Synthesis of diferrocenylmonomethyl carbinol [C5H5FeC5Hj2C(CH3)OH (Ha) derivative. For this purpose 0.01 mol (4.32 g) of 6zs-ferroce-nylmonomethylchloride [C5H5FeC5H4]2C(CH3)Cl, 50 ml H2O-/-C3H7OH in ratio of (1:10) is mixed from solvent in the range of 0-100C and 5% NaOH solution is added drop by drop and is mixed within 0.5 hour. Then mixing is stopped and the reaction mixture is added into 3% HCl aqueous solution. Then 20 ml of upper organic part is extracted with hexane 3 times. Extract-ants are assembled and hexane is heated and distilled. To purify dark brown residue from primary substances it is washed with pentane or light fraction of gasoline in ratio of 3:10 ml.
As a result 3.44 g or with 83% yield dark brown [C5H5FeC5H4]2C(CH3)OH (IIa) carbinol derivative with rmelt=119-1200C is obtained. According to the results of element analysis the compound conforms to C22H22Fe2O chemical formula. Tdecomp>2380C
3. Synthesis of triferrocenylcarbinol [CsHsFeCsH^C-OH (IIIa) derivative. For this purpose 25 ml (1.14 g) of KOH which is dissolved in 0.2 mol water is added into 0.01 mol (5.72 g) of ¿ró-ferrocenylmonochlorinemethane [C5H5FeC5H4 ]3CCl and 100 ml of heptane and mixed. As a result of processing the reaction mixture using the method 2 dark yellow (IIIa) compound is added. The compound is obtained with 79% yield. According to the results of element analysis it conforms to C31H28Fe3O chemical formula. Melting temperature of (IIa) is 141-1420C; Tdecomp>2960C.
Composite forming components: polymer matrix type photosensitive composite samples were prepared by hot pressing method on the basis of mono-, bi- and trinuclear carbinol [C5H5FeC5H4]„CR1R.2OH derivatives of ferrocene and as a carrier high density polyethylene
(HDPE), low density polyethylene (LDPE), po-lyvinylidenftorid (PVDF). For this purpose composite samples are prepared by mixing the components and hot pressing method. To prepare photocomposites with varying thickness the pressing temperature of which is in the 120-1500C range, pressing pressure is in 10-40 mm, the process is carried out under varying condition in 1.0-3.0 MPa range. During pressing to prevent the defects of the sample pressing must not be more than 25%. When relevant composite samples are prepared mas ratio of polymer to ferrocenylcarbinol is taken as follows:
1) mononuclear (Ia) ferrocenylcarbinol -HDPE (PVDF) C5H5FeC5H4C(CH3)2OH+HDPE was taken in mass ratios 0.20:1, 0.40:1, 0.5:1, 1:1; composite samples were prepared at 250C under P=1.8 MPa pressure;
2) composite samples were prepared with relevant mass ratios 0.20:1, 0.40:1, 0.5, 1:1 by binuclear ferrocenylcarbinol [C5H5FeC5H4]2C(CH3)OH (IIa) + HDPE and (lIa) + (PVDF);
3) composite samples were prepared by hot pressing under P=1.8 MPa pressure at 250C, tri-nuclear ferrocenylcarbinol [C5H5FeC5H4]3C-OH (IIIa) + HDPE (PVDF) in relevant mas ratios 0.20:1, 0.40:1, 0.5:1, 1:1 thin film F=10 mm, «=0.03 mol and are used in testing.
Results and discussion
As mentioned above one of the factors influencing on photo inhibition effect of electric conductivity in ferrocene-polymer double phase photocomposite samples occurs due to the 1:1 ratio of ferrocene to polymer matrix in composite [5]. As a ferrocene derivative - polymer photocomposite sample mono-, bi- and trinuclear ferrocenylcarbinol compounds were synthesized and studied. For this purpose according to reaction equation (I) mononuclear ferrocenyl dimethyl carbinol C5H5FeC5^C(CH3)2OH (Ia) derivative was synthesized and the composition, structure and some physical and chemical properties were studied:
heptan HClIH
C5H5FeC5H4 Li+C^-C-CH > C5H5FeC5H4-C(CHз)20L1 —¡-p
II LiC • O
(Ia) compound synthesized with (1) reaction equation was obtained in the range of 79.5-85% for ferrocene with varying yield. Unlike ferrocene mononuclear (Ia) ferrocenylcarbinol derivative is a light yellow compound which has lower Tmelt=67-680C, and shows good dissolution ability in most hydrocarbon solvents, but it is badly dissolved in water. When kept in open air for a long period it
II
Tmeit 119-1200C of (IIa) compound, Tdecomp >1580C and it shows high dissolution ability in hidrocarbon solvents.
(IIa) carbinol is more stable than (Ia) carbinol. As to the synthesis of trinuclear ferrocenylcarbinol [C5H5FeC5H4]3C-OH (IIIa) derivative it should be noted that is it conducted at (2) reaction
III
(IIIa) ferrocenylcarbinol compound has higher Tmelt (141-142)0C and Tdecomp >196°C.
In the paper we determined and studied the structure, chemical conversion possibilities and thermal stability properties of each three (Ia, IIa, IIIa) ferrocenylcarbinol compounds. For this purpose when detecting structural properties of ferrocenylcarbinols which were studied using modern physico-chemical and spectral methods (MAESP, IR, 1HNMR, DTA and so on), in IR and 1HNMR spectra it was observed that in these compounds they have two multiplet type OH structures. In electron absorption spectrum (EAS) these compounds have an arm shape absorption bond in (Ia) Xmax=270 nm, (IIa) Xmax=278 nm, (IIIa) Xmax= 285 nm of each carbinol. As mentioned above in the work newly synthesized (Ia), (IIa) and (IIIa) ferro-
2O
p C5H5FeC5H4C(CH3)2OH (1) Ia
was oxidized, darkened and decomposed. Binuclear [C5H5FeC5H4]2C(CH3)OH - bis-fer-rocenylmonomethylcarbinol derivative of ferrocene (IIa) was obtained byreaction equation in water-isopropyl medium of diferrocenyl-chlormethylmethane by processing with 5% NaOH. In this case yield of (IIa) to ferrocene is 83%.
(2)
IIa
medium the reaction will not go selectively, part of the product is contaminated with mixtures containing complex compounds. That's why when using reaction (3) with KOH in the range of 0-100C the product will be obtained with 79% yield.
(IIIa) compound relative to (Ia) and (IIa) metalcarbinols
(3)
IIIa
cenylcarbinol derivatives melt and decompose at lower temperature than ferrocen. According to the results of thermogravimetric analysis of these compounds beginnings of the decomposition of these compounds are (Ia): Td.t.>2070C, Td.e. 3100C; (IIa): Td.t>2380C, Td.e. 28 80C; (IIIa): Td.t>2960C, Td.e.3150C (where d.t. is decomposition temperature, d.e. is the end of decomposition). Final decomposition products of ferrocenylcarbinols are cyclopentadien polymer resin and FeO.
In IR spectra of carbinols taken in pa-raffinic oil intensities of OH groups entirely change depending on the structure of carbinol.
Thus, according to the results of spectral method of coordination bond formed by vOH= 2668-2725 cm-1 multiplet OH groups with in-tramolecule Fe is connected to OH group,
1 . i-PrOH I H20(10:1)
2 0-100C
[C5H5FeC5H4 bCCC^Cl +NaOH 0 1 ^ci-> [C5H5FeC5H4 bCCC^OH .
2KOHIH2O-heptan [C5H5FeC5H4]зCa- ^ p > [C5H5FeC5H4]зC-0H .
multiplet valence absorption bonds in vOH= associates between endo-, exo- and free OH 2910-3040 cm1 range confirms the formation of qroups. different intramolecular and intermolecular
+
Fe Fe-H-Q
Fe
C —R1 C—QH
R _- Ä R
A
B
C
R
R
Fe
Fe
I n,Hs I
C^VQ"C"
RR
R l/Q
R
C - H/
R H—Q R
Fe
Fe
Diagram. Probable intramolecular equilibrium dynamics of ferrocenylcarbinols.
The same result was obtained in 1HNMR spectra. In ferrocenylcarbinol samples taken in deuterium acetone (D3C)2CO medium spectrum SOH=344 ppm and Soh=4.12 ppm confirmed the existence of two multiplets, relating to two types OH-groups. It was determined SOH=344 ppm signals shifted to strong part of spectrum can be related to OH-groups connected to Fe atom with intramolecular coordination bond of OH-group protons, but SOH=4.12 ppm signals can be related to free OH-group protons. Structural properties of HDPE samples prepared on the basis of ferro-cenylcarbinol samples of SOH =412, 416 ppm multiplet OH-groups were studied by IR spectrum method. It was found that they are exposed to high interaction both between carbon atom with polyvinyldiendifluoride hydrogens of polyethylene and cyclopentadien rings.
According to the experimental result we may note that in polymer ferrocenylcarbinol photocomposites a number of trap with different structure and property are formed due to intramolecular bonds of different types and this provides photoinhibition of electric conductivity with the absorption of a light by these trap.
In the work structural and thermal properties of both ferrocenylcarbinol compounds were studied. When studying structural properties of car-binols obtained by the modern physicochemical and specral methods, in spectra of ferrocenyl compounds, IR and 1HNMR the existence of two multiplet OH groups in these compounds was observed. Depending on the number of ferrocene radicals using (Ia), (IIa) and (IIIa) fer-rocenylcarbinol derivatives which were synthesized and characterized according to (1), (3) reaction equation and valence vibration characterizing coordination bonds of two types OH-groups, polymer matrix photocomposite samples were prepared by hot pressing method and research works on detecting the effectivity of photoinhibition of physical phenomenon - electric conductivity in them due to the effect of a light were conducted. As it was noted in the experimental part of the work basic mass ratios of HDPE with f=10 mm diameter, thickness h=0.1 mm and PVDF and HDPE matrix (Ia) - ferroce-nyldimethylcarbinol, (IIa) - ferrocenylmonome-tylcarbinol and (IIIa) - trisferrocenylcarbiol compounds:
(Ia)+HDPE mas (0.5:1); (Ia)+HDPE mas (0.40:1); (Ia)+HDPE mas (0.20:1); (lIa)+PVDF mas (0.2:1) (IIa)+PVDF mas (0.4:1); (IIa)+PVDF mas (0.2:1); (IIIa)+HDPE mas (0.5:1); (IIIa)+HDPE mas (0.40:1); (IIIa)+HDPE mas (0.2:1).
As a result of researches it was determined that maximum photo inhibition effect of ferrocene-polymer photocomposite samples occurs in samples taken at 0.5-1 mas ratio [4]. In (Ia), (IIa), (IIIa) base - polymer photocomposites maximum photoinhibition effect changes not depending on mas ratio of ferrocene molecule in composite, but on amount of ferrocene. Figure shows the dependence of R/R ratio on the amount of ferrocene nucleus in photocomposite. As Figure shows, depending on a number of ferrocene nucleus taken as composite forming agent positively influences on photoinhibition effect of composites.
Change of R/R0 ratio depending on the amount of nucleus (N) in photocomposite, 1 - change of PVDF-ferrocenyldimethylcarbinol (1:0.35); 2 - HDPE-diferrocenylmonomethylcarbinol (1:0.30); 3 - volume of PVDF-triferrocenylcar-binol (1:0.25); 4 - HDPE-ferrocene (1:1); £/=100 V; £=4000 V/m2.
One of the main approaches of characteristics of polymer - mono- and multinuclear ferrocene derivative photocomposite material is the study of dependences of their properties on volume ratio of separate phases. For this purpose firstly, the dependence of R/R ratio on volume ratio of ferrocene derivative phase must be conducted. Mono-, bi- and trinuclear ferro-cenylcarbinol Fc-OH (Ia), Fc2C(CH3)OH (IIa), Fc3COH (IIIa) polyethylene samples of ferrocene was exposed to 100 V tension and its surface was
affected by light rays with £=4000 V/m intensity in visiblity zone. In this case the results show that in each samples negative electric effect - sharp photoinhibition occurs, depending on a number of ferrocene molecule it changs linear and increases with a higher rate than linear dependence. R/Ro=/(E) dependence changes depending on phase ratio of polymer in composite.
Besides, inhibition effect of photo conductivity depends on intensity of a light, angle of incidence and is expressed by equation (4).
During absorption of light quanta with hv energy in polymer-ferrocene composite the transition probability of electric charge carriers reduces with the increase in thickness of interphase layer. In this case volume loads gather in he composite and photoinduced dipol is formed. It compensates external electric field which is applied to dipol sample. Depending on intensity of a light concentration of dipols increases and is observed with non-linearity of R/R =/(£) dependence and can be solved by equation (4).
ARf
tga =-f = 18 . 8-105 Om/W. (4)
AE
Thus, traps are formed in matrix composite which are created by ferrocene particles dispersed with ferrocene particles of polyethylene and polyvinylidenfluoride and this leads to absorption of a light on a surface and this creation of photoinhibition effect of electric conductivity becomes inevitable. Reversibility of reduction reactions and low activation energy are important conditions. Reversible physico-chemical effects and formation of intraphase transition layer in ferrocene phase in polymer matrix under the interaction of a light and electric field transforms polymer-ferrocene composite to an interesting object as a light sensitive material. Photo inhibition effect of an electric conductivity which is explained by the increase in thickness of transition layer in polymer-ferrocene composite, provides the use of it in technology as elements with high negative electric conductivity coefficient of composite materials.
The mentioned above confirms the experimental results on photo inhibition effect of electric conductivity for polyethylene ferrocene and ferrocene composites with high density.
Dipolar moment of polyethylene equals to zero. That's why since polyethylene-ferrocene composite is not polar, thickness of intraphase transition layer is different in composites. This difference results in a favour of polyethylene-fer-rocenylcarbinol derivative. We think that this effect is an important factor in higher electric photo inhibition coefficient of HDPE-ferrocene composite than PVDF-ferrocene composite.
Electro negative photoconductivity effect found in multinuclear derivative of polymer-ferrocene double phase matrix type systems is related to the creation of local electric field due to stabilization of electric charges in local levels and compensation of external electric field. Ferrocene derivatives are photogeneration phases of electric charge carriers; they provide photogeneration under the effect of electric field and a light. Electric field formed by volume charges sufficiently compensates external electric field, provides formation of photo inhibition effect of electric conductivity in these composites. The phase which provides reversible localization of electric charge carriers in composite is ferrocene. Interphase transition layer formed due to dissolution of polymer macromolecule segments, their functional groups and ferrocene molecule can be a phase for reversible stabilization of electric charge carriers. Effect of such localization centers are reduced with the decrease of thickness of interphase layer in polymer-ferrocene composite.
Formation mechanism of photo inhibition effect of electric conductivity in mono- and
multinuclear carbinol composite of polymer-ferrocene is primary and requires detailed determination of the nature of reversible localization centers. To define the nature of reversible stabilization centers, the influence of ferrocene and its derivatives on photoinhibition effect of electric conductivity more exactly additional researches must be conducted and the impact of value external electric field on this effect is to be studied.
References
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2. Давиденко Н.А., Давиденко И.И., Деревянко Н.А., Ищенко А.А., Костенко Л.И., Мокринская Е.В., Студзинский С.Л., Тонкопиева Л.С., Чуприна Н.Г. Отрицательная фотопроводимость пленок ферроценсодержащего олигомера с мероциа-ниновым красителем // Химия высоких энергий. 2011. Т. 45. № 1. С. 271-275.
3. Давиденко Н.А., Дехтяренко С.В., Кокозей В.Н. Особенности фотопроводимости полимерных пленочных композитов, содержащих разно-металлически Fe(II)/Zn(II) комплексы // Химия высоких энергий. 2010. Т. 44. № 5. С. 455-457.
4. Stepnicka P. Ferrocenes: Liqands. Materials and bi-omolecules. Prague; Willey, February 2008. С. 655.
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FERROSENIN BÍR-, ÍKÍ- VO ÛÇNÛVOLI KARBÍNOL TÖROMOLORiNiN SÍNTEZÍ, ONLAR OSASINDA POLiMER MATRiSALI NAZiK TOBOQO FOTOKOMPOZÍTLORÍNÍN ALINMA TEXNOLOGiYALARININ ͧLONMOSÍ VO BOZi ELEKTROFÍZÍKÍ XASSOLORiNiN TODQiQi
G.Z.Süleymanov, M.A.Qurbanov, O.H.Okbarov, Z.M.Mammadova, A.F.Qoçuyeva
Maqalada ferrosenin bir-, iki- va ûçnûvali karbinol [C5H5FeC5H4]nС-0H (n=1, 2, 3) töramalarinin sintezi ûçûn müvafiq texnologiya içlanib hazirlanmasi va onlann polimer matrisali nazik tabaqa fotokompozit materiallannin alinma texnologiyasi verilir. Fotokompozitin fotosönma effektliyi ferrosen-polimer kompozitinda ferrosenin miqdarindan asili olaraq dayiçirsa, içda alinmiç kompozit nümunalarinda sönma effektinin ferrosen nüvasinin sayindan asili olaraq dayiçmasina aid eksperimental naticalarda öz aksini tapmiçdir. Hamçinin maqalada polimer-ferrosenin bir va çox nüvali karbinollann asasinda alinmiç nümunalarda elektrik keçiriciliyinin fotosönma effektinin yaranma sabablari va onun ehtimal olunan mexanizmi ila reallaçmasi masalalari da verilmiçdir.
Açar sözlzr: bir, iki vэ ûç птэН ferrosenil karbinol [C5H5FeC5H4]nC-OH (n=1, 2, 3) polimer, fotokompozit materiallari, fotosönmэ effekti.
СИНТЕЗ МОНО-, ДВУХ- И ТРЕХЯДЕРНЫХ КАРБИНОЛЬНЫХ ПРОИЗВОДНЫХ ФЕРРОЦЕНА,
РАЗРАБОТКА ТЕХНОЛОГИЙ ПОЛУЧЕНИЯ НА ИХ ОСНОВЕ ТОНКИХ ПОКРЫТИЙ ФОТОКОМПОЗИТОВ С ПОЛИМЕРНЫМИ МАТРИЦАМИ И ИССЛЕДОВАНИЕ НЕКОТОРЫХ
ЭЛЕКТРОФИЗИЧЕСКИХ СВОЙСТВ
Г.З.Сулейманов, М.А.Курбанов, А.Х.Акперов, З.М.Мамедова, А.Ф.Гочуева
Разработана технология синтеза моно-, двух- и трехядерных карбинольных производных ферроцена [C5H5FeC5H4]nC-OH (n=1, 2, 3) и получены тонкие покрытия фотокомпозитных материалов с полимерными матрицами. Учитывая зависимость эффективности фотогашения фотокомпозита ферроцен-полимер от количества ферроцена, в работе приведены экспериментальные результаты этой зависимости в полученных композиционных образцах от числа ядер ферроцена. Также выявлены причины возникновения электропроводности фотогашения в полученных образцах на основе моно- и многоядерных карбинолов полимер-ферроцен и предложен механизм действия эффекта фотогашения.
Ключевые слова: моно-, двух- и трехядерный ферроценилкарбинолы [C5H5FeC5H4]nC-OH (n=1, 2, 3), полимерные фотокомпозитные материалы, эффект фотогашения.
