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Dalton Transactions
DOI: 10.1039/C6DT04160D
ARTICLE
flask was charged with 3 mL of a Ce /CF
Journal Name
IV
3
3
SO H aqueous 1H), 10.87 (s, 0.5H), 8.67 (d, J = 1.8 Hz, 1H), 8.07 (d, J = 1.9 Hz,
-
solution was stired magnetically (initial pH 1.0, the 1H), 1.44 (s, 9H). HRMS-ESI: calcd for [M-H] , 366.1705; found,
IV
concentration of Ce is 0.166 M) and deaerated with argon for 366.1723.
3
0 min. Subsequently, the catalyst (100 μL, 0.5 mM in
Complex 1. A mixture of ligand
H
3
L
(184 mg, 0.5 mmol),
N (0.5 mL) in DMF
CF CH OH) was injected into the solution through a septum Ru(DMSO)
3
2
4
Cl (242 mg, 0.5 mmol) and Et
2
3
o
cap. The amount of oxygen evolved was detected by the (15 mL) was heated overnight at 110 C. The colour of the
oxygen sensor and calibrated by GC after the end of oxygen solution gradually became dark green from light yellow.
2
evolution. Initial rates of O generation catalytic by different Subsequently, excess 4-picoline (1.5 mL) was added and the
o
concentrations (7.3-33.4 μM) catalysts were measured similar mixture was kept at 90 C for additional 10 h. After cooling to
IV
to the method mentioned above, with excess Ce (>4000 room temperature, the solvent was removed under reduced
equivalent, and can be regarded as constant).
pressure and the raw product was purified by chromatography
OH/CH Cl (1:50, v v) as eluents. Complex 1
was maintained at 20 C by a circulating water-cooling system was obtained as a dark green solid (145 mg, 39% yield). HRMS-
For photochemical oxygen generation, the reaction system over silica with CH
3
2
2
:
o
+
and the oxygen generated was measured by GC. Generally, the ESI: Calcd. for [M+H] , 746.2406; found, 746.2413. Calcd. for
-5
+
three-component system of catalyst (5.5 × 10 M), sensitizer [M + Na] , 768.2226; found, 768.2233. Elem. anal: Calcd. (%)
2
+
-4
2-
Ru(bpy) (dcb)] (5.5 × 10 M), and electron acceptor S O (1 for C H N O Ru: C 64.41, H 5.77, N 7.51; found, C 64.23, H
[
2
2
8
40 43
4
4
-2
×
10 M) in pH 6.86 phosphate buffer/ CF CH OH (10:1, v:v; 5.32, N 7.78.
3 2
total 11 mL) was degassed by argon for 20 min (the
background was collected by GC) and then irradiated. After 2
min irradiation, the GC started sampling manually every 5 min.
A Clark-type oxygen electrode (DW2/2 unit with an S1
electrode)was also applied to monitor light-driven water
oxidation (more information about the Clark-type electrode
can be obtained from the web site of Hansatech Instruments
Ltd.).
Acknowledgements
This work was supported by the National Basic Research
Program of China (973 program, 2014CB239402), the National
Natural Science Foundation of China (21120102036, 91233201
and 21573033), the Fundamental Research Funds for the
Central Universities (DUT13RC(3)103, DUT15LK08), the Basic
Research Project of Key Laboratory of Liaoning (LZ2015015),
the Swedish Energy Agency and the K & A Wallenberg
Synthesis
3
4
35
36
cis-Ru(DMSO) Cl , Ru(bpy) Cl , [Ru(bpy) (dcb)](PF ) , and Foundation.
4
2
3
2
2
6 2
37, 38
H3L
were prepared according to the respectively reported
procedures. All other materials were commercially available
and used as received without any treatment, unless otherwise
noted.
Notes and references
1.
K. J. Young, B. J. Brennan, R. Tagore and G. W. Brudvig,
As shown in Scheme 2, starting from carbazole, after
alkylation, bromination, cyano-substitution and hydrolyzation,
the desired ligand H3L was successfully synthesized.
Acc. Chem. Res., 2015, 48, 567.
J. D. Blakemore, R. H. Crabtree and G. W. Brudvig, Chem.
Rev., 2015, 115, 12974.
M. D. Karkas, O. Verho, E. V. Johnston and B. Akermark,
Chem. Rev., 2014, 114, 11863.
J. L. Fillol, Z. Codola, I. Garcia-Bosch, L. Gomez, J. J. Pla and
M. Costas, Nat. Chem., 2011, 3, 807.
B. Zhang, F. Li, F. Yu, H. Cui, X. Zhou, H. Li, Y. Wang and L.
Sun, Chem. Asian. J., 2014, 9, 1515.
D. Hong, S. Mandal, Y. Yamada, Y. M. Lee, W. Nam, A.
Llobet and S. Fukuzumi, Inorg. Chem., 2013, 52, 9522.
D. Wang, G. Ghirlanda and J. P. Allen, J. Am. Chem. Soc.,
2
3
4
5
6
7
8
9
1
1
1
1
.
.
.
.
.
.
2
014, 136, 10198.
.
M. T. Zhang, Z. Chen, P. Kang and T. J. Meyer, J. Am. Chem.
Soc., 2013, 135, 2048.
S. M. Barnett, K. I. Goldberg and J. M. Mayer, Nat. Chem.,
2012, 4, 498.
D. K. Dogutan, R. McGuire, Jr. and D. G. Nocera, J. Am.
Chem. Soc., 2011, 133, 9178.
N. S. McCool, D. M. Robinson, J. E. Sheats and G. C.
Dismukes, J. Am. Chem. Soc., 2011, 133, 11446.
W.-T. Lee, S. B. Muñoz, D. A. Dickie and J. M. Smith,
Angew. Chem., Int. Ed., 2014, 53, 9856.
Scheme 2. The synthetic pathway for
3
H L.
.
3
,6-Di-tert-butyl-9H-carbazole-1,8-dicarboxylic Acid (H L).
3
0.
1.
2.
3.
A suspending aqueous solution (10 mL) containing 3,6-di-tert-
butylcarbazole-1,8-dicarbonitrile (330 mg, 1 mmol) and NaOH
(400 mg, 10 mmol) was refluxed overnight until the reagent
was completely dissolved. After cooling to room temperature,
pH value of the reaction solution was adjusted to 1 using 6.0 M
hydrochloric acid, white product was precipitated
immediately. Then collected the precipitate, washed with
Z. Codola, J. M. Cardoso, B. Royo, M. Costas and J. Lloret-
Fillol, Chem.-Eur. J., 2013, 19, 7203.
water and dried in vacuum to obtain the ligand H3L (353 mg,
1
6% yield). H NMR (400 MHz, d -DMSO): δ (ppm) 13.32 (s,
14.
J. DePasquale, I. Nieto, L. E. Reuther, C. J. Herbst-
Gervasoni, J. J. Paul, V. Mochalin, M. Zeller, C. M. Thomas,
9
6
6
| J. Name., 2012, 00, 1-3
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