Silicon(IV) complexes of octaaryl-substituted porphyrazines and corrolazines: influence of macrocycle contraction on spectral-luminescence, acid-base, and redox properties
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11160%2F23%3A10471238" target="_blank" >RIV/00216208:11160/23:10471238 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=8UolRxG_io" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=8UolRxG_io</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d3dt00319a" target="_blank" >10.1039/d3dt00319a</a>
Alternative languages
Result language
angličtina
Original language name
Silicon(IV) complexes of octaaryl-substituted porphyrazines and corrolazines: influence of macrocycle contraction on spectral-luminescence, acid-base, and redox properties
Original language description
The template cyclomerization of the iminoimide derivatives (obtained by the treatment of diarylfumarodinitriles with NH3 in methanol containing catalytic amounts of dissolved Na) in the presence of SiCl4 in pyridine leads to silicon(IV) octaarylporphyrazine complexes ((HO)2SiPzAr8, Ar = Ph, tBuPh) as a main reaction product. In the case of phenyl-substituted derivative, the formation of a distinctive Si(IV) complex as a byproduct was observed, which according to mass-spectroscopy measurement contains the macrocycle with five diphenylpyrrolic units. The treatment of bishydroxy complexes with tripropylchlorosilane in the presence of magnesium in pyridine leads to the formation of axially siloxylated porphyrazines (Pr3SiO)2SiPzAr8, followed by the reductive contraction of the macrocycle and formation of the corresponding corrolazine complexes (Pr3SiO)SiCzAr8. It is shown that the addition of acid (trifluoroacetic acid, TFA) facilitates the detachment of one siloxy group in (Pr3SiO)2SiPzAr8 and is essential for its Pz -> Cz transformation. In the presence of TFA, only one meso-nitrogen is protonated in the porphyrazine complexes (Pr3SiO)2SiPzAr8 (stability constant of the protonated form pK(s1) = -0.45 for Ar = Ph; pK(s1) = 0.68 for Ar = tBuPh), while two consequent protonation stages are observed for the more basic corrolazine complex (Pr3SiO)SiCzPh8 (pK(s1) = 0.93, pK(s2) = 0.45). Both types of Si(IV) complexes are poorly fluorescent (Phi(F) < 0.07). The porphyrazine complexes have low ability to generate singlet oxygen (Phi(Delta) < 0.15), whereas the corrolazine derivative (Pr3SiO)SiCzPh8 is a very efficient photosensitizer (Phi(Delta) = 0.76).
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
30104 - Pharmacology and pharmacy
Result continuities
Project
<a href="/en/project/GC21-14919J" target="_blank" >GC21-14919J: Non-metal complexes of porphyrazinoids for design of novel perspective photosensitizers and fluorescence sensors</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
1477-9234
Volume of the periodical
52
Issue of the periodical within the volume
20
Country of publishing house
GB - UNITED KINGDOM
Number of pages
10
Pages from-to
6831-6840
UT code for WoS article
000980571600001
EID of the result in the Scopus database
2-s2.0-85159121185