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Luminescence Features of Neodymium(III) Compounds with Various Tetrapyrrole Macrocycles Люминесцентные Свойс

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Luminescence Features of Neodymium(III) Compounds with Various Tetrapyrrole Macrocycles Люминесцентные Свойс Porphyrins Paper Порфирины Статья DOI: 10.6060/mhc170621r Luminescence Features of Neodymium(III) Compounds with Various Tetrapyrrole Macrocycles Nikolay N. Semenishyn,a Sergii S. Smola,a Natalya V. Rusakova,a@ Gerbert L. Kamalov,a Yulia G. Gorbunova,b,c and Aslan Yu. Tsivadzeb,c aA.V. Bogatsky Physico-Chemical Institute, 65080 Odessa, Ukraine bA.N. Frumkin Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences, 119071 Moscow, Russia cN.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991 Moscow, Russia @Corresponding author E-mail: [email protected] We considered the changes in the luminescent properties in the series of neodymium(III) complexes of various coordination types with different tetrapyrrole macrocycles (porphyrins, phthalocyanines and corroles): mono- nuclear complexes (metal-ligand ratio 1:1), sandwich type complexes (metal-ligand ratio 1:2 or 2:3), peripheral binding (on the basis of ditopic tetrapyrrole, metal-ligand ratio 1:1). 4f-Luminescence in the near infrared region is observed in all studied Nd-complexes as a result of intramolecular transfer of excitation energy. Each kind of com- plexes has its unique features, which are discussed. The peripheral complexes are dual-emissive: they display both neodymium(III) 4f-emission and molecular fluorescence. The values of quantum yield of molecular fluorescence as well as 4f-luminescence are estimated. It was found that binding type plays a key role in excited state relaxation pathways in the molecule. Corroles have unusual behaviour in terms of Nd sensitization. Keywords: Tetrapyrroles, luminescence, neodymium, porphyrin, phthalocyanine, corrole. Люминесцентные свойства соединений неодима(III) с различными тетрапиррольными макроциклами Н. Н. Семенишин,a С. С. Смола,a Н. В. Русакова,a@ Г. Л. Камалов,a Ю. Г. Горбунова,b,c А. Ю. Цивадзеb,c aФизико-химический институт им. А.В. Богатского НАН Украины, 65080 Одесса, Украина bИнститут физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук, 119071 Москва, Россия cИнститут общей и неорганической химии им. Н.С. Курнакова Российской академии наук, 119991 Москва, Россия @E-mail: [email protected] Мы изучили изменения люминесцентных свойств класса комплексов неодима(III) различных координацион- ных типов с несколькими тетрапиррольными макроциклами (порфиринами, фталоцианинами и корролами): моноядерных комплексов (соотношение металл-лиганд 1:1), комплексов сэндвич-типа (соотношение металл- лиганд 1:2 или 2:3), периферического связывания (на основе дитопического тетрапиррола, соотношение металл-лиганд 1:1). 4f-Люминесценция в ближней инфракрасной области наблюдается во всех изученных Nd-комплексах в результате внутримолекулярного переноса энергии возбуждения. Обсуждаются уникаль- ные особенности каждого вида комплексов. Периферические комплексы являются двухэмиссионными: они проявляют, как 4f-эмиссию, так и молекулярную флуоресценцию. Были оценены значения квантового выхода молекулярной флуоресценции, а также 4f-люминесценции. Было обнаружено, что тип связывания катиона неодима играет ключевую роль в формировании энергетических путей релаксации возбужденных состояний в молекуле. Корролы характеризуются необычным поведением с точки зрения сенсибилизации неодима. Ключевые слова: Тетрапирролы, люминесценция, неодим, порфирин, фталоцианин, коррол. 268 © ISUCT Publishing Макрогетероциклы / Macroheterocycles 2017 10(3) 268-272 N. V. Rusakova et al. Introduction orolog FL 3-22" "Horiba Jobin Yvon" (Хе-lamp 450 W). Spectra of 4f-luminescence of Nd3+ were registered at 850–1150 nm (tran- 4 4 4 4 One of the most important parts of investigations sitions F3/2→ I13/2, F3/2→ I11/2; note, that signal of the third transi- 4 4 in the field of lanthanides is their opportunity to form lu- tion F3/2→ I13/2 was very weak, so we did not take it into account). minescent compounds with different organic chromophores. Spectra of molecular fluorescence of porphyrins, corroles and phthalocyanines were registered at 550–800 nm (S –S tran- Luminescence properties of such compounds always depend 1 0 sitions). Luminescence integral intensity was measured using on the nature of the lanthanide ion and the chromophore, software of the device. The relative quantum yield of molecular which are included in the structure of such complexes, theirs fluorescence was determined using solution of Zn-tpp (H tpp – [1] 2 quantity, medium and other factors. 5,10,15,20-tetraphenylporphyrin) in ethanol as a primary standard Note that 4f-luminescence (luminescence of 4f-ele- (0.022).[7,11] Determination of the relative quantum yield (accu- ments) in the near infrared (NIR) region is one of the most racy is ±10 %) of molecular fluorescence and 4f-luminescence demanded for medicine (as markers) and technology (as a base was made using formula: for optical devices like fiber-optics, etc.) due to several very 2 2 important reasons: φх=φ0IxA0nx /(I0Axn0 ), – light of NIR range can penetrate biological tissues where φ and φ – luminescence quantum yield of the standard much more effectively in comparison to UV/VIS 0 х and of the sample, respectively, A and A – absorption at ranges (UV – ultraviolet, VIS – visual) due to the weak 0 x the wavelenght of Soret band of the standard and of the sample, overlapping with absorption of bioobjects; respectively, I and I – integral luminescence intensity of the stan- – NIR light is absolutely safe for human in comparison x 0 dard and of the sample, respectively, n0 and nx – refractive index to UV range, which action can generate dangerous of the standard solvent and of the sample solvent, respectively. radical species; Fluorescence lifetime was measured under excitation – NIR photons undergo much less scattering in compari- at the Soret band. son to UV/VIS light. Tetrapyrroles are the best candidates for obtaining NIR emitting objects. Their low-energy donor triplet (T) levels Results and Discussion are suitable for intramolecular energy transfer to the reso- nant levels of such NIR emitting lanthanide ions like Nd3+, All polytopic porphyrins and corroles were synthe- Ho3+, Er3+, and Yb3+. These macrocycles have a very strong sized through the acylation of parental aminoderivatives absorption in near UV region and in visual region. (H2atpp – 5-(4-aminophenyl)-10,15,20-triphenylporphyrin Lanthanide porphyrins as NIR-emitting agents have and H3dpfc – 10-(4-aminophenyl)-5,15-di(pentafluorophe- been studied starting from 1974.[2] It is interesting that por- nyl)corrole) by bis-anhydrides (BA) of aminopolycarbonic phyrins were the first macrocyclic compounds that showed acids (ethylenediamine-N,N,N’,N’-tetraacetic acid, H4edta sensitization of 4f-luminescence. The investigation of these and diethylenetriamine-N,N,N’,N’,N’’-pentaacetic acid, compounds always deals with several main drawbacks H5dtpa). The structure of all studied compounds (ligands such as relative lability (a result of discrepancy of the core and complexes) is presented in Figure 1. Unfortunately, neo- of porphyrins and lanthanide ions radii; only some lan- dymium-porphyrins are labile compounds, but the complex thanide ions have stable complexes with porphyrins due Nd-tpp(Acac) (Acac – acetylacetonate) was used only for to lanthanide compression) and relatively low efficiency comparison. The lanthanide complexes with the functional- of NIR emission of lanthanide ion. To avoid the problem ized porphyrins and corroles are formed with ratio Ln:L=1:1. of stability of complexes there were presented different Thus, in this work we consider several types of Nd- approaches of external porphyrin-lanthanide binding, complexes: mononuclear complex (metal-ligand ratio 1:1), reviewed in [3]. It is very important to mention that there double-decker complex (metal-ligand ratio 1:2), peripheral is no any significant decreasing of 4f-emission efficiency binding (on the base of ditopic tetrapyrrole, metal-ligand under such conditions of sensitization.[4] Recently the first ratio 1:1). example of near-infrared 4f-luminescence of sanswich type Previously we showed that peripheral complexes lanthanide phthalocyanines was demonstrated using Er(III) Ln-edta-tetrapyrroles have two coordinated water mol- and Yb(III) complexes.[5] ecules, while the Ln-dtpa-tetrapyrroles do not contain Many systems containing Nd3+ have been regarded water in their structure. This difference was attributed as the most popular luminescent materials for laser sys- to the larger coordination number of the lanthanide ions tem applications.[6] Thus, we have investigated influence in dtpa-derivatives than in edta-derivatives.[7] Note, that of different parameters of the structure on their luminescent water is undesirable component of the inner coordination properties and stability: e.g. nature of tetrapyrrole, quantity sphere of Nd3+. Its presence leads to energy dissipation due 4 4 −1 of metal ions and the type of coordination. to overlapping of the F3/2→ I15/2-transition (5400 cm ) with the O–H bond vibrational quanta ν=2 (6900 cm−1) and such an excitation of vibration state leads to effective quenching 4 Experimental of the F3/2-state. 4f-Emitting was fixed in all Nd-containing complexes. Syntheses of the corrole, porphyrin and phthalocyanine deriv- Full coincidence of the absorption and excitation spectra atives, as well as their complexes were described previously.[4,7-10] of these compounds clearly shows that the 4f-luminescence Spectra of molecular fluorescence, 4f-luminescence of Nd3+ takes place as a result of ligand-to-lanthanide
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