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. 2023 Oct 27:19:1630-1650.
doi: 10.3762/bjoc.19.120. eCollection 2023.

Tying a knot between crown ethers and porphyrins

Maksym Matviyishyn  1 , Bartosz Szyszko  1
Affiliations

Tying a knot between crown ethers and porphyrins

Maksym Matviyishyn et al. Beilstein J Org Chem. .

Abstract

Porphyrins and crown ether hybrids have emerged as a promising class of molecules composed of elements of a tetrapyrrole macrocycle and an oligo(ethylene glycol) segment. These hybrid systems constitute a broad group of compounds, including crowned porphyrins, crownphyrins, and calixpyrrole-crown ether systems forming Pacman complexes with transition metals. Their unique nature accustoms them as excellent ligands and hosts capable of binding guest molecules/ions, but also to undergo unusual transformations, such as metal-induced expansion/contraction. Depending on the design of the particular hybrid, they present unique features involving intriguing redox chemistry, interesting optical properties, and reactivity towards transition metals. In this perspective article, the overview of both the early designs of porphyrin-crown ether hybrids, as well as the most recent advances in the synthesis and characterisation of this remarkable group of macrocyclic systems, are addressed. The discussion covers the strategies employed in synthesising these systems, including cyclisation reactions, self-assembly, and their remarkable reactivity. The potential applications of porphyrin-crown ether hybrids are also highlighted. Moreover, the discussion identifies the challenges associated with synthesising and characterising hybrids, outlining the possible future directions.

Keywords: crown ethers; porphyrinoids; self-assembly; sensors; supramolecular chemistry.

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Figures

Figure 1
Figure 1
Porphyrin and crown ether.
Figure 2
Figure 2
Timeline demonstrating the contributions into the crown ether–porphyrin chemistry.
Figure 3
Figure 3
Tetra-crowned porphyrin 1 and dimer 2 formed upon K+ binding.
Figure 4
Figure 4
meso-Crowned 25-oxasmaragdyrins 3a–c and their boron(III) complexes (3a–c)-BF2.
Scheme 1
Scheme 1
CsF ion-pair binding of 4. The molecular structure of 4-CsF is shown on the right [101].
Figure 5
Figure 5
CsF ion pair binding by 5. The molecular structure of 5-CsF is shown on the right [102].
Scheme 2
Scheme 2
Ion-pair binding by 6. The molecular structure of (6-CsCl)2 is shown on the right [103].
Scheme 3
Scheme 3
Hydrated fluoride binding by 7 [104].
Figure 6
Figure 6
β-Crowned porphyrin 8.
Figure 7
Figure 7
Crown ether-capped porphyrins 9.
Figure 8
Figure 8
The capped porphyrin 10 and complex [10-PQ](PF6)2.
Figure 9
Figure 9
The double-capped porphyrin 11.
Figure 10
Figure 10
Selected examples of iminoporphyrinoids [58,122].
Scheme 4
Scheme 4
The synthesis of 13.
Scheme 5
Scheme 5
Tripyrrane-based crown ether-embedding porphyrinoid 15.
Figure 11
Figure 11
Macrocycles 16–19 and their coordination compounds.
Scheme 6
Scheme 6
The flexibility of 16-Co [66].
Figure 12
Figure 12
Hexagonal wheel composed of six 16-Co(III) monomers [66].
Scheme 7
Scheme 7
The synthesis of 16-V [67].
Figure 13
Figure 13
The molecular structure of dimers [16-Mn]2 [67].
Scheme 8
Scheme 8
Synthesis of crownphyrins 28–33. Compounds 23a/b and 29a/b were obtained from 4,7,10-trioxa-1,13-tridecanediamine.
Figure 14
Figure 14
The molecular structures of 22a, 34a·(HCl)2, and 29b [69].
Figure 15
Figure 15
Molecular structures of 22a-Pb and (29b)2-Zn [69].
Scheme 9
Scheme 9
Reactivity of 29a/b.
Scheme 10
Scheme 10
Synthesis of 36 and 37 [131].
Scheme 11
Scheme 11
Synthesis of 40–45.
Figure 16
Figure 16
Potential applications of porphyrin-crown ether hybrids.
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