tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, fisher...
TRANSCRIPT
![Page 1: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/1.jpg)
1
Supporting information
Tailored design of ruthenium molecular catalysts with 2, 2 -́bypyridine-6,
6 -́dicarboxylate and pyrazole based ligand for water oxidation
Quentin Daniela, Lei Wanga, Lele Duana ,Fusheng Lia and Licheng Sunab*
aDepartment of Chemistry, KTH Royal Institute of Technology, 10044 Stockholm, Sweden.
bState Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Center on
Molecular Devices, Dalian University of Technology (DUT), Dalian 116024, P. R. China.
CONTENTS 1H-NMR study ................................................................................................................................................................ 2
O2 detection ................................................................................................................................................................... 8
Differential pulse voltammetry ................................................................................................................................... 11
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2016
![Page 2: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/2.jpg)
2
1H-NMR STUDY
Figure S1. 1H NMR of A-1* in dichloromethane-d2 (DCM-d2).
![Page 3: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/3.jpg)
3
Figure S2. 1H NMR of A-1* in methanol-d4.
![Page 4: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/4.jpg)
4
Figure S3. Stability test of A-1* in D2O solution.
The loss of the equatorial ligand occurs in time scale of seconds while the loss of the axial
pyrazole occurs an hour time scale.
![Page 5: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/5.jpg)
5
Figure S4. 1H NMR of A-2* in dichloromethane-d2 (DCM-d2).
![Page 6: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/6.jpg)
6
Figure S5. 1H NMR of B-1* in dichloromethane-d2 (DCM-d2).
![Page 7: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/7.jpg)
7
Figure S6. 1H NMR of B-2* in in dichloromethane-d2 (DCM-d2).
![Page 8: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/8.jpg)
8
Figure S7. 1H NMR of B-2 in in acetonitril-d3.(methyl group of 4-bromo, 3-methyl pyrazole is
merged with the solvent peak and are therefore not shown)
![Page 9: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/9.jpg)
9
O2 DETECTION
CeIV in pH 1.0 solutions for kinetic and stoichiometric measurements were prepared from
(NH4)2Ce(NO3)6 (99.99+%, Aldrich) and nitric acid (trace metal grade, 70%, purified by re-
distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure
transducer (Omega PX138-030A5 V) driven by a power supply (TTi-PL601) at 8.00 V versus
time, then the amount of oxygen was calibrated by GC (GC-2014 Shimadzu). First, the solution
of (NH4)2[Ce(NO3)6] in 0.1 M HNO3 (3.2 mL) was added into the flask, then the aqueous
solution of the catalyst (20−400 μL, 1 to 2 mM) containing 20% in volume of TFE were injected
into the above solution under vigorous stirring at ambient temperature (20 °C). Secondly, 500 μL
gas phase of the air tight flask was analyzed by Gas chromatography (GC). The end-point
oxygen generated was converted to TON as reported (the oxygen in air present in the flask prior
measurement was subtracted from the final value).
![Page 10: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/10.jpg)
10
Figure S8. CVs of the influence of the 2,2,2-Trifluoroethanol (TFE) on the activity and the peak
definition. Condition: 1mM catalyst, scan rate 100mV/s, Ionic Strength: 0.1.
![Page 11: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/11.jpg)
11
DIFFERENTIAL PULSE VOLTAMMETRY
Figure S9: DPV scans at various pH of A-1 for the realisation of the Pourbaix diagram (Only few
scans are shown for sake of clarity).
![Page 12: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/12.jpg)
12
Figure S10: DPV scans at various pH of A-2 for the realisation of the Pourbaix diagram (Only
few scans are shown for sake of clarity).
![Page 13: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/13.jpg)
13
Figure S11. O2 generation with different amount of A-2 under excess of CeIV in 0.1 M HNO3
solution. A) 0.2mmol of A-2; B) 0.4mmol of A-2; C)0.6mmol of A-2; D)0.8mmol of A-2.
![Page 14: Tailored design of ruthenium molecular catalysts with 2, 2 ... · distillation, 99.999%, Fisher Scientific).The oxygen evolution data was monitored by a pressure transducer (Omega](https://reader030.vdocuments.net/reader030/viewer/2022041201/5d497ee488c99347278b69ff/html5/thumbnails/14.jpg)
14
Figure S12. Detection of the oxygen produced by A-2 under CeIV conditions by gas
chromatography (GC).