Multichromophoric perylene bisimide dyes

Abstract

ABSTRACT:

Chromophores are responsible for the color of matter. The control of molecular interactions in multichromophores lead to functional dyes with novel properties. Furthermore, tailormade spectroscopic properties could be achieved, which are a prerequisite for applications that require dyes with absorption and emission in a specific region of the visible spectrum. With this special interest, we targeted to synthesize a multichromophoric macromolecule containing two different chromophores – a perylene and naphthalene. We have designed a molecular architecture of, and synthesized a novel multichromphoric macromolecule, N,N’-bis-{N-(3-[4-(3-amino-propyl)-piperazin-1-yl]-propyl)-N’-[1-dehdroabiety]-1,4,5,8-naphthalenetetracarboxydiimidly}-3,4,9,10 perylenebis(dicarboximide)bisimides (NPM) which was carried out in three consecutive steps. Our focus was also to enlarge both the absorption and emission ranges of the macromolecule and to investigate consequent optical properties. The first step includes the synthesis of a perylene dye, N-N’-bis-{3-[4-(3-amino-propyl)- piperazin-1-yl]-propyl}-3,4,9,10-perylenebis(dicarboximide) (PDI) where as in the second step, a naphthalene monoimide, N-(1-dehydroabietyl)-1,4,5,8-naphthalenetetracarboxylic-1,8-anhydride-4,5-imide (NMI) was synthesized. Finally, the designed macromolecule dye (NPM) was synthesized by using the above synthesized compounds, PDI and NMI. All the synthesized compounds were characterized in detail by IR, MS, NMR, UV-vis, DSC and TGA measurements. A much enlarged absorption (325 nm – 550 nm) and emission (375 nm – 700 nm) ranges were achieved by the synthesized macromolecule dye which was appreciably soluble in most of the commercial organic solvents. All the three synthesized compounds were photochemically and thermally stable and found no glass transition temperature in the DSC runs until 300 oC. The fluorescence quantum yields of the compounds were measured and PDI was reported high quantum yield among the three synthesized compounds. Several optical parameters were also calculated and reported.

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ÖZ:

Madelere rengini veren gruplar kromoforlardır. Çok kromoforlu yapılarda moleküler etkilesimlerin kontrolü, yaratılan özellikler ile fonksiyonel boyalarda yeni ufuklar açmaktadır. Bununla birlikte, görünür bölge absorpsiyon ve emisyon özelliklerinin önemli oldugu uygulamalarda özel olarak tasarlanmıs spektroskopik özellikler saglanabilmektedir. Bu çalısmada perilen ve naftalin kromoforlarını içeren çok kromoforlu bir makromolekül sentezlenmistir. Tez kapsamında yeni bir çok kromoforlu makromolekül olan N,N’-bis-{N-(3-[4-(3- amino-propil)-piperazin-1-yl]-propil)-N’-[1-dehidroabietil]-1,4,5,8- naftalintetrakarboksidiimid}-3,4,9,10 perilenbis(dikarboksiimid)bisimid (NPM) üç basamakta sentezlenmistir. Böylelikle sentezlenen makromolekülün absorpsiyon ve emisyon aralıgı genisletilmis ve optik özellikleri arastırılmıstır. _lk basamakda bir perilen diimid, N,N’-bis-{3-[4-(3-amino-propil)-piperazin-1-yl]- propil}-3,4,9,10-perilenbis(dikarboksiimid) (PDI), ikinci basamakta ise bir naftalin monoimid, N-[1-dehidroabietil]-1,4,5,8-naftalintetrakarboksilik-1,8-anhidrid-4,5- imid (NMI) sentezlenmistir. Son basamakta ise sentezlenmis olan PDI ve NMI kullanılarak makromolekül boya (NPM) sentezlenmistir. Sentezlenen tüm bilesikler IR, MS, NMR, UV-vis, DSC ve TGA ölçümleri ile karakterize edilmislerdir. Sentezlenen makromolekül, birçok organik çözücüde çözünürlüge sahip olup genis absorpsiyon (325 nm – 550 nm) ve emisyon (375 nm – 700 nm) aralıkları saglanmıstır. Sentezlenmis olan üç bilesik de fotokimyasal ve termal kararlılıga sahip olup DSC ölçümlerinde 300 oC sıcaklıga kadar camsı geçis sıcaklıgı gözlemlenmemistir. Bilesiklerin floresans kuantum verimleri ölçülmüs ve PDI en yüksek floresans kuantum verimine sahip bilesik olarak bulunmustur. Diger optik özellikler de hesaplanmıstır ve yorumlanmıstır.