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Synthesis and Functionalization of Corroles. an Insight on Their Nonlinear Optical Absorption Properties

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Synthesis and Functionalization of Corroles. an Insight on Their Nonlinear Optical Absorption Properties Send Orders for Reprints to [email protected] Current Organic Synthesis, 2014, 11, 29-41 29 Synthesis and Functionalization of Corroles. An Insight on Their Nonlinear Optical Absorption Properties Carla I.M. Santosa, Joana F.B. Barataa, Mário J.F. Calvetea, Luís S.H.P. Valea, Danilo Dinib*, Moreno Meneghettic, Maria G.P.M.S. Nevesa*, Maria A.F. Faustinoa, Augusto C. Toméa and José A.S. Cavaleiroa aDepartment of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal; bDepartment of Chemistry, University of Rome “La Sapienza”, 00185 Rome, Italy; cDepartment of Chemical Sciences, University of Padua, 35131 Padua, Italy Abstract: The development of efficient synthetic methodologies and post-functionalization procedures gave access to a wide variety of new corrole derivatives with potential applications in different areas. This paper reviews the preparation of meso-triaarylcorroles and their functionalization, namely via cycloaddition transformations, and describes the nonlinear optical (NLO) properties of a series of metal-free and gallium corroles with different peripheral substituents. The corroles studied were the free base 5,10,15-tris- (pentafluorophenyl)corrole, the corresponding gallium(III) complex and adducts obtained from 1,3-dipolar cycloaddition reaction. Corre- lations between the structure and the NLO effect of optical power limiting were attempted in our comparative analysis. The present con- tribution is one of the first reports on the effect of reverse saturable absorption in the visible spectrum generated by corrole-based com- plexes. Keywords: Corroles, cycloaddition reactions, functionalization, nanosecond pulse, optical limiting, reverse saturable absorption. 1. INTRODUCTION In analogy with porphyrins and phthalocyanines, corroles [1] are considered now an independent class of molecules within the N N C F C6F5 largest family of tetrapyrrolic compounds. This upgrade is mainly + C6F5CHO 6 5 M due to the high number of corrole derivatives that have been syn- N thesized in the last decade [2], and the knowledge of their own dis- H N N tinctive properties, derived from the structural characteristics con- ferred by the low symmetry [3], ring tension due to the direct - pyrrole connection [4], trivalent coordination core [5] and C6F5 tautomeric isomerism [6]. In terms of electronic structure, corroles are aromatic macrocycles with a 18 -electron conjugated system 1, M=3H similar to porphyrins, [7] which are able to stabilize high-valence 1a, M=Ga(py) metal ions through ring coordination much more effectively than porphyrins. In the review here presented we will focus on the syn- Scheme 1. thesis of meso-substituted corroles, particularly the 5,10,15- tris(pentafluorophenyl)corrole, as well as its functionalization, be particularly suitable for the synthesis of A3-type corroles from along with an insight on the nonlinear optical properties of such aldehydes with strong electron-withdrawing substituents. For in- materials. stance, the 5,10,15-tris(pentafluorophenyl)corrole 1 was obtained in 11% yield. The route developed by Paolesse and co-workers [22] was based on the acidic conditions developed by Adler for the syn- 2. CORROLE SYNTHESIS thesis of meso-tetraarylporphyrins [23]. In this case, corrole 1 was Although corroles are not found in biological systems, the obtained in low yield (4%) [24]. Based on these synthetic ap- number of articles dedicated to the synthesis and applications of proaches, new progresses were made by other research groups. In these compounds has increased significantly over the past decade, particular, Gryko´s group was able to refine the experimental condi- and currently the popularity of corroles is, in some cases, approach- tions giving access to meso-substituted A3- and trans-A2B-corroles ing that of the related porphyrins [8-20]. [25-29]. In fact, three different sets of experimental conditions were explored, based on the (reactivity of the aldehyde, catalyst, solvent, This huge progress started in 1999, with the development of ef- concentration, time etc), in order to open access to a series of meso- ficient synthetic methodologies leading to meso-substituted cor- A -corroles. The condensation of aldehyde with pyrrole, in a water- roles, such as 5,10,15-tris(pentafluorophenyl)corrole 1 (Scheme 1) 3 methanol mixture in the presence of HCl was also reported [30]. from simple procedures developed by Gross [21] and Paolesse [22]. Collman and Decréau also considered the use of microwave ir- The procedure proposed by Gross and co-workers [21] involves radiation in the synthesis of tri-arylcorroles [31]. Compared with the condensation of pyrrole in the absence of solvent and proved to the conventional heating methodology, the microwave irradiation affords noticeably cleaner reaction mixtures and higher yields of the corrole. Chauhan and Kumari [32] reported the synthesis in the *Address correspondence to these authors at the Department of Chemistry, University presence of Amberlyst 15 catalyst and under solvent-free condi- of Rome “La Sapienza”, 00185 Rome, Italy; Tel: +39-06-49913335; Fax: +39-06-490324; E-mail: [email protected], and Department of Chemistry, University of Aveiro tions. In these conditions 5,10,15-tris(pentafluorophenyl)corrole 1 3810-193 Aveiro, Portugal; Tel: +351234370710; E-mail: [email protected] was isolated in 30% yield. Recently Nocera et al. [33] carried out 1875-6271/14 $58.00+.00 © 2014 Bentham Science Publishers 30 Current Organic Synthesis, 2014, Vol. 11, No. 1 Santos et al. HO HO O C6F5 SO N OH 2 H OH HO N N M C6F5 HO O N N SO2 N OH H OH C6F5 3 O O O O C6F5 N SO2 O O O O N N C F M O 6 5 O N O O N N SO2 O O O O C6F5 4 O SO2Cl ClO2S C6F5 N N NH O SO C F M C6F5 2 6 5 N N O N N C6F5 M N N C F 6 5 2 SO2 NH O C6F5 5 C6F5 SO N COOH 2 H N N M C6F5 N N SO2 COOH N H 6 C6F5 C6F5 SO2 NH N N C6F5 M N N N H O H N C H SO NH N C6F5 2 7 S O N H H Scheme 2. Synthesis and Functionalization of Corroles Current Organic Synthesis, 2014, Vol. 11, No. 1 31 NH HN C6F5 C6F5 N HN C6F5 pentacene, 1,2,4-trichlorobenzene , 200 °C NH HN NH HN NH HN C F C F 6 5 6 5 C F C F + C6F5 C6F5 + 6 5 6 5 N HN N HN N HN C6F5 C6F5 C6F5 8 9 10 Scheme 3. the synthesis of 5,10,15-tris(pentafluorophenyl)corrole in large The introduction of nitro and amino groups at the -pyrrolic po- scale. sitions of corroles allowed further modifications of these com- pounds [55-61]. The ionic liquid [Bmim][BF4] was also reported as a suitable reaction medium in the preparation of meso-substituted trans-A2B- Approaches involving reagents or catalysts based on transition corroles [34]. metal compounds are also being explored to modify the corrole core. Most of these strategies are based on transformations cata- 3. FUNCTIONALIZATION OF CORROLES lysed by palladium(0) using meso-4,6-dichloropyrimidin-5-yl- substituted corroles and meso-arylcorroles bearing bromine sub- The progress in synthetic methodologies leading to meso- stituents in -pyrrolic positions or in the phenyl groups [62-72]. triarylcorroles was accompanied by a considerable effort to develop The versatility of cycloaddition reactions was explored by different strategies for the functionalization of meso-triarylcorroles. For ex- groups, including ours, as an efficient methodology to functionalize ample, the nucleophilic aromatic substitution reaction of the para-F corrole core. For instance, the reaction of corrole 1 with pentacene atoms in 5,10,15-trispentafluorophenylcorrole 1, which is fre- afforded the expected oxidized Diels-Alder adducts 8 and 9 along quently used for the modification of porphyrins [35], is often used with the [4+4] cycloadduct 10 (Scheme 3) [73]. for its functionalization. Osuka and co-workers explored this ap- proach to introduce several amines into corrole 1 [36], while Following interest in Diels-Alder reactions, the reactivity of Cavaleiro and co-workers used it to link galactose residues [37] or corrole 11 (Scheme 4) bearing a vinyl group as 2 and 4 compo- to functionalize it with silica particles [16]. Maes and co-workers nents was also studied [17,18]. This derivatives was obtained considered the nucleophilic aromatic substitution of chloro atoms in through a Wittig reaction, from the corresponding formyl derivative the 4,6-dichloropyrimidin-5-yl units of meso-pyrimidinyl- obtained by Vilsmeier-Haack reaction [56, 74]. substituted corroles as a post-functionalization of this type of plat- Considering the vinyl corrole 11 as diene, its reactivity was form [38, 39]. tested with 1,4-benzoquinone, 1,4-naphthoquinone and dimethyl Several procedures were established for the insertion of halogen acetylenedicarboxylate affording the expected oxidized compounds atoms (Br, I, Cl) into the -pyrrolic positions of the corrole macro- 12, 13 and 15, respectively (Scheme 4). The unexpected formation cycle [38, 40-46]. Conventional procedures, such as sulfonation, of compound 14 with dimethyl acetylenedicarboxylate was justified chlorosulfonation afforded the expected derivatives in excellent by a cyclotrimerization process [75]. yields. In particular, the 2,17-dichlorosulfonated corrole 2 has been As dienophile, the Diels-Alder cycloadducts 16 were obtained extensively used as a versatile precursor of corroles with sulfona- in the presence of o-quinone methides generated in situ from mide groups to be used for advanced applications and materials Knoevenagel reaction of 4-hydroxycoumarin or 4-hydroxy-6- [47-54]. The water-soluble carbohydrate corroles 3, pegylated cor- methylcoumarin with paraformaldehyde (Scheme 4) [17]. roles 4, donor-acceptor dyads 5, amino acid corroles 6 and corrole- biotin conjugates 7 are examples of such compounds (Scheme 2).
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