New synthesis of tetraazachlorins and tetraazabacteriochlorins by Diels–Alder reaction of tetraazaporphine

The absorption, fluorescence, and excitation spectra of free base tetraazaporphine (H 2 TAP) trapped in Ne, N 2 , and Ar matrices have been recorded at cryogenic temperatures. Normal Raman spectra of H 2 TAP were recorded in KBr discs and predicted with density functional theory (DFT) using large basis sets calculations. The vibrational frequencies observed in the Raman Spectrum exhibit reasonable agreement with those deduced from the emission spectra, as well as with frequencies predicted from large basis set DFT computations. The upper state vibrational frequencies, obtained from highly resolved, site selected excitation spectra, are consistently lower than the ground state frequencies. This contrasts with the situation in free base phthalocyanine, where the upper state shows little changes in vibrational frequencies and geometry when compared with the ground state. Investigations of the photochemical properties of H 2 TAP isolated in the three matrices have been performed using the method of persistent spectral hole-burning (PSHB). This technique has been used to reveal sites corresponding to distinct N-H tautomers which were not evident in the absorption spectra. An analysis of the holes and antiholes produced with PSHB in the Q x (0-0) absorption band made it possible to identify inter-conversion of distinct host sites. © 2014 AIP Publishing LLC.

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“…H 2 TAP was provided by the Minsk group utilising the synthetic method of Makarova et al 23 . The cryostat, described in Ref.…”

Section: A Experimentalmentioning

confidence: 99%

Free base tetraazaporphine isolated in inert gas hosts: Matrix influence on its spectroscopic and photochemical properties

Henchy

McCaffrey

Arabei

et al. 2014

The Journal of Chemical Physics

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“…A related work involved the reaction of the tetraazaporphyrin 66 with anthracene and naphthacene to yield the corresponding tetraazachlorins 67 and 68 (Scheme 15). 37 Bis-adducts of the bacteriochlorin and isobacteriochlorin types are also obtained. …”

Section: Scheme 13mentioning

confidence: 99%

Cycloaddition reactions of porphyrins

Cavaleiro¹,

Neves²,

Tomé³

2003

Arkivoc

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Adequately substituted porphyrins can participate in pericyclic reactions as dienes, dienophiles, dipolarophiles and as 1,3-dipoles. They also show interesting dipolar 1,5-electrocyclizations and cheletropic reactions with carbenes. All these different types of reactivity have been exploited in order to synthesize new potential biologically active porphyrin derivatives, mainly chlorins and bacteriochlorins. This paper reviews the most recent works where porphyrins have participated in pericyclic reactions.

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“…[213][214][215][216] Depending on the reaction temperature and the nature of the diene, tetraazachlorins (TACs), tetraazabacteriochlorins (TABs), and tetraazaisobacteriochlorins (TAiBs) could be isolated from the reaction mixture (Schemes 21, 22). [213][214][215] For instance, the Diels-Alder reaction between unsubstituted porphyrazine 50 and anthracene derivatives at 130 o C results in the selective formation of tetraazachlorins 51, while raising the reaction temperature leads to the formation of tetraazabacteriochlorins 52 and tetraazaisobacteriochlorins 53 as the major products (Scheme 21); 213 similar results were obtained in the cyclopentadiene series. 216 Similarly, [3+2] cycloaddition reaction between tetraazaporphyrins 50, 54 or 56 and generated in situ dipolar reactants results in formation of respective tetraazachlorins 55, 57, or 59 along with tetraazabacteriochlorins 60 and 61 or tetraazaisobacteriochlorin 58 (Scheme 22).…”

Section: Cycloaddition Reactionsmentioning

confidence: 96%

Synthetic approaches to asymmetric phthalocyanines and their analogues

Nemykin¹,

Dudkin²,

Dumoulin³

et al. 2014

Arkivoc

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This review summarizes synthetic strategies for the preparation of asymmetric phthalocyanines and their analogues. Cross-condensation between two phthalonitrile components, crosscondensation between one phthalonitrile and one non-nitrile component, targeted synthesis of AABB-type compounds, the subphthalocyanine ring-expansion method, as well as postmodification approaches on pre-formed symmetric and asymmetric systems, are discussed. Methodologies for targeted preparation of specific types of asymmetric phthalocyanines and their analogues are also briefly overviewed.

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New synthesis of tetraazachlorins and tetraazabacteriochlorins by Diels–Alder reaction of tetraazaporphine

Cited by 25 publications

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Free base tetraazaporphine isolated in inert gas hosts: Matrix influence on its spectroscopic and photochemical properties

Free base tetraazaporphine isolated in inert gas hosts: Matrix influence on its spectroscopic and photochemical properties

Cycloaddition reactions of porphyrins

Synthetic approaches to asymmetric phthalocyanines and their analogues

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