Review
Porphyrin silanes

https://doi.org/10.1016/j.ccr.2021.214183Get rights and content

Highlights

  • Porphyrin silanes have been known since 1967.

  • Not nearly as well explored as many other metalloporphyrins.

  • Their covalent axial ligands serve as a handle to modulate structure and properties.

  • This comprehensive review summarizes all work to date on porphyrin silanes.

Abstract

Porphyrin silanes (PorSils) are a unique class of metalloporphyrins that contain a hexacoordinate silicon center. This review chronicles the comprehensive body of research on PorSils to-date, beginning with their first discovery in 1967 by Boylan and Calvin. In the intervening five-plus decades, the synthesis of PorSils have been varied and optimized. PorSils possessing a variety of substituents – both axial and peripherally – have been reported; such functionalization can impact the properties with electronic and/or steric influence. We explore the structural, physical, electronic, and spectral attributes of PorSils, outlining and comparing this data. The unique properties of PorSils have widened the scope for the applications of metalloporphyrins: researchers have reported the use of PorSils for GC/MS analysis, electric and photoelectric applications, dual luminophores for pressure and oxygen sensing, photocatalysis, and photodynamic therapy. This review provides the first comprehensive summary of the development of PorSils, their unique features, and their contribution to the field of porphyrin chemistry.

Section snippets

Background and importance

The word “porphyrin” is derived from the Greek word “porphua”, meaning “purple” [1]. The class of molecules we call porphyrins are indeed typically purple, and are aromatic macrocyclic rings comprised of four pyrrole rings connected by methine bridges (Fig. 1a) [1], [2], [3]. Porphyrins are naturally occurring and many synthetic variants [4], [5], [6], [7], [8], [9] have been made; they have found application in a wide range of fields such as alternative energy [10], medicine [11], [12], [13],

Use of silicon tetrachloride, hexachlorodisiloxane, or hexachlorodisilane

(Por)SiCl2 and (Por)Si(OH)2 are often used as basic building blocks for the synthesis of PorSil derivatives. The first synthesis of a PorSil was reported in 1967 by Boylan and Calvin, in which etioporphyrin I (Etio-I) (1) was reacted with silicon tetrachloride or hexachlorodisiloxane and anhydrous pyridine [21]. This was followed by hydrolysis in dilute aqueous ethanolic hydrochloric acid (Fig. 3) to give (Etio-I)Si(OH)2 (1-Si(OH)2) [21], [40]. The conversion of the base porphyrin to the PorSil

Geometric considerations and planarity

The geometry of PorSils has been investigated using X-ray crystallography (Table 1) and computational methods. These investigations have provided information on the isomerism, planarity, bond lengths, and bond angles of PorSils [25], [57], [35], [58], [60], [34], [72]. Hexacoordinate silicon complexes are typically cis-coordinated with respect to labile, highly electronegative substituents. On the contrary, the axial ligands of all reported PorSils’ crystal structures necessarily demonstrate a

Volatile porphyrin silanes for GC/MS analysis

Geoporphyrins and petroporphyrins are present in sediments and crude oils [50], [80]. They represent the “molecular fossils” of chlorophylls, bacteriochlorophylls, and hemes in organisms [50]. These complex mixtures found in geological materials are best separated through powerful separation techniques, such as gas chromatography and combined GC–MS [40]. However, the structural determination of porphyrins from oil shale rocks, shale oils, and petroleum have been limited because of their low

Conclusion

This review highlights the importance and potential of PorSils. Since their discovery in 1967, synthetic methods to access them have evolved and a variety of PorSils have been synthesized. A wide range of axial substituents can be installed, which impact the physical and electronic properties of PorSils. Their structural, electronic, and photophysical properties have broadened the application scope of porphyrins; the uses of PorSils in the applications described in this review highlight the

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

The authors thank Ryerson University and NSERC for financial support of this work. The authors also thank Prof. Robert Gossage (Ryerson University) and Prof. Russell Viirre (Ryerson University) for helpful discussions, as well as Prof. Bryan Koivisto (Ryerson University) for additional support.

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