Diaza-dioxa substitue ftalosiyanin, oksim ve kompleksleri
Diaza-dioxa substitue phthalocyanine, oxime and complexes
Yazar: ESİN HAMURYUDAN
Danışman: PROF.DR. ÖZER BEKAROĞLU
İstanbul Teknik Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı
Derece: Doktora, 1994
Konu: Kimya = Chemistry
Dizin: Diazo bileşikleri = Diazo compounds ; Ftalosiyaninler = Phthalocyanines ; Oksimler = Oximes ; Sübstitüe = Substitue

Özet:
ÖZET Fîalosiyaninier ve vic-dioksimlerle yapılan kompleksler gösterdikleri çeşitli özellikler sebebiyle geniş uygulama alanlarına sahiptirler. Substitüe olmayan ftalosiyanin ve oksim kompleksleri suda ve organik çözücülerde hiç çözünmediklerinden yapılan araştırmaların önemli bir hedefide çözünür ürünler elde etmektir. Bu bileşiklerin çözünürlükleri; hacimli substitüentler, polar gruplar veya makro hetero halkalar ilavesiyle artırılabilmektedir. Bu sayede gerek yapı, gerekse reaksiyonlarının incelenebilmesi de mümkün olabilmektedir. Bu çalışmada o-nitro fenolden yola çıkarak önce 1,2- bis ( 2'-aminofenoksimetil ) -4,5- dibromobenzen 2 elde edilmiş, daha sonra çalışma ftalosiyanin sentezi ve oksim komplekslerinin sentezi olmak üzere iki yönde yürütülmüştür. Çalışmanın birinci bölümünde; 2 bileşiğinden başlayarak 16-üyeli tetrabenzodiazadioksa makrosiklik bileşiği ile periferal pozisyonlarda substitüe olmuş bakır ftalosiyanin sentezlenmiştir. Çalışmanın ikinci bölümünde; 2 bileşiğinin anti- dikîorgîioksim ile reaksiyonundan 14-üyeli diazadioksa makrosikliği taşıyan yeni bir vic-dioksim ve bunun mono- di-, tri- ve penta-nükleer kompleksleri elde edilmiştir. Elde edilen yeni maddelerin yapıları; Elemente! analiz, İR, NMR, atomik absorpsiyon, UV-VIS, kütle spekîrograf isi ve elektronik ölçümlerle aydınlatılmıştır.

Abstract:
SUGARY DIAZA-DSOXA SUBSTITUE PHTHALOCYANÎNE, OXiiVIE AND COMPLEXES One of the major areas of interest is coordination chemistry, in which the interaction of a central atom with surrounding atoms, ions or molecules is studied. Coordination compounds containing mac no cyclic ligands have been known and studied since the beginning of this century; however, until quite recently, the number and variety of these compounds was limited. In 1967 a new series of macrocyclic compounds which have the ability to function as complexing agents was reported by Pedersen. He prepared more than 60 compounds with a variety of ring sizes, a number of ether oxygens and substituent groups. After the crown compounds; macrocycies containing oxygen donor atoms, nitrogen donor atoms, sulphur donor atoms and mixed donor atoms has been synthesised. The development of syntheses for new macrocyclic systems of potential interest for discrimination studies has been a major thrust of the program of research. In particular, emphasis has been given to the preparation of new oxygen-nitrogen donor macrocycies. These iigands, which incorporate various combinations and numbers of donor atoms, are intermediate in structure between the crown polyeters and the category of macrocycies which incorporate mainly nitrogen donors. The aim of this.study is to synthesised anew macrocyclic compound containing N, O donor atoms which will be suitable to us^e as starting for phthalocyanine and vic-dioxime complexes. VÎThe special nature of the macrocycle phthalocyanine and its metal complexes has been known for 60 years. Since then the unique physical and chemical properties of this class of coordination compounds have been exploited from both the practical as well as theoretical point of view. Recently, a compelling reason to study the detailed coordination chemistry of metallophtalocyanines has arisen. The great activity in bioinorganic chemistry has led to a variable avalanche of work on metal- loporphyrins and other naturally occurring macrocyclic coordination compounds. In addition to their extensive use as dyes and pigments, unsubstituted and substituted phtalocyanines have found wide application in optical recording, photoconductive materials, photodynamic therapy, electrochromic processes as thin films, materials for electrophotography, charge separation in photovoltaic cells and as chemical censors. For this broad range of applications, the stable phtalocyanine core should be amenable to modifications which can be accomplished either by changing the central metal ion or by adding functional groups on the periphery. insolubility in most common organic solvents is also a characteristic property of phthalocyanines and its numerous metal complexes. We have been interested in the possibility of modifying the complexing ability and selectivity of various macrocyclic donor groups towards metal ions by attaching them as peripheral substituents onto phthalocyanines. in the first part of this work a 16-member symmetrical tetrabenzodiazadioxa macrocycle has been synthesised and a copper phthalocyanine derived from it. Starting from o-nitropheno! and 1,2-bis(bromethyI)- 4, 5-dibromobenzene, the synthetic rate is outlined in Scheme 1. A. Williamson ether synthesis gave the 2,2'- dinitro compound 1, which was reduced to the diamino derivative 2 by iron powder in a w-eakly acidic medium maintained by addition of acetic acid. Tosylation of the amino groups was carried out in pyridine with toluene-p-sulf onyl chloride 3. For the cyclization reaction 4; 3 and 1, 2-bis(bromomethyl)benzene were VI!allowed to react in N, SM-dimethylformamide(DMF) in the presence of anhydrous potassium carbonate at room temperature. The cyclotetramerization of 4 with copper(l)cyanide in teiramethylurea(TMU) gave the desired copper phthalocyanine 5. Although the yield of the crude produce was rather high, the purification steps were tedious and required a final column chromatography with neutral alumina and it was soluble in chloroform, dichloromethane, DMF and 1,1,2,2- tetrachloroethane. Y-A Scheme 1. Synthetic route of Cu phthalocyanine The reaction sequence in this work is clearly followed by a combination of the IR and NMR spectra data. The IR spectrum of the macrocycle 4 exhibits characteristic frequencies at 3060(Ch ar), 2960-2840 (CH aiiph), 1340 and 1150(SO2) and 620cm"1 (C-Br). The 1H-NMR spectrum is also consistent with the proposed structure; in addition to the aromatic protons, CH2-0 and CH2-N protons appear at 4.82 and 4.50 ppm. In the UV-VİS spectrum, the characteristic Q band transition of copper phthalocyanine with-- D4h symmetry is observed as a single band of high intensity at 673nm. In extremely dilute solutions(ca; 1 0"6moi. dm"3) chloroform the phthalocyanine molecules are present as monomers. Gradual increases in ooncontration result viain a lowering in the intensity of the Q band at 673nm together with a slight increase in the absorption at 649 nm denoting the formation of aggregated species. On the other hand; oxime compounds are widely recognised for their unique properties such as chelation oxygen-scavenging, biodegradability and unusual activity in biological and photo-chemical reactions. Oximes are used both as end products and ntermediates. The successful design and synthesis m P be sim as a a o ıııiBi uicutoics. i lie suuiscsaiui ussiyn auu sjiiuicsis of iigands capable of forming multinuclear complexes are of great interest for obtaining special effects in -lagnetic, optical and electrical properties. For this urpose, the Iigands need to carry multidonor groups to able to bind more than one metal ion ultaneously. Macrocyclic iigands can be considered «a an important candidate for one of the components of these Iigands. Although many example,of macrocyclic synthetic Iigands contain identical donor groups being liable to more donors sites has been also employed to tune the selectivity and stability. Incorporation of a vic-dioxime moiety onto the macrocycle provides an efficient binding site for transition metal ions through formation of an MN4 core with additional two hydrogen bridges. The high stability of the complex prepared with vic- dioxime Iigands has been extensively used for various purposes including model compound for vitamin B 1 2 or trace metal analysis. Recently the two H-bridges have been substituted with metal complexes to obtain tri- nuclear compounds in order to investigate the magnetic interactions of the metal ions. In the second part of these work; our aim was to undertake the synthesis of a vic-dioxime ligand carrying a 14-member N2O2 macrocycle. The synthetic route is outlined in Scheme 2. Mono-, di-, tri- and penta-nuclear complexes of this new ligand were isolated and characterized. The basic of N donors in this macrocycle is rather low while they take place just near the oxime groups; i.e. their basic is comparable with amides. However, three-nuclear complexes have been obtained arisen by deprotonation of these NH groups. The synthesis of a penta-nuclear complex has been also accomplished by insertion of the 1,10- phenantroline complex of Cu in the place of bridge hydrogens. At the beginning; 1,2-bis(2'- aminophenoxymethyi)-4, 5-dibromo benzen 2 was IXprepared by the same method as described in part. The macrocyclic vic-dioxime " ' ligand the (LH4) first has ime ıg the neutralize HCI formed. In the 1H- NMR spectrum of LH4, a single chemical paıı. i no ma^ıuuyt^ııu vit-uiuAinis ııy aııu \ ı_ n 4 / 11 been prepared by the reaction of anti-dichloroglyoxii with 2. Solid NaHC03 in excess is added during t reaction in order to shift for OH 1^1 m rx p w o i i u 1 1 1 ^ ı u 114, a anisic wiicniiwai gıııı 1 1 kj 1 w protons indicates that the oxime groups are in the ant form. This single disappears by deuterium exchange. NOH HON NOH H NH HN Cl//^ NOH Kono-nllkleer Kompleks Di-nUkleer kompleks Tri-nUklaer kompleksler Penta-nllkleer kompleksler Scheme 2. Synthetic route of vic-dioxime and complexes N i ( II ) complex of LH4 has a m e ta I : I i g a n d ratio of 1:2 and the ligand coordinates only through the N,N atoms of the vic-dioxime. The ( O H... O ) bridge is characterized by a broad absorbtion for the bending vibrations at 1720 cm"1. As expected for a d8 confi guration in a square-planar field (LH3)2Ni is diamag- netic as confirmed by the N M R spectrum. In contrast to Ni(ii) ion which gives only mononuclear complexes with LH4, tri-nuclear complexes are obtained with Cu(il), Co(ll), Co(lll) and Pd(ll); for each macrocycle one metal ion is coordinated to two aza- and two oxa-groups of each macrocycle, while the third metal ion is coordinated through the N,N atoms of each oxime group in the two ligand molecules. These complexes have a metakligand ratio of 3:2. (LH)2Co3 is oxidized to a diamagnetic octahedral Co(lll) derivative by bubbling air through a solution of the complex in the presence of pyridine. However, attempts to reduce the Co(lli) complex to Co(l), aprocedure used extensively to prepare alkyl cobaloxime derivatives of dimethylglyoxime and other vic-dioximes, were not successful. The six coordinated complex with Co(lll) should be of the type (LH)2Co3(py)3CÎ3. Pyridine ligands are coordinated axially to the metal in these octahedral complexes. Di-nuclear U02 complex was prepared from the uranyl acetate salt and the ligand in analysis of the complex ind ratio is 1:1. Uranyi complexes metahligand ratio are rather reported a binuclear complex The IR spectrum is also structure. A strong band around 900 cm characteristic frequency for (0 = U = 0) vibrations methanol. The elemental icated that metal : figan d of vic-dioximes with this few although we have with n-hydroxo bridges. consistent with dimeric "1 is the in this study we have accomplished the synthesis of penta-nuclear C u (II) complex with (LH)2Cu3 as the bridging ligand and 1,10-phenanthroline as an end-cap ligand. Formation of this pentanuclear complex is verified by the M * peak at 1917 which has been obtained by mass spectrometry. The last two Cu ions in penta-nuclear complex need to be tetra coordinated with two nitrogens of phen and two oxygens of oxime. The nitrate ions are out of the coordination sphere as observed by the NO stretching vibrations around 1380 cm"1 which is a typical value for io-nic nitrate group. With the electrochemical measurements of tri-nuclear Cu(ll); two one-electron reduction waves were observed. One of them is irreversible and the other is quasireversible. Three one-electron reduction waves and two one-electron oxydation waves were observed for penta-nuclear complex. XI