Synthesis, crystal structure, characterization of pyrazine diaminotriazine based complexes and their systematic comparative study with pyridyl diaminotriazine based complexes for light-driven hydrogen production

Rajak, Sanil; Schott, Olivier; Kaur, Prabhjyot; Maris, Thierry; Hanan, Garry S.; Duong, Adam

doi:10.1016/j.poly.2020.114412

Cited by 9 publications

(15 citation statements)

References 54 publications

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“…The bands at ∼2270 cm −1 in the spectra of 11 and 12 could be attributed to the −CN bond of coordinated acetonitrile molecules. For 8,9,11,and 12, the bands corresponding to perchlorate (ClO 4 − ) are observed between 1000 and 1100 cm −1 . For 10, the band at 1020 cm −1 is ascribed to tetrafluoroborate (BF 4 − ).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…6-(Pyridin-2-yl)-1,3,5-triazine-2,4-diamine 2 and 6-(pyridin-4-yl)-1,3,5triazine-2,4-diamine 4 were synthesized according to the reported methods. 11 Complexes 8−12 were prepared following the method below. All the other chemicals were commercially available and were purchased and used without any additional purification.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…The results obtained in the present work demonstrated an enhanced HER activity with the presence of amidine/amidinate groups in 9 and 10 as compared to that of 7. 11 Hence, a modification in the preparatory strategy led to novel complexes with different structures and improved hydrogen evolution, emphasizing the relationship between a compound's structure and its properties.…”

Section: ■ Introductionmentioning

confidence: 99%

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Amidine/Amidinate Cobalt Complexes: One-Pot Synthesis, Mechanism, and Photocatalytic Application for Hydrogen Production

et al. 2020

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A new synthetic route was carried out via a one-pot reaction to prepare a novel series of amidine/amidinate cobalt complexes 8−10 by mixing ligand 2 (6-pyridin-2-yl-[1,3,5]triazine-2,4-diamine) with Co(II) in acetonitrile or benzonitrile. We observed that a change of solvent from methanol (used in complex 7, previously reported) to nitrile solvents (MeCN and PhCN) led to the in situ incorporation of the amidine group, ultimately forming 8−10. So far, this is a unique method reported to introduce amidine/amidinate groups into a pyridinyl-substituted diaminotriazine complex. Remarkably, the single crystal X-ray diffraction study (SCXRD) of these new compounds reveals associations involving Janus DATamidine and Janus DATamidinate. A mechanism is proposed to explain the formation of amidine/ amidinate groups by investigating the single crystal structures of the possible intermediates 11 and 12 where the cobalt ion acts as a template. These amidine/amidinate cobalt complexes were used as a model to assess the photocatalytic activity for the hydrogen evolution reaction (HER). Complexes 9 and 10 show a 74% and 86% enhancement, respectively, of the catalytic activity towards the HER compared to complex 7. This highlights the structure−property relationship. By examining the novel cobalt complexes described here, we discovered the following: (i) a method to introduce an amidine group into a pyridine DAT-based complex, (ii) the efficiency of amidine complexes to form multiple hydrogen bonds to direct the molecular organization, (iii) the plausible mechanism of formation of amidines based on the SCXRD study, (iv) the modification of the final structure and hence the final properties by varying the reaction conditions, and (v) the utility of amidine complexes towards photocatalytic HER activity.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Amidine/Amidinate Cobalt Complexes: One-Pot Synthesis, Mechanism, and Photocatalytic Application for Hydrogen Production

et al. 2020

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“…2,4-Diamino-6-pyridyl-1,3,5-triazine (DPT) was synthesized according to a literature procedure. 25 Physical Characterization. Scanning electron microscopy (SEM, GeminiSEM 500), transmission electron microscopy (TEM, SU8020), and energy dispersive X-ray spectroscopy (EDS) were applied to investigate the morphology and microstructures of the catalysts.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

“…Deionized water was obtained by a nanopure water system (5–16 MΩ·cm). 2,4-Diamino-6-pyridyl-1,3,5-triazine (DPT) was synthesized according to a literature procedure …”

Section: Experimental Methodsmentioning

confidence: 99%

Roles of Co Dopants in Electrocatalytic Hydrogen Evolution by N-Rich Carbon Nanotubes Grafted on Carbon Layers

Liu

Pan

et al. 2021

ACS Appl. Nano Mater.

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The development of efficient and cost-effective electrocatalysts for hydrogen evolution reaction (HER) is of current interest. Pyrolysis of 3d metal complexes or mixtures of 3d metal ions and N-containing organic ligands has been found to be an efficient way to afford cost-effective metal-and N-doped carbon electrocatalysts for HER. However, due to the multiplecomponents nature of the catalysts, it is a challenge to clarify the role of each component. Herein, we report a facile approach to prepare Co-and N-doped carbon catalysts with carbon nanotubes uniformly grafted over the carbon layers via pyrolysis of a Co complex precursor bearing 2,4-diamino-6-pyridyl-1,3,5-triazine ligand. Among the prepared catalysts, Co−N/CNT/C-850 exhibits the best performance as a pH-universal electrocatalyst for HERs, which requires small overpotentials of 120, 190, and 134 mV to achieve a current density of 10 mA cm −2 in 1 M KOH, 1 M phosphate buffer solution (PBS, pH = 7), and 0.5 M H 2 SO 4 , respectively. Experimental results and theoretical calculations revealed that the Co 2+ dopant played a vital role in tuning the electronic structure of the carbon skeleton, leading to boosted HER catalytic activity of adjacent carbon atoms. Our work should provide insight into the design of metal carbon composites materials for energy conversion.

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Recent progress on the design and development of diaminotriazine based molecular catalysts for light-driven hydrogen production

Rajak

Kaur

et al. 2022

Coordination Chemistry Reviews

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Synthesis, crystal structure, characterization of pyrazine diaminotriazine based complexes and their systematic comparative study with pyridyl diaminotriazine based complexes for light-driven hydrogen production

Cited by 9 publications

References 54 publications

Amidine/Amidinate Cobalt Complexes: One-Pot Synthesis, Mechanism, and Photocatalytic Application for Hydrogen Production

Amidine/Amidinate Cobalt Complexes: One-Pot Synthesis, Mechanism, and Photocatalytic Application for Hydrogen Production

Roles of Co Dopants in Electrocatalytic Hydrogen Evolution by N-Rich Carbon Nanotubes Grafted on Carbon Layers

Recent progress on the design and development of diaminotriazine based molecular catalysts for light-driven hydrogen production

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