153114-01-3Relevant academic research and scientific papers
Phthalocyanine D-pi-A type asymmetric disc-shaped dye and preparation method thereof
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Paragraph 0065-0067; 0135-0137, (2020/10/14)
The invention provides a phthalocyanine D-pi-A type asymmetric disc-shaped dye and a preparation method thereof, and belongs to the field of organic photoelectric material synthesis. According to thepreparation method, different alkyl or alkoxy, dialkylam
Predominant effect of connecting atom and position of substituents on azomethine nitrogens' basicity in phthalocyanines
Cidlina, Antonin,Svec, Jan,Ludvová, Lucie,Kune?, Ji?í,Zimcik, Petr,Novakova, Veronika
, p. 1122 - 1133 (2016/12/16)
The basicity of azomethine nitrogens was studied on a series of phthalocyanines (Pcs) that differed in a position of substituent, i.e. peripherally (β-series) and non-peripherally substituted Pcs (a-series), and in a type of substituent (alkylsulfanyl, alkyloxy or alkyl). Appropriate 3,6-or 4,5-disubstituted phthalonitriles were prepared either by nucleophilic substitution or by Negishi coupling. Target zinc Pcs were synthesized by Linstead method. The basicity was studied by the mean of absorption and 1H NMR spectroscopies in chloroform upon titration with trifluoroacetic acid. Equilibrium constants (log K) indicated significant difference within the series. Basicity decreased as follows: α-alkyloxy > α-alkylsulfanyl > β-alkyloxy > β-alkyl > β-alkylsulfanyl ~ α-alkyl with log K higher than 7 down to 2.6 M-1. Increased basicity of a-alkyloxy and a-alkylsulfanyl Pcs is caused by the stabilization of trapped hydrogen at azomethine nitrogen via hydrogen bonding and van der Waals interactions, respectively. The basicity of b-series clearly correlated with the electronic effects of substituents. 1H NMR studies confirmed the possibility of the weak bonding interactions in a-alkyloxy and α-alkylsulfanyl Pcs, however, the position of the 1H NMR signal of azomethine-NH proton was even more influenced by the electronic effects of present substituents than by the weak interactions.
Synthesis of 2,3,9,10,16,17,23,24-octaalkynylphthalocyanines and the effects of concentration and temperature on their 1H NMR spectra
Terekhov, Dmitri S.,Nolan, Kieran J. M.,McArthur, Colin R.,Leznoff, Clifford C.
, p. 3034 - 3040 (2007/10/03)
The syntheses of 3,4- and 4,5-diiodophthalonitriles are described. Coupling of the latter compound with Pd(PPh3)2Cl2 and 1-octyne, 1-heptyne, 1-hexyne, 1-pentyne, and 3,3-dimethyl-1-butyne gave a series of 4,5-dialkynylphthalonitriles. Hydrogenation of 4,5-bis(1-pentynyl)phthalonitrile and 4,5-bis(3,3-dimethyl-1-butynyl)phthalonitrile gave 4,5-dipentylphthalonitrile and 4,5-bis(3,3-dimethylbutyl)phthalonitriles. Condensation of the dialkynylphthalonitriles with lithium 1-pentoxide in 1-pentanol gave 2,3,9,10,16,17,23,24-octaalkynylphthalocyanines, while intervention of the intermediate dilithium phthalocyanines with zinc acetate gave the related zinc(II) phthalocyanines. 1H NMR spectroscopy of these octaalkynylphthalocyanines exhibited large chemical shifts (1-2 ppm) of the internal and aromatic protons at concentrations ranging from 10-2 to 10-5 M and at temperatures from 27 to 147°C. The effects of aggregation phenomena are discussed. The importance of reporting concentration and temperature values for NMR spectra of phthalocyanines is stressed.
