Synthesis, Characterization, and Water Oxidation Activity of Isomeric Ru Complexes

Hoque, Md Asmaul; Chowdhury, Abhishek Dutta; Maji, Somnath; Benet-Buchholz, Jordi; Ertem, Mehmed Z.; Gimbert-Suriñach, Carolina; Lahiri, Goutam Kumar; Llobet, Antoni

doi:10.1021/acs.inorgchem.1c00112

Synthesis, Characterization, and Water Oxidation Activity of Isomeric Ru Complexes

Journal Article · Thu Apr 08 00:00:00 EDT 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c00112· OSTI ID:1797362

Hoque, Md Asmaul ^[1]; Chowdhury, Abhishek Dutta ^[2]; Maji, Somnath ^[1]; ^[1]; ^[3]; ^[4]; ^[2]; ^[4]

Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ)
Indian Institute of Technology Bombay, Mumbai (India)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Univ. Autonoma de Barcelona (Spain)

The synthesis and characterization of the isomeric ruthenium complexes with the general formula cis- and trans-[Ru(trpy)(qc)X]ⁿ⁺ (trpy is 2,2':6',2"-terpyridine, qc is 8-quinolinecarboxylate, cis-1 and trans-1, X = Cl, n = 0; cis-2 and trans-2, X=OH2, n = 1) with respect to the relative disposition of the carboxylate and X ligands are reported. For comparison purposes, another set of ruthenium complexes with general formula cis- and trans-[Ru(trpy)(pic)(OH₂)]+ (pic is 2-picolinate (cis-3, trans-3)) have been prepared. The complexes with a qc ligand show a more distorted geometry compared to the complexes with a pic ligand. In all of the cases, the trans isomers show lower potential values for all of the redox couples relative to the cis isomers. Furthermore, complexes cis-2 and trans-2 with six-member chelate rings show higher catalytic activity than cis-3 and trans-3. Overall, it was shown that the electronic perturbation to the metal center exerted by different orientation and geometry of the ligands significantly influences both redox properties and catalytic performance.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: AGAUR; FEDER; MICIN; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0012704

OSTI ID:: 1797362

Report Number(s):: BNL--221667-2021-JAAM

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 8 Vol. 60; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2055520: Experimental Crystal Structure Determination Asmaul, Hoque, Md; Dutta, Chowdhury, Abhishek; Somnath, Maji, https://doi.org/10.5517/ccdc.csd.cc26zy38 The current record is supplemented by this dataset	dataset	January 2021
CCDC 2055521: Experimental Crystal Structure Determination Asmaul, Hoque, Md; Dutta, Chowdhury, Abhishek; Somnath, Maji, https://doi.org/10.5517/ccdc.csd.cc26zy49 The current record is supplemented by this dataset	dataset	January 2021
CCDC 2055522: Experimental Crystal Structure Determination Asmaul, Hoque, Md; Dutta, Chowdhury, Abhishek; Somnath, Maji, https://doi.org/10.5517/ccdc.csd.cc26zy5b The current record is supplemented by this dataset	dataset	January 2021
CCDC 2055523: Experimental Crystal Structure Determination Asmaul, Hoque, Md; Dutta, Chowdhury, Abhishek; Somnath, Maji, https://doi.org/10.5517/ccdc.csd.cc26zy6c The current record is supplemented by this dataset	dataset	January 2021

Synthesis, Characterization, and Water Oxidation Activity of Isomeric Ru Complexes

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