Porphyrazines with peripheral phosphorous and naphthalene groups

Abstract

Peripherally functionalized porphyrazines have the potential to exhibit novel optical, magnetic and electronic properties; also maintain some additional features superior to the values met in related materials. The transition metal ion in the inner core offers new ways to induce, modify and control molecular properties. The starting point for a novel porphyrazine structure with eight naphlhyl units bound to the periphery through flexible methylthio-chains is l,2-bis(l-naphthylmethylthio)maleonitrile (I) which was obtained from disodium salt of dithiomaleonitrile and l-(chloromethyl)naphthalene. By the template effect of magnesium, blue-green colored magnesium porphyrazinate (2) substituted with eight naphthylmelhyl groups on the peripheral positions has been synthesized by cycloletramerization of 1 in the presence of magnesium butanolate. The metal-free derivative (3) was obtained by its treatment with trifluoroacetic acid and further reaction of this product with copper(ll) acetate, zinc(ll) acetate and cobalt(ll) acetate led to the metal porphyrazinates (4-6) $(M^{+2}= Cu^{+2}, Zn^{+2}, Co^{+2})$. In order to obtain triphenylphosphine substituted porphyrazines which is the main goal of this study, (2-carboxy-1-methylethyl) triphenylphosphonium bromide (9) is obtained by the reaction of triphenylphosphine and methacrylic acid with hydrobromic acid. Then, the -OH groups of octakis(2-hydroxyetyhylthio)porphyrazinatomagnesium (8) are reacted with 9 for esterification. The novel compounds were characterized by FT-IR, EPR,$^1H$ NMR, $^{31}P$ NMR, UV-Vis spectral techniques and elemental analysis.

Özet

Magnezyum butanolat varlığında l,2-bis(l-naftilmetiltiyo)maleonitril 'in (1) siklotetramerizasyonuyla periferalposizyonlardan bağlanmış sekiz adet naftilmetil grubu içeren sübstitiie mavi-yeşil renkli magnezyum porfirazin (2) sentez edilmiştir. Trifluoroasetik asitle muamele edilerek metalsiz türevine (3) geçilmiş ve bu ürünün çeşitli metal tuzlarıyla reaksiyona sokulmasıyla metal porfirazinler (4-6) elde edilmiştir $(M^{+2}= Cu^{+2}, Zn^{+2}, Co^{+2})$. Bu çalışmanın ana hedefini oluşturan trifenilfosfin sübstitiie porfirazinler elde etmek için önce trifenilfosfinin metakrilik asit ve hidrobromik asit ile reaksiyonu sonucu oluşan (2-karboksi-l-meliletil)trifenilfosfonyum bromür 'ün (9), oktakis(2-hidroksietiltiyo)porfirazinatomagnezyum 'un (8) -OH grupları ile esterleştirme reaksiyonu yapılmıştır. Yeni bileşikler FT-IR, EPR, $^1H$ ve $^{31}P$ NMR, UV-görünür bölge spektrumlarıyla ve elementel analizle karakterize edilmiştir.