Synthesis and spectroscopic investigation of trifluoroethoxy-coated phthalocyanine linked with fullerene

Sukeguchi, Daisuke; Yoshiyama, Hideyuki; Shibata, Norio; Nakamura, Shuichi; Toru, Takeshi; Hayashi, Yûji; Soga, Tetsuo

doi:10.1016/j.jfluchem.2008.11.005

Cited by 32 publications

(7 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A strong quenching of the SubPc fluorescence compared to the reference precursor 2 f is observed, irrespective of the solvent, which can be attributed to a substantial amount of electron‐transfer from the SubPc moiety to the fullerene acceptor. It is interesting to note that the TFEO‐coated SubPc moiety still acts as a donor in this dyad 8 , since the TFEO‐Pc can no longer act as a donor in the TFEO‐Pc–C 60 dyad 9e. This phenomenon is also supported by fluorescence quantum yield data (Table 2).…”

Section: Resultssupporting

confidence: 57%

Trifluoroethoxy‐Coating Improves the Axial Ligand Substitution of Subphthalocyanine

Shibata

Das

Tokunaga

et al. 2010

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

A novel trifluoroethoxy (TFEO)-coated SubPc (1) and various axially functionalised derivatives thereof (2) have been efficiently synthesised. The advantage of the TFEO-coating on SubPcs compared to conventional fluorine-coated or uncoated molecules has been clearly demonstrated, as axial derivatisation has been realised in very good yields. Among various SubPcs synthesised, formyl-SubPc 2f has been further used as a building block for the synthesis of donor-acceptor SubPc-C(60) hybrid 8, while iodo-SubPc 2e has been used for the synthesis of trifluoroethoxy-coated SubPc-Pc dyads 9 and 10. All of these compounds are highly soluble in all common organic solvents, which greatly facilitates their purification and characterisation. The SubPcs 2a-c incorporating oligoethylene glycol moieties are attractive from a biological point of view, while SubPcs 8-10 may prove useful for studies of intramolecular electron- and energy-transfer processes.

show abstract

Section: Resultssupporting

confidence: 57%

Trifluoroethoxy‐Coating Improves the Axial Ligand Substitution of Subphthalocyanine

Shibata

Das

Tokunaga

et al. 2010

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…Recently, two Pc−C 60 dyads ( 30a , b ) have been prepared, in which a fullerene moiety has been connected covalently to a Pc bearing either tert -butyl (i.e., 30a ) or trifluoroethoxy (i.e., 30b ) groups at its peripheral positions (Figure ) . Both dyads were obtained starting from a common fullerene derivative bearing a terminal phthalonitrile moiety that was then reacted with 3- tert -butylphthalonitrile or a persubstituted, trifluoroethoxy-coated phthalonitrile, leading to Pc−C 60 dyads 30a and 30b , respectively.…”

Section: Phthalocyanine−fullerene Donor−acceptor Systemsmentioning

confidence: 99%

“…Recently, two Pc-C 60 dyads (30a,b) have been prepared, in which a fullerene moiety has been connected covalently to a Pc bearing either tert-butyl (i.e., 30a) or trifluoroethoxy (i.e., 30b) groups at its peripheral positions (Figure 4). 93 Both dyads were obtained starting from a common fullerene derivative bearing a terminal phthalonitrile moiety that was then reacted with 3-tert-butylphthalonitrile or a persubstituted, trifluoroethoxy-coated phthalonitrile, leading to Pc-C 60 dyads 30a and 30b, respectively. Electrochemical and spectroscopic studies on both dyad systems revealed that whereas in the case of ensemble 30a the occurrence of an efficient intramolecular PET process was detected, dyad 30b did not show any sign of electronic communication between Pc and C 60.…”

Section: Covalently Linked Phthalocyanine-fullerene Systemsmentioning

confidence: 99%

Covalent and Noncovalent Phthalocyanine−Carbon Nanostructure Systems: Synthesis, Photoinduced Electron Transfer, and Application to Molecular Photovoltaics

et al. 2010

View full text Add to dashboard Cite

ground-state electronic communication between the two spatially close, active units (i.e., Pc and C 60 ).Electrochemical investigation showed that the Pc-based oxidation and reduction potentials were positively shifted in the dyads 8a,b in comparison to the redox potentials of some reference compounds (i.e., Pcs 10a,b and a fullerene derivative lacking the Pc moiety). Conversely, the C 60 -based reduction potentials for 8a,b were negatively shifted with respect to those of a fullerene derivative reference compound, thus inferring some degree of ground-state intra-and/or intermolecular interactions between the electron-donating Pc to the electron-accepting fullerene moiety.A thorough analysis on the photophysical properties (i.e., steady-state and time-resolved fluorescence measurements and transient absorption measurements) of dyads 8a-c in solution was also carried out, confirming the occurrence of Scheme 2. General Reaction Conditions for the Preparation of Pc-C 60 Dyads 8a-c a a Reagents and conditions: (i) ZnCl 2 for 5a or Cu(AcO) 2 for 5c, (dimethylamino)methanol (DMAE), reflux, argon; for 5b, lithium, 1-pentanol, amyl alcohol, reflux, argon; (ii) tributylvinyltin, Pd(PPh 3 ) 4 , toluene, 100 °C; (iii) OsO 4 , NaIO 4 , THF, room temperature (rt); (iv) C 60 fullerene, N-methylglycine, toluene, reflux; (v) C 60 fullerene, N-methylglycine, toluene, reflux; (vi) only for 8a, 4-tert-butylphthalonitrile (6), ZnCl 2 , DMAE/o-DCB, reflux. Scheme 3. General Reaction Conditions for the Preparation of Pc-C 60 Dyad 13 a a Reagents and conditions: (i) NaBH 4 , ethanol, rt; (ii) 4-tert-butylphthalonitrile (6), Zn(OAc) 2 , DMAE, reflux; (iii) SO 3 -pyridine complex, NEt 3 , dry dimethyl sulfoxide, argon, 50 °C; (iv) C 60 fullerene, tert-butylcarbamate-protected, N-functionalized glycine 16, toluene, reflux; (v) trifluoroacetic acid, CH 2 Cl 2 , rt.

show abstract

“…6 ) [ 103 – 104 ]. However, such energy transfer does not occur in the hybrid of TFEO-ZnPc and fullerene 20b because the strong electron-withdrawing property of fluorine reverses the relationship between the electronic states of both units [ 105 ]. It was suggested that TFEO-Pc has an orbital energy closer to that of [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) [ 106 – 107 ], which is a known acceptor molecule, than to poly(3-hexylthiophene-2,5-diyl) (P3HT) [ 107 ], which is a known donor molecule.…”

Section: Reviewmentioning

confidence: 99%

Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

Mori

Shibata

2017

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

Phthalocyanines and subphthalocyanines are attracting attention as functional dyes that are applicable to organic solar cells, photodynamic therapy, organic electronic devices, and other applications. However, phthalocyanines are generally difficult to handle due to their strong ability to aggregate, so this property must be controlled for further applications of phthalocyanines. On the other hand, trifluoroethoxy-substituted phthalocyanines are known to suppress aggregation due to repulsion of the trifluoroethoxy group. Furthermore, the electronic characteristics of phthalocyanines are significantly changed by the strong electronegativity of fluorine. Therefore, it is expected that trifluoroethoxy-substituted phthalocyanines can be applied to new industrial fields. This review summarizes the synthesis and application of trifluoroethoxy-substituted phthalocyanine and subphthalocyanine derivatives.

show abstract

Synthesis and spectroscopic investigation of trifluoroethoxy-coated phthalocyanine linked with fullerene

Cited by 32 publications

References 20 publications

Trifluoroethoxy‐Coating Improves the Axial Ligand Substitution of Subphthalocyanine

Trifluoroethoxy‐Coating Improves the Axial Ligand Substitution of Subphthalocyanine

Covalent and Noncovalent Phthalocyanine−Carbon Nanostructure Systems: Synthesis, Photoinduced Electron Transfer, and Application to Molecular Photovoltaics

Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

Contact Info

Product

Resources

About