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Supramolecular Chirality in Porphyrin Chemistry Symmetry 2014, 6, 256-294; doi:10.3390/sym6020256 OPEN ACCESS symmetry ISSN 2073-8994 www.mdpi.com/journal/symmetry Review Supramolecular Chirality in Porphyrin Chemistry Victor Borovkov Department of Applied Chemistry, Osaka University, 2-1 Yamada-Oka, Suita, Osaka Prefecture 565-0871, Japan; E-Mail: [email protected]; Tel.: +81-6-6879-4128; Fax: +81-6-6879-7923 Received: 18 March 2014; in revised form: 18 April 2014 / Accepted: 21 April 2014 / Published: 23 April 2014 Abstract: Supramolecular chirality, being an intelligent combination of supramolecular chemistry and chiral science, plays a decisive role in the functioning of various natural assemblies and has attracted much attention from the scientific community, due to different applications in modern technologies, medicine, pharmacology, catalysis and biomimetic research. Porphyrin molecules are of particular interest to study this phenomenon owing to their unique spectral, physico-chemical and synthetic properties. This review highlights the most important types of chiral porphyrin structures by using the best-suited representative examples, which are frequently used in the area of supramolecular chirality. Keywords: supramolecular chirality; supramolecular chemistry; chirality; porphyrin; host-guest; self-assembly; conformation 1. Introduction Chirality is one of the most fundamental principles of nature and describes the ability of any object to exist as a pair of non-superimposable mirror images, which are termed enantiomers (Figure 1). In the case of supramolecular chirality, the processes associated with the chirality phenomena are driven by various types of noncovalent interactions between the components of these systems. In this respect, the chiral properties of porphyrinoids are of particular interest, due to their direct relevance to many vital biological processes, such as oxygen transport, electron transfer, enzyme functioning and photosynthesis [1]. Furthermore, these compounds have turned out to be particularly well suited for investigating different chiral processes and, particularly, supramolecular chirality, because of their specific and highly appropriate spectral, physico-chemical and synthetic characteristics, facile handling and superior propensity to form various supramolecular assemblies [2]. Furthermore, this kind of molecular and supramolecular system, so far, has attracted considerable attention of the scientific Symmetry 2014, 6 257 community on account of the wide applicability in different fields of fundamental and applied sciences and modern technologies lying behind the judicious design of various chiroptical devices and sensors, molecular switches and machines, enantioselective materials and catalysts, as well documented in numerous reviews discussing these topics to a greater or lesser extent [3–15]. In general, chirality in the porphyrin-based supramolecular systems may be generated either via the intrinsic chiral modification of achiral porphyrinoids, by employing naturally occurring chiral pigments or via the external chiral field. In the case of dimeric and multimeric porphyrinoids, the asymmetry induction can be additionally achieved by a chiral linkage. Taking into account the vast number of publications in this area, only the most illustrative examples of each type of structural organization are overviewed in this review article. From the chirality point of view, the rigidly fixed bis- and multi-porphyrinoid systems exhibit a more straightforward relationship between their structures and properties, thus being more suitable systems for comprehensive rationalization, and therefore, their discussion should come first. Figure 1. A pair of enantiomers as represented by the amino acid, alanine. Chiral carbons (here and in other figures) are marked with the asterisk. CH3 CH3 NH2 NH2 C* C* H COOH COOH H 2. Chirality and Supramolecular Chirality of Covalently Fixed Rigid Architectures Generally, in chemistry, the chirality phenomenon most conventionally relates to molecules and/or (supra-) molecular systems, the intrinsic components of which (atoms or functional groups) are asymmetrically arranged in three spatial dimensions around a center, axis or plane. In this regard, the rigidly linked structures provide direct access to the chiral architectures. In the case of bis- and multi-porphyrinoids, this has come about through the introduction of stereogenic element(s) either into the macrocycle directly or into the connecting linkage. Besides, there is another type of multiporphyrin structure, which is based upon the asymmetrical spatial fixation of macrocycles, whilst neither porphyrin units nor covalent linkages themselves have stereogenic centers. Typically, the conformational stability of the overall structure may be ensured by two covalent bridges on the opposite sides of the porphyrin ring or by a single rigid linkage. At first, bis-porphyrinoid structures on the basis of chirally modified macrocycles connected by achiral covalent bridges are discussed. Symmetry 2014, 6 258 2.1. Chirality Introduced via Chiral Porphyrinoids One of the most representative examples of the first structural type is a series of doubly-strapped bis-porphyrins, 1–3 (Figure 2) [16,17]. In this case, chirality was introduced via the alkylation of one of the pyrrole nitrogens, making the alkylated porphyrin asymmetrical, whilst the rigidity of whole structure prevented the inversion process. The mirror image circular dichroism (CD) spectra were obtained for the corresponding enantiomers. The supramolecular chirality of 1–3 was explored upon the noncovalent interaction with the appropriate host molecules. Particularly, the interporphyrin cavity of these bis-porphyrins was designed to accommodate spheroidal fullerenes, especially C76, whilst the chiral properties were applied for discriminating the enantiomers of C76 (by 3) and enantioselective extraction (by 1), resulting in 7% enantiomeric excess (ee) in a single procedure. Figure 2. Structures of the doubly-strapped bis-porphyrins, 1–3. Another kind of covalent linkage was employed for the preparation of fixed bis-porphyrins, 4–7 (Figure 3) [18–21]. The chiral modification was carried out at two meso positions of each porphyrin ring, thus yielding four stereogenic centers correspondingly. Since the synthesis was based on enantiopure phenylalaninal, the chirality of 4–7 was predetermined as R or S exclusively. Two porphyrin moieties were rigidly connected by various aromatic bridges, resulting in the different spatial arrangement of macrocycles. In this case, supramolecular chirality was a result of noncovalent interaction with single-walled carbon nanotubes (SWCN). The judicious combination of chirality and the molecular geometry of these bis-porphyrins allowed the size selective discrimination of left- and right-handed SWCN, with the ee value of extracted SWCN being as high as 67% (in the case of 7). Chiral dimeric structures can also be obtained by the direct connection of porphyrin and chlorin structures, which is an intrinsically chiral macrocycle, or two chiral porphyrinoids. This type of linkage and the spatially bulky peripheral aromatic substituents are able to provide the conformational rigidity of the overall geometry (Figure 4). Hence, the thermal self-cycloaddition of symmetrical Symmetry 2014, 6 259 (tetra-β,β’-sulfolenoporphyrinato)zinc with the subsequent extrusion of SO2 yields the racemic chlorin-porphyrin complex, 8, the chiral property of which has not been explored yet, because the corresponding enantiomers have not been resolved [22]. However, in the case of β,β′-bonded chiral porphyrinoids, the corresponding enantiomers were successfully obtained [23]. In particular, the C21 methylation of 3,3′-bis(N-confused nickel porphyrin) resulted in the corresponding di-methylated derivative, 9. The asymmetry was derived as from the two homochiral subunits and from the rigid chiral conformation, which allowed memorizing chirality in the configurationally stable free base bis-porphyrinoid, 10, obtained upon demetalation of 9. Other examples of conformational chirality in bis-porphyrinoids will be discussed in the corresponding topic below. The chiral properties of 9 and 10 were characterized by the corresponding CD spectra exhibiting a typical bisignate pattern of exciton couplets in the region of porphyrinoid absorption, whilst the supramolecular chirality features are yet to be explored. Figure 3. Structures of the bis-porphyrins, 4–7, rigidly fixed with various aromatic spacers. Figure 4. Structures of the bis-porphyrinoids consisting of porphyrin and chlorin structures, 8, and two C21 methylated N-confused porphyrins, 9 and 10. Symmetry 2014, 6 260 Figure 4. Cont. 2.2. Chirality Introduced via Chiral Linkage Besides the asymmetry generated by chiral macrocycles itself, the chirality of bis- and multi-porphyrins may be produced via a rigid chiral linkage. In this case, both the double and single rigid bridges are also commonly employed. For example, two chiral straps containing the leucine residue brought about two porphyrin moieties in the bis-porphyrin, 11 (Figure 5), into the helical conformation. This spatial arrangement was evidenced by the characteristic exciton couplet in the corresponding CD spectra of porphyrin absorption [24]. Essentially, the L- and D-leucine derivatives resulted in the right- and left-handed orientation, respectively. The supramolecular chirality property of 11 was employed for optical resolution of a series of bidentate artificial oligopeptides (OPs)
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