Poly‐<i>Ortho</i>‐Functionalizable Tetraarylporphycene Platform–Synthesis of Octacationic Derivatives Towards the Layer‐by‐Layer Design of Versatile Graphene Oxide Photoelectrodes

Brenner, Wolfgang; Malig, Jenny; Costa, Rubén D.; Guldi, Dirk M.; Jux, Norbert

doi:10.1002/adma.201203459

Cited by 34 publications

(11 citation statements)

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“…Temocene and its derivatives, 135 , 136 and 137 , and 138 , , are promising in PDT because of their stronger absorption, higher photostability, and lower dark toxicity compared to temoporfin. Other potentially applicable aryl-substituted porphycenes are poly-ortho-functionalizable derivatives 139 – 141 , shown in Scheme . They have been tested as building blocks in photoelectrochemical cells, showing good photoresponse profiles.…”

Section: Electronic Spectroscopymentioning

confidence: 99%

Spectroscopy and Tautomerization Studies of Porphycenes

2016

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Tautomerization in porphycenes, constitutional isomers of porphyrins, is strongly entangled with spectral and photophysical parameters. The intramolecular double hydrogen transfer occurring in the ground and electronically excited states leads to uncommon spectroscopic characteristics, such as depolarized emission, viscosity-dependent radiationless depopulation, and vibrational-mode-specific tunneling splittings. This review starts with documentation of the electronic spectra of porphycenes: Absorption and magnetic circular dichroism are discussed, together with their analysis based on the perimeter model. Next, photophysical characteristics are presented, setting the stage for the final part, which discusses the developments in research on tautomerism. Porphycenes have been studied in different experimental regimes: molecules in condensed phases, isolated in supersonic jets and helium nanodroplets, and, recently also on the level of single molecules investigated by optical and scanning probe microscopies. Because of the rich and detailed information obtained from these diverse investigations, porphycenes emerge as very good models for studying the complex, multidimensional phenomena involved in the process of intramolecular double hydrogen transfer.

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Section: Electronic Spectroscopymentioning

confidence: 99%

Spectroscopy and Tautomerization Studies of Porphycenes

2016

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“…Among these studies, particularly important in terms of possible applications are those devoted to spectral and photophysical properties. , Porphycenes are very promising as sensitizers in photodynamic therapy, the main, but not the only theme of numerous patents. Other areas of possible use of porphycenes based on interaction with light include photoelectrochemical devices, near-IR absorbing and emitting fluorophores, − preparation of new electrochromic, liquid crystalline, and elastomeric materials. However, comparative research on the photophysical properties of different porphycenes has been rather limited.…”

Section: Introductionmentioning

confidence: 99%

2 + 2 Can Make Nearly a Thousand! Comparison of Di- and Tetra-Meso-Alkyl-Substituted Porphycenes

et al. 2020

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Two porphycenes, substituted at the meso positions with two and four methyl groups, respectively, reveal similar absorption spectra, but their photophysical properties are completely different. 9,20-dimethylporphycene emits fluorescence with about 20% quantum yield, independent of the solvent. In contrast, fluorescence of 9,10,19,20-tetramethylporphycene is extremely weak in nonviscous solvents, but it can be recovered by placing the chromophore in a rigid environment. We propose a model that explains these differences, based on calculations and structural analogies with other extremely weakly emitting derivatives, dibenzo[ cde , mno ]porphycenes. The efficient S 1 deactivation involves delocalization of two inner cavity protons coupled with proton translocation toward a high-energy cis tautomer. The latter process leads to distortion from planarity. The probability of deactivation increases with the strength of the intramolecular NH···N hydrogen bonds. The model also explains the observation of biexponential fluorescence decay in weakly emitting porphycenes. It can be extended to other derivatives, in particular, the asymmetrically substituted ones. We also point to the possibility of using specific porphycenes as viscosity sensors, in particular, when working in single molecule regime.

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“… 2 Porphycene derivatives have attracted considerable attention in photodynamic therapy, 3 protein mimicry, 4–7 catalysis, 8,9 tautomerism, 10–12 and materials chemistry. 13,14 Various porphycenes with meso - and β-substituents and their metal complexes have been reported to have tunable functionalities, crystallinities and solubilities. 15–31 …”

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confidence: 99%