Please do not adjust margins
New Journal of Chemistry
Page 8 of 9
DOI: 10.1039/C7NJ00791D
ARTICLE
Journal Name
Table 6. Photooxidation of cyclohexene.
White LED
Sun Light
Time
Conversion (Oxidative
TON [TOF
(hꢀ1)]
Time
Conversion (Oxidative
stability) (%)
TON [TOF
(hꢀ1)]
Photosensitizers
stability) (%)
(h)
48
48
48
(h)
24
24
24
H2TPP@nanoAmb
H2T(2ꢀCl)PP@nanoAmb
H2T(2ꢀMe)PP@nanoAmb
a
89 (60)
95 (61)
80 (88)
8900 [185]
9500 [198]
8000 [167]
90 [51]
92 [65]
68 [90]
9000 [375]
9200 [383]
6800 [283]
Catalyst and cyclohexene were used in 1:10000 molar ratio in acetonitrile. 2ꢀcyclohexeneꢀ1ꢀone was the major product (Supporting Information, S3). See the
footnotes of Table 3 for more details.
No detectable changes were observed in the intensity of the case
of
H2T(2ꢀMe)PP@nanoAmb
and
H2T(2ꢀ
absorption band at 410 nm. The addition of Cl)PP@nanoAmb, respectively.
H2TPP@nanoAmb led to gradual decrease in the
absorbance at 410 nm (Figure 9) that provides considerable
evidence for the involvement of singlet oxygen as the major
ROS. On the other hand, the oxidation of cyclooctene was
conducted in the presence of 1,4ꢀbenzoquinone (in 1:2 molar
ratio relative to cyclooctene) as a superoxide anion radical
scavenger[51ꢀ52] and no change in the yield of the oxidation
product was observed. It should be noted that the order of
photocatalytic activity of the catalyst in different solvents was
also in a good agreement with the lifetime of singlet oxygen
in these solvents.
Acknowledgements
Financial support of this work by Institute for Advanced
Studies in Basic Sciences (IASBS) is acknowledged.
References
[1] R. Bonnett, Chem. Soc. Rev. 1995, 24, 19-33.
[2] M. Klaper, W. Fudickar and T. Linker, J. Am. Chem. Soc. 2016,
138, 7024–7029.
[3 E. Secret, M. Maynadier, A.Gallud, M. Gary-Bobo, A. Chaix, E.
Belamie, P. Maillard, M. J. Sailor, M. Garcia, J.-O. Durand and F.
Cunin, Chem. Commun. 2013, 49, 4202-4204.
[4] H. Liu, W. Feng, C. W. Kee, Y. Zhao, D. Leow, Y. Pan and C.H.
Tan, Green Chem. 2010, 12, 953-956.
[5] D. Topkaya, D. Lafont, F. Poyer, G. Garcia, F. Albrieux, P.
Maillard, Y. Bretonnière and F. Dumoulin, New J. Chem. 2016,
40, 2044-2050 .
[6] X.-H. Dai, Z.-M. Wang, L.-Y. Gao, J.-M. Pan, X.-H. Wang, Yong-
S. Yan and D.-M. Liu, New J. Chem. 2014, 38, 3569-3578.
[7] P. R. Ogilby, Chem. Soc. Rev. 2010, 39, 3181-3209.
[8] M. C. DeRosa and R. J. Crutchley, Coord. Chem. Rev. 2002,
233, 351-371.
[9] Ana M. Perez-Lopez, Elsa Valero and Mark Bradley, New J.
Chem. 2017, In press.
[10] M. Pineiro, A. L. Carvalho, M. M. Pereira, A. d. A. Gonsalves,
Conclusion
A
series of mesoꢀtetra(aryl)porphyrins supported on
Amberlyst 15 nanoparticles via acid base reaction were used
as highly efficient heterogeneous photocatalysts (TON
values in the range of 8000ꢀ10000) for the aerobic oxidation
of olefins and found that: (i) The polymer nanoparticles with
an average diameter less than 200 nm can be readiliy
sythesized by stirring the polymer beads in ethyl acetate for
24 h; (ii) the concomitant protonation and immobilization of
porphyrins led to a significant increase in the oxidative
stability of porphyrins with respect to their nonꢀimmobilized
counterparts so that the porphyrins may be recovered and
reused at least four times without significant decrease in their
catalytic activity; (iii) the very limited solubility or insolubility of
L. G. Arnaut and S. J. Formosinho, Chem. Eur. J. 1998, 4, 2299-
2307.
porphyrins in acetonitrile that is
homogeneous photocatalysis of
a
disadvantage in
[11] D. Yao, V. Hugues, M. Blanchard-Desce, O. Mongin, C. O.
Paul-Roth and F. Paul New J. Chem. 2015, 39, 7730-7733.
[12] S. Campestrini and U. Tonellato, Eur. J. Org. Chem. 2002, 22
oxidation reactions
,
catalyzed by nonꢀmetallated porphyrins was used as an
advantage to design a heterogeneous catalytic system with
noꢀcatalyst leaching over long reaction times; (iv) porphyrin
dications may be prepared in safe, nonꢀtoxic and ecoꢀfriendly
solvents. Also, the loaded porphyrin may be readily
separated from the polymer by a simple alkaline treatment
and measured by UVꢀvis spectroscopy. Furthermore, the
polymer can be recovered and reused after an acid
treatment; (v) with the exception of some highly electronꢀ
deficient porphyrins, all previously synthesized porphyrins
may be readily immobilized on Amberlystꢀ15 nanoparticles as
a strong acid to form a large library of heterogeneous
porphyrinic photosensitizers; (vi) interestingly, the maximum
catalyst performance was observed in the presence of a
,
3827-3832.
[13]S. Zakavi and S. Hoseini, RSC Adv. 2015, 5, 106774-106786;
[14] A. Rosa, G. Ricciardi, E. J. Baerends, A. Romeo and L. Monsù
Scolaro, J. Phys. Chem. A 2003, 107, 11468-11482.
[15] H. H. Thanga and A. L. Verma, New J. Chem., 2002, 26
342-346.
,
[16]N. E. Leadbeater and M. Marco, Chem. Soc. Rev. 2002, 102
3217-3274.
,
[17] S. M. Ribeiro, A. C. Serra and A. d. A. R. Gonsalves,
Tetrahedron 2007, 63, 7885-7891.
[18] J. Bhaumik, G. Gogia, S. Kirar, L. Vijay, N. S. Thakur, U. C.
Banerjee and J. K. Laha, New J. Chem. 2016, 40, 724-731.
[19] K. Teramura, H. Tsuneoka, K. Ogura, T. Sugimoto, T.
Shishido and T. Tanaka, ChemCatChem 2014, 6, 2276-2281.
remarkably low degree of porphyrin loading; (vii) the highest [20]E. Brule and Y. R. de Miguel, Org. Biomol. Chem. 2006,
4,
599-609.
[21] L. Fernández, V. I. Esteves, Â. Cunha, R. J. Schneider and J. P.
Tomé, J. Porphyrins Phthalocyanines 2016, 20, 150-166.
oxidative stability and catalytic activity were observed in the
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins