ReviewPorphyrin silanes
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.
References (107)
- et al.
Porphyrin-based nanomedicines for cancer treatment
Bioconjug. Chem.
(2019) - et al.
Porphyrin-containing molecular squares: design and applications
Coord. Chem. Rev.
(2006) - et al.
Visible light induced oxygenation of alkenes with water sensitized by silicon-porphyrins with the second most earth-abundant element
J. Photochem. Photobiol. A Chem.
(2015) - et al.
Computerised Gas Chromatographic-Mass Spectrometric Analysis of Complex Mixtures of Alkyl Porphyrins
J. Chromatogr.
(1984) - et al.
Computerised Capillary Gas Chromatographic Mass Spectrometric Studies of the Petroporphyrins of the Gilstonite Bitumen
J. Chromatogr.
(1985) - et al.
Determination of porphyrin carbon isotopic composition using gas chromatography-isotope ratio monitoring mass spectrometry
J. Chromatogr. A
(2000) - et al.
A new protonated form of porphyrins in solutions
Mendeleev Commun.
(2012) - et al.
Comparative Computerised Gas Chromatographic-Mass Spectrometric Analysis of Petroporphyrins
J. Chromatogr. A
(1986) - et al.
Metallo-Mesogens and Liquid Crystals with a Heart of Gold
Polyhedron
(1988) - et al.
Electrochemistry of Hexacoordinate Tetra(Aryl)Porphyrinatosilicon(IV) Complexes
Pdf. J. Electrochem.
(1996)
Synthesis of polystyrene beads loaded with dual luminophors for self-referenced oxygen sensing
Talanta
The Use of Spectrophotometry UV-Vis for the Study of Porphyrins
Macro To Nano Spectrosc.
A systematic approach toward designing functional ionic porphyrin crystalline materials
J. Phys. Chem. C.
A new porphyrin synthesis. the synthesis of porphin
J. Am. Chem. Soc.
Mechanistic investigations of porphyrin syntheses. I. Preliminary studies on Ms-tetraphenylporphin
J. Am. Chem. Soc.
A simplified synthesis for meso-tetraphenylporphin
J. Org. Chem.
conjugated porphyrin arrays: synthesis, properties and applications for functional materials
Chem. Soc. Rev.
Porphyrin polymers and organic frameworks
Polym. Int.
Synthetic expanded porphyrin chemistry
Angew. Chemie - Int. Ed.
Porphyrin-sensitized solar cells
Chem. Soc. Rev.
Porphysome nanovesicles generated by porphyrin bilayers for use as multimodal biophotonic contrast agents
Nat. Mater.
Tailoring porphyrin conjugation for nanoassembly-driven phototheranostic properties
ACS Nano
Supramolecular chemistry of metalloporphyrins
Chem. Rev.
Multifunctional and chiral porphyrins: model receptors for chiral recognition
Accounts Chem. Res.
Recent developments in the coordination chemistry of porphyrin complexes containing non-metallic and semi-metallic elements
J. Porphyr. Phthalocyanines
Some interesting things about polysiloxanes
Acc. Chem. Res.
High-efficiency crystalline silicon solar cells: status and perspectives
Energy Environ. Sci.
Volatile silicon complexes of etioporphyrin
J. Am. Chem. Soc.
Selective Si–C bond cleavage on a diorganosilicon porphyrin complex bearing different axial ligands
Chem. Lett.
Near-infrared fluorescence of silicon phthalocyanine carboxylate esters
Sci. Rep.
Bis(Trifluoromethanesulfonato)(Tetra-p-Tolylporphyrinato)Silicon(IV), (TTP)Si(OTf)2: The First Structurally Characterized (Porphyrinato)Silicon(IV) Complex
Inorg. Chem.
Near infrared light-triggered drug generation and release from gold nanoparticle carriers for photodynamic therapy
Small
Synthesis, Properties and Drug Potential of the Photosensitive Alkyl- and Alkylsiloxy-Ligated Silicon Phthalocyanine Pc 227
Photochem. Photobiol. Sci.
Solution-Processable Silicon Phthalocyanines in Electroluminescent and Photovoltaic Devices
ACS Appl. Mater. Interfaces
State Selective Electron Injection in Non-Aggregated Titanium Phthalocyanine Sensitised Nanocrystalline TiO2 Films
Chem. Commun.
Axial Reactivity of Soluble Silicon(IV) Phthalocyanines
Inorg. Chem.
Substituent Effects on the Spectroscopic Properties and Reactivity of Hexacoordinate Silicon(IV) Porphyrin Complexes
Inorg. Chem.
Recent Advances in Phthalocyanine-Based Sensitizers for Dye-Sensitized Solar Cells
European J. Org. Chem.
A Photoresponsive Silicon Radical within a Porphyrin π-Cloud: Photolysis of Organo- and Nitroxysilicon Porphyrins with Visible Light
J. Am. Chem. Soc.
Photophysics of Reduced Silicon Tetraphenylporphyrin
J. Phys. Chem. B
An Antiaromatic Porphyrin Complex: Tetraphenylporphyrinato(Silicon)(L) 2 (L = THF or Pyridine)
J. Am. Chem. Soc.
Push-Pull Zinc Porphyrins as Light-Harvesters for Efficient Dye-Sensitized Solar Cells
Front. Chem.
Emerging Applications of Porphyrins and Metalloporphyrins in Biomedicine and Diagnostic Magnetic Resonance Imaging
Biosensors
Nomenclature of Tetrapyrroles: Recommendations 1986
Eur. J. Biochem.
Glossary of Class Names of Organic Compounds and Reactivity Intermediates Based on Structure (IUPAC Recommendations 1995)
Pure Appl. Chem.
Application of Gas Chromatography and Mass Spectrometry to Porphyrin Microanalysis
Pergamon Press Ltd
Spin-Orbit Coupling and Luminescence of Group IV Complexes
J. Chem. Phys.
Methoxo- Und Phenoxo-Metallkomplexe Des Octaiithylporphins Mit Zentralionen Des Typs M3@, M4e Und MO3“
Neue Wolfram- Und Rheniumporphine. Chem. Ber.
Cited by (9)
Eight-membered and larger rings
2023, Progress in Heterocyclic ChemistryFacile construction of luminescent silicone elastomers from the compatibilization of porphyrins via the Piers-Rubinsztajn reaction
2022, Colloids and Surfaces A: Physicochemical and Engineering AspectsCitation Excerpt :Due to their unique conjugated 18 π-electron macrocyclic ring system, porphyrins and porphyrinoids exhibit excellent coordination abilities that permit the incorporation of different metal ions in their core, as well as distinct photophysical and electronic properties [6,7]. Thus, they have been widely applied in catalysis, organic semiconductor devices, solar cells, model photosynthetic systems, and organic electroluminescence applications; [8–14] however, aggregation-induced quenching of porphyrin molecules reduces their quantum yield, which greatly limits their practical applications in the aggregated state, such as films and elastomers [15,16]. Polydimethylsiloxane (PDMS) is a silicon-based linear polymer, mainly used for the production of elastomers.
Bipolar charge transport in a robust hexacoordinate organosilane
2022, Journal of Organometallic ChemistryCitation Excerpt :The silatranes with an SiO3NX skeleton and a sterically constrained transannular N→Si bond are an important class of pentacoordinate silanes that have been explored for a wide range of applications including immobilization of biomolecules [7], cross-coupling reactions [8], and hair-growth and pharmacological applications [9,10]. The silicon porphyrins [11] and phthalocyanines with an SiN4X2 skeleton are another significant class of hypercoordinate silicon complexes that have been explored for biological [12–17] and energy-related applications [18–24]. In both cases, incorporation of the formally neutral, nitrogen base sites within a polydentate ligand framework prevents dissociation and imparts the moisture and thermal stability necessary for many applications (Fig. 1).
Ultrafast electron injection in TiO<inf>2</inf>surface-anchored aluminum(III) porphyrin stacks
2023, Journal of Porphyrins and Phthalocyanines