Yeni tip kalkon ile türevlendirilmiş ftalosiyanin sentezi ve karakterizasyonu
Synthesis and characterization of phthalocyanine derived with a new chalcone
Yazar: ÖZLEM GÜVEN
Danışman: DOÇ. DR. HÜSEYİN KARACA
Sakarya Üniversitesi / Fen Bilimleri Enstitüsü / Kimyagerlik Ana Bilim Dalı / Anorganik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2024
Konu: Kimya = Chemistry

Özet:
Hem metal içeren hem de metal içermeyen ftalosiyaninler yaklaşık bir asırdır
bilinmektedir ve biyolojik olarak oluşan porfirinlerle aynı gruptadır, bu da onları belki
de en kapsamlı şekilde çalışılan makrosiklik moleküllerden biri haline getirmektedir.
Ftalosiyaninlerin intramoleküler π-π etkileşimleri güçlü moleküller arası etkileşimlere
yol açmakta, bu da moleküllerin çözünürlüğünü olumsuz yönde etkileyen agregasyona
neden olmaktadır. Bu nedenle, bu yapıların olağanüstü özelliklerinden faydalanılması
baltalanmaktadır. Bundan kaçınmak için, farklı fonksiyonel gruplar veya yeni
tasarlanmış moleküller ftalosiyaninlere periferal veya non-periferal pozisyonlardan
bağlanır. Bağlanan bu gruplar veya moleküller ftalosiyaninlere farklı benzersiz
özellikler kazandırır.
Hedef Pc lerimi sentezlemek için ilk olarak kalkon 3 bileşiği elde ettim. Bunun için 4
hidroksibenziladehit molekülüne 4-Metoksiasetofenon ekleyerek KOH katalizörü
eşliğinde 24 saat boyunca devam ederek kalkon 3 bileşiği sentezledim. Bunun için 4-
hidroksibenzaldehit ve 4-Metoksiasetofenon dan yola çıkılarak etanol su karışımında
%28,4'lük bir verimle kalkon 3 bileşiği elde etmiş oldum. Kalkon 3 bileşiğimi kalkon
5 bileşiğini sentezlemek için ana ürün olarak kullandım. Kalkon 3 bileşiğime 4-
nitroftalonitrili DSMO içinde çözündürerek potasyum karbonat ekleyip 24 saat
boyunca reaksiyonuma devam ettim ve kalkon 5 bileşiğimi sentezledim. Sentezlenen
bu kalkon bileşiği 4-nitroftalonitril ile %52,1'lik bir verimle oda sıcaklığında
ftalosiyanin başlangıç maddesi olacaktır. Kalkon 3 ve kalkon 5'in yapılarını belirlemek
için 1H ve 13C NMR spektrumları kullanıldı. Sentezlenen kalkon 3 ve kalkon 5
molekülleri FT-IR spektrumları ile onaylandı. Ftalonitril bileşiği 5,
metalloftalosiyaninler (MPc'ler) için başlangıç malzemesi olarak kullanılmıştır.
Kalkon 3 ve kalkon 5 bileşiği ftalosiyaninlerin periferal konumlarında "(E)-3-(4-
hidroksifenil)-1-(4-metoksifenil) prop-2-en-1-on" bağlanmış olarak tetrahedral
metalloftalosiyanin sentezi başarı ile gerçekleştirilmiştir. Daha sonra bu monomer ile
160 ⁰C'de azot atmosferi altında Zn(OAc)2.2H2O, Co(OAc)2.4H2O tuzları ve
Kadmiyum asetat dihidrat ftalosiyaninlerin merkezi için metal iyon kaynağı olmak
üzere kullanılarak, Pc-6 için Zn+2, Pc-7 için Co+2 ve Pc-8 için Cd+2 idi. Çinko, kobalt
ve kadmiyum tuzları ile reaksiyona sokularak metalloftalosiyaninler elde edildi.
Siklotetramerizasyon reaksiyonundan sonra beklendiği gibi istenen MPc'lerin
izomerik bir karışımı elde edildi. Elde edilen yeni bileşikler yüksek çözünürlükte,
yaygın organik solventler kullanılarak Pc-6, Pc-7, Pc-8 için 1H ve 13C NMR, FTIR,
HRMS ve UV-Vis spektroskopisi ile karakterizasyonu gerçekleştirilmiştir.
Anahtar kelimeler: Kalkon, Ftalosiyanin, Redoks, spektroelektrokimya, Kataliz, UV
Görünür

Abstract:
Phthalocyanines set up by chance have been the subject of numerous inquiries and
these (Leznoff and Lever, 1989b; McKeown, 1998). Phthalocyanine (Pc), which
means"dark blue mineral oil painting" in Greek, was discovered at the morning of the
twentieth century as an undoable and dark colored by product during the conflation of
o-cyanobenzamide from phthalimide and acetic anhydride, but its molecular structure
wasn't illustrated for further than a quarter of a century (De Diesbach and Von der
Weid, 1927; Leznoff and Lever, 1989b). Although phthalocyanines are composed of
pyrrole units and are structurally veritably analogous to motes set up spontaneously in
nature, similar as chlorophyll a, hemoglobin and porphyrin, they're produced entirely
synthetically (García-Sánchezetal.,2013). Phthalocyanines are veritably stable blue or
green colors and colorings, an important class of commercially available chemicals
in numerous fields of technology.
The two hydrogen tittles in the patch's central depression are one of further than 70
central can be substituted with essence, and a variety of Substituents can be attached
to both supplemental and axial positions. (De la Torre et al; Elemans et al, 2006;
Engelkamp and Middelbeek, 1999) In particular, supplemental or list of different
groups to thenon-peripheral positions and Pc depression, making it easier to synthesize
motes. PCs are red photodynamic remedy in recent times because they absorb in the
hereafter region (600- 800 nm). PDT) system, which can be used in the alternate
generation print detectors class. Eldar et al, 1990; Haimovici et al, 2002; Spesia et al,
2009).
The phthalocyanine emulsion, a tetrapyrrole outgrowth, was first synthesized in 1907
in the South Metropolitan- cyanobenzamidine by Braun and Tcherniac at the Gas
Company (London) reported as a result of its accidental appearance as a colored byproduct during product. Braun and Tcherniac, 1907). Latterly, in 1927, the University
of Fribourg By Diesbach and von Weid, o- dibromobenzene was synthesized from
bobby cyanide and pyridine bobby (II) as a blue product formed by hotting at high
temperature in the presence of phthalocyanine (Pc) was attained but its structure wasn't
illustrated (De Diesbach and Von 2 der Weid, 1927) in 1934, a symmetric, 18 π,
conforming of four iminoisoindoline units. The structure of sweet phthalocyanine (Pc)
with electrons was delved by Linstead and Robertson's X-ray studies. (Linstead, 1934;
Linstead and Lowe, 1934). Phthalocyanine, with its naturally being porphyrin structure
similarity, with the differences arising from the four benzo groups and nitrogen tittles
in each of the four meso positions (McKeown, 2003; Robertson,)
Both metal-containing and metal-free phthalocyanines have been known for nearly a
century and are in the same group as biologically occurring porphyrins, making them
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perhaps one of the most extensively studied macrocyclic molecules. Due to their
beneficial properties, such as optical, electronic, electrical, photoelectric and
electrochemical properties, they have become among the most studied candidates for
use in the production of new electronic devices, gas sensors and detectors, many
catalytic reactions and solar cells. The intramolecular π-π interactions of
phthalocyanines lead to strong intermolecular interactions, which in turn cause
aggregation, which negatively affects the solubility of the molecules. Therefore, the
utilization of the extraordinary properties of these structures is undermined. To avoid
this, different functional groups or newly designed molecules are attached to
phthalocyanines from peripheral or non-peripheral positions. These bonded groups or
molecules confer different unique properties to phthalocyanines.
Chalcones, which are aromatic ketones and enones, are the basis of many biological
compounds and have important properties such as anti-cancer antioxidant,
antimicrobial, cytotoxic, analgesic and antipyretic They are also known as precursors
of flavonoids and isoflavonoids. The synthesis of a basic chalcone compound is carried
out via aldol condensation and is formed by a sodium hydroxide-catalyzed reaction
between an aldehyde and a ketone. Chalcones, which are compatible with their
biological activity and have good solubility, can be easily used in biological systems.
In areas such as electrocatalysis, photodynamic therapy, enzyme inhibitory effects,
photodiode properties, photophysical and photochemical properties, metal sensing
applications, DNA binding, enzyme inhibition synthesis of chalcone-substituted
metallophthalocyanines, spectral, electrochemical and spectroelectrochemical
properties are of increasing interest for both experimental and theoretical studies.
In this study, the synthesis of a chalcone-derived phthalocyanine and its
electrochemical and spectroelectrochemical behavior will be investigated and the
experimental spectroscopic data will be compared with the theoretical data calculated
by FTIR method.
To synthesize my target Pc's, I first obtained chalcone 3 compound. For this, I
synthesized chalcone 3 compound by adding 4-Methoxyacetophenone to 4-
hydroxybenzyldehyde molecule in the presence of KOH catalyst for 24 hours. For this,
starting from 4-hydroxybenzyldehyde and 4-Methoxyacetophenone, I obtained
chalcone 3 compound with a yield of 28.4% in ethanol water mixture. I used my
chalcone 3 compound as the main product to synthesize chalcone 5. I added potassium
carbonate to my chalcone 3 compound by dissolving 4-nitrophthalonitrile in DSMO
and continued my reaction for 24 hours and synthesized my chalcone 5 compound.
This synthesized chalcone compound will be the starting material of phthalocyanine
at room temperature with 4-nitrophthalonitrile in a yield of 52.1%. 1H and 13C NMR
spectra were used to determine the structures of chalcone 3 and chalcone 5. The
synthesized chalcone 3 and chalcone 5 molecules were confirmed by FT-IR spectra.
The phthalonitrile compound 5 was used as starting material for
metallophthalocyanines (MPc's). Chalcone 3 and chalcone 5 were successfully
synthesized as tetrahedral metallophthalocyanines with "(E)-3-(4-hydroxyphenyl)-1-
(4-methoxyphenyl) prop-2-en-1-one"attached at the peripheral positions of the
phthalocyanines. This monomer was then reacted with Zn(OAc)2.2H2O,
Co(OAc)2.4H2O salts and cadmium acetate dihydrate at 160 ⁰C under nitrogen
atmosphere at 160 ⁰C using Zn+2 for Pc-6, Co+2 for Pc-7 and Cd+2 for Pc-8 as metal
ion sources for the center of phthalocyanines. Metallophthalocyanines were obtained
by reaction with zinc, cobalt and cadmium salts. After the cyclotetramerization
reaction, an isomeric mixture of the desired MPc's was obtained as expected. The
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synthesized new phthalocyanines Pc-6, Pc-7, Pc-8 were characterized by 1H and 13C
NMR, FTIR, HRMS and UV-Vis spectroscopy
Keywords: Chalcone, Phthalocyanine, Redox, spectroelectrochemistry, Catalysis, UV
Visible