Donor–acceptor bridge 2,5-bis(2-oxido-phenyl)thiazolo-[5,4-<i>d</i>]thiazole derived diruthenium and diosmium systems. Structural and competitive electronic events as a function of metal ion, bridge and ancillary ligand

Lahiri, Goutam Kumar; Dhara, Suman; Seikh, Liton; Chakraborty, Saswati

doi:10.1039/d3dt00929g

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“… Ru II -bpy- and Ru II -pap-based mononuclear 2 + and isomeric 3 + / 4 + , respectively, underwent mixed ligand (L – → L • ) and metal (Ru II → Ru III )-based oxidation (O1). Interestingly, the extent of the involvement of L – in the oxidation process significantly enhanced on moving from 2 2+ to 3 2+ / 4 2+ , primarily due to the impact of stronger π-acceptance of pap . Unfortunately, instability of 2 2+ - 4 2+ at the electrolysis time scale (5–10 min) prevented to check their EPR profile.…”

Section: Resultsmentioning

confidence: 99%

“…The tc -configuration of pap units ( tc = trans and cis ) in the precursor was retained in the corresponding crystals of [ 3 ]ClO 4 , [ 4 ]ClO 4 , and [ 5 ](ClO 4 ) 3 . The average N–N (azo) distances of pap of 1.294, 1.298, and 1.278 Å in [ 3 ]ClO 4 , [ 4 ]ClO 4 , and [ 5 ](ClO 4 ) 3 , respectively, supported its unreduced neutral state . The shorter Ru II –N(azo, pap) distances, 1.970/2.009/1.999 Å, as compared Ru II –N(pyridine, pap) distances, 2.028/2.054/2.041 Å, in [ 3 ]ClO 4 /[ 4 ]ClO 4 /[ 5 ](ClO 4 ) 3 , respectively, reflected dπ(Ru II ) → π*(azo) back-bonding interaction …”

Section: Resultsmentioning

confidence: 99%

“…The average Ru III –O(acac) (1.999 Å), ,, Ru II –N(bpy) (2.043 Å), , Ru II –N(pap) (1.999/2.031/2.020 Å), and Ru II –P(PPh 3 )/Ru II –C(CO) (2.352/1.816–2.347/1.813) ,,, in [ 1 ]ClO 4 , [ 2 ]ClO 4 , [ 3 ]ClO 4 /[ 4 ]ClO 4 /[ 5 ](ClO 4 ) 3 , and [ 7 ]ClO 4 –[ 8 ]ClO 4 , respectively, matched well with those reported for the analogous complexes.…”

Section: Resultsmentioning

confidence: 99%

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Diverse Coordination Modes and Bidirectional Noninnocence of Pyridyl-β-diketonate on Ruthenium Platforms as a Function of Coligands

Biswas,

Mobin,

Dey

et al. 2024

Inorg. Chem.

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The article demonstrated diverse binding modes of deprotonated 1,3-di(2-pyridinyl)-1,3-propanedione (HL) (κ2-[O,O]−, κ2-[N,O]−, and μ-bis-κ2-[N,O]−) on selective ruthenium platforms: Ru(acac)2 (dimeric [1]ClO4), Ru(bpy)2 (monomeric [2]ClO4), Ru(pap)2 (isomeric monomeric [3]ClO4/[4]ClO4, dimeric [5](ClO4)3), and Ru(PPh3)2(CO) (monomeric 6, isomeric dimeric [7]ClO4/[8]ClO4) (acac = acetylacetonate, bpy = 2,2′-bipyridine, pap = 2-phenylazopyridine). Structural authentication of the complexes revealed (i) diverse binding mode of L– including its unprecedented bridging mode in [8]ClO4, (ii) varying degrees of nonplanarity of L–, and (iii) development of 1D polymeric chains or dimeric/tetrameric forms via intermolecular π–π interactions. The preferential binding feature of L– in the complexes could also be corroborated by their calculated relative energies. The analysis of the multiredox steps of the complexes suggested severe mixing of metal–ligand frontier orbitals, which in effect pinpointed the involvement of L– in both the oxidative and reductive processes along the redox chain, suggesting its bidirectional noninnocence under the present coordination situations. Though α-diketone or β-diketiminate was reported to activate O2 on the selective Ru(acac)2 platform, the inability of analogous β-diketonate-derived [1]ClO4 could be attributed to its calculated greater HOMO–LUMO energy gap, which disfavored electron exchange at the metal(RuIII)–ligand(L – ) interface to introduce the required unpaired spin at the ligand backbone toward the 3O2 activation event.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%