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Synthesis and Spectroscopic Properties of Phthalocyanine–[60]Fullerene Conjugates Connected Directly by Means of a Four‐Membered Ring
Author(s) -
Fukuda Takamitsu,
Kikukawa Yuu,
Takaishi Shiori,
Kobayashi Nagao
Publication year - 2012
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201100850
Subject(s) - chemistry , phthalocyanine , cycloaddition , moiety , conjugate , porphyrin , conjugated system , trimethylsilyl , medicinal chemistry , circular dichroism , coupling reaction , stereochemistry , crystallography , photochemistry , organic chemistry , catalysis , mathematical analysis , polymer , mathematics
New covalently C 60 ‐conjugated phthalocyanine (Pc) analogues in which the Pc and C 60 components are connected by means of a four‐membered ring have been synthesized by taking advantage of a [2+2] cycloaddition reaction of C 60 with benzyne units generated from either a phthalocyanine derivative ( 8 ) or its precursor ( 1 ). The reaction of 1 with PhI(OAc) 2 and trifluoromethanesulfonic acid (TfOH) followed by the [2+2] cycloaddition of C 60 in the presence of tetra‐ n ‐butylammonium fluoride (TBAF) yielded the C 60 ‐substituted Pc precursor ( 3 ). Mixed condensation of 3 and 4,5‐dibutylsulfonylphthalonitrile ( 4 ) in a thermally promoted template reaction using a nickel salt successfully gave the Pc–C 60 conjugate ( 5 ). Results of mass spectrometry and 1 H and 13 C NMR spectroscopy clearly indicate the formation of the anticipated Pc–C 60 conjugate. Direct coupling of C 60 with the Pc analogue that contained eight peripheral trimethylsilyl (TMS) groups ( 8 ) also proceeded successfully, such that mono and bis C 60 ‐adducts were detected by their mass, although the isolation of each derivative was difficult. The absorption and magnetic circular dichroism (MCD) spectra of 5 and the reference compound ( 7 ) differ from each other in the Q‐band region, thereby suggesting that the presence of the C 60 moiety affects the electronic structure of the conjugate. The reduction and oxidation potentials of 5 and 7 obtained by cyclic voltammetry are comparative, except for the C 60 ‐centered reduction couple at −1.53 V versus Fc + /Fc in o ‐dichlorobenzene ( o ‐DCB). A one‐electron reduction of 5 and 7 in tetrahydrofuran (THF) by using the sodium mirror technique results in the loss of band intensity in the Q‐band region, whereas the characteristic marker bands for Pc‐ring‐centered reduction appear at around 430, 600, and 900 nm for both compounds. The final spectral shapes of 5 and 7 upon the reduction resemble each other, thus indicating that no significant molecular orbital (MO) interactions between the C 60 and Pc units are present for the reduced species of 5 . In contrast, the oxidized species of 5 and 7 generated by the addition of NOBF 4 in CH 2 Cl 2 show significantly different absorption spectra from each other. Whereas the broad bands at approximately 400–550 nm of 7 + are indicative of the cationic π‐radical species of metallo‐Pcs and can be assigned to a transition from a low‐lying MO to the half‐filled MO, no corresponding bands were observed for 5 + . These spectral characteristics have been tentatively assigned to the delocalized occupied frontier MOs for 5 + . The experimental results are broadly supported by DFT calculations.