Fine Tuning between Radical versus Nonradical States of Azoheteroarenes on Selective Osmium Platforms.

The article highlights the cooperative impact of azoheteroarenes [abbt: 2,2'-azobis(benzothiazole), L1-L3; bmpd: (E)-1,2-bis(1-methyl-1H-pyrazole-3-yl) diazene, L4] and coligands [bpy: 2,2'-bipyridine; pap: 2-phenylazopyridine] in tuning radical (N-N•-) versus nonradical (N═N0) states of L on selective OsII-platforms in structurally/spectroscopically characterized monomeric [1]ClO4-[6]ClO4 and [1](ClO4)2-[2](ClO4)2/[7](ClO4)2-[8](ClO4)2, respectively. The preferred syn-configuration of L in the complexes prevented obtaining ligand bridged dimeric species. It revealed that {Os(bpy)2} facilitated the stabilization of both nonradical ([1](ClO4)2-[2](ClO4)2) and radical ([1]ClO4-[2]ClO4) states of L1/L2, while it delivered exclusively the radical form for L3 in [3]ClO4. In contrast, {Os(pap)2} generated radical states of L1-L3 in [4]ClO4-[6]ClO4, respectively, without any alteration of the redox state of OsII and azo (N═N0) function of the pap coligand. The neutral state of L4 was, however, ascertained in [7](ClO4)2 or [8](ClO4)2 irrespective of the nature of the metal fragment {Os(bpy)2} or {Os(pap)2}, respectively. Switching between radical and nonradical forms of L in the complexes as a function L and coligand could be addressed based on their relative FMO (frontier molecular orbital) energies. Multiple close redox steps of the complexes extended a competitive electron transfer scenario between the redox active components including metal/L/bpy/pap, leading to delicate electronic forms in each case.

Sequential Oxygenation of Bis(ß-diketiminate) on a Selective Diruthenium Platform.

This article demonstrated the redox-noninnocent phenylene-linked bis(ß-diketiminate) (L2-)-bridged first example of isomeric diruthenium(III)-acac species (acac = acetylacetonate) and its ability to activate dioxygen. The coordination of deprotonated L2- to the {Ru(acac)2} in bis(bidentate) mode led to isomeric {(acac)2RuIII}2(µ-L2-) (S = 1, 1-trans/1-cis, green). 1 displayed Ru(III)-based anisotropic EPR in CH3CN but without the resolution of the forbidden (ΔMs = 2) g1/2 signal at 77 K. 1-cis, however, slowly transformed to the energetically favored 1-trans form. 1 underwent two-step oxygenation at the Cß sites of L2- to form the ß-diketiminate/α-ketodiimine (L'-)-bridged mixed valent (acac)2RuIII(µ-L'-)RuII(acac)2 (2, S = 1/2, pink) followed by bis(α-ketodiimine) (L″)-bridged isovalent (acac)2RuII(µ-L″)RuII(acac)2 (3, S = 0, red). The role of O2 toward 1 → 2/3 was corroborated by 18O2 labeling experiment. Redox steps of 1-3 varied as a function of isomeric identity, bridge, and metal oxidation state. The calculated MOs and Mulliken spin densities attributed to the noninnocence of L2-, L'-, and L″ in the respective complexes. Spectrophotometric monitoring of 1 → 2 revealed pseudo-first-order rate constants (105k s-1) of 1.8 (303 K), 3.5 (313 K), 7.7 (323 K), and 17.0 (333 K) and ΔH⧧/ΔS⧧/ΔG⧧ of 14.3 kcal mol-1/-33.1 cal mol-1 K-1/24.2 kcal mol-1 (298 K), respectively. Moreover, characterization of the short-lived blue intermediate obtained during the conversion of 1 → 2/3 upon exposure to O2 supported its valence tautomeric form (VT1, RuIII-L2--RuIII ↔ RuIII-L•--RuII, S = 1), which in effect facilitated oxygen activation at the ligand backbone.

Inner-Sphere Electron Transfer Induced Reversible Electron Reservoir Feature of Azoheteroarene Bridged Diruthenium Frameworks.

This article demonstrates the stabilization of ground- and redox-induced metal-to-ligand charge transfer excited states on coordination of azo-coupled bmpd(L4) [bmpd = (E)-1,2-bis(1-methyl-1H-pyrazol-3-yl)diazene; L4 = -N═N-] to the electron-rich {Ru(acac)2} (acac = acetylacetonate) unit in mononuclear RuII(acac)2(L4) (1) and diastereomeric dinuclear (acac)2Ru2.5(µ-L4•-)Ru2.5(acac)2 [rac, ΔΔ/ΛΛ (2a)/meso, ΔΛ (2b)] complexes, respectively. It also develops further one-step intramolecular electron transfer induced L4•- bridged isovalent higher analogue [(acac)2RuIII(µ-L4•-)RuIII(acac)2]ClO4 in diastereomeric forms, rac-[2a]ClO4/meso-[2b]ClO4. On the contrary, under identical reaction conditions electronically and sterically permuted bimpd [L5, (E)-1,2-bis(4-iodo-1-methyl-1H-pyrazol-3-yl)diazene)] delivered mononuclear RuII(acac)2(L5) (3) as an exclusive product. Further, the generation of unprecedented heterotrinuclear complex [(acac)2RuII(µ-L4)AgI(µ-L4)RuII(acac)2]ClO4 ([4]ClO4) involving unreduced L4 via the reaction of 1 and AgClO4 revealed the absence of any inner-sphere electron transfer (IET) as in precursor 1, which in turn reaffirmed an IET (at the interface of electron-rich Ru(acac)2 and acceptor L4) mediated stabilization of 2. Structural authentication of the complexes with special reference to the tunable azo distance (N═N, N-N•-, N-N2-) of L and their spectro-electrochemical events in accessible redox states including the reversible electron reservoir feature of 2 → 2+/2+ → 2 were evaluated in conjunction with density functional theory/time-dependent density functional theory calculations. The varying extent of IET as a function of heteroaromatics appended to the azo group of L (L1 = abpy = 2,2'-azobipyridine, L2 = abbt = 2,2'-azobis(benzothiazole), L3 = abim = azobis(1-methylbenzimidazole), L4 and L5, Schemes 1 & 2) in the Ru(acac)2-derived respective molecular setup has been addressed.

The isomer-sensitive electrochemical HER of ruthenium(II)-hydrido complexes involving redox-active azoheteroaromatics.

The article deals with the development of isomeric ruthenium(II)-hydrido complexes [RuII(H)(L1)(PPh3)2(CO)]ClO4 ([1a]ClO4-[1b]ClO4)/[RuII(H)(L2)(PPh3)2(CO)]ClO4 ([2a]ClO4-[2b]ClO4) involving azo coupled L1 [L1: (E)-1,2-bis(1-methyl-1H-pyrazol-3-yl)diazene]/L2 [L2: (E)-1,2-bis(4-iodo-1-methyl-1H-pyrazol-3-yl)diazene], respectively. Structural evaluation of the complexes affirmed the syn conformation of the coordinated/uncoordinated pyrazole groups of L and its unperturbed neutral azo (NN) state. Isomeric forms in [1a]ClO4/[1b]ClO4 or [2a]ClO4/[2b]ClO4 differed with respect to the cis and trans orientations of the coordinated CO and N(azo) donor of L, respectively. It also demonstrated the formation of intermolecular hydrogen-bonded dimeric or 1D-polymeric chains in [1a]ClO4/[2b]ClO4 or [1b]ClO4, respectively. Successive two-electron reductions of the complexes varied to an appreciable extent as a function of the heterocycles connected to L. The involvement of the azo function of L towards the reductions ([NN]0 → [NN]˙- → [NN]2-) was supported by the DFT calculated MOs and Mulliken spin density at the paramagnetic state, which was further validated by the radical EPR profile of the first reduced (S = 1/2) state. Isomeric [1a]ClO4/[1b]ClO4 or [2a]ClO4/[2b]ClO4 immobilised on the carbon cloth support underwent various electrochemical acidic HERs (hydrogen evolution reactions) with TOF/10-1 s-1: [1a]ClO4 (0.83) > [1b]ClO4 (0.68) > [2a]ClO4 (0.50) > [2b]ClO4 (0.37).

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

The article deals with the structural and electronic forms of hitherto unexplored L2- (H2L = 2,5-bis(2-hydroxyphenyl)thiazolo-[5,4-d]thiazole) bridged analogous diruthenium [{(AL1/AL2)2 RuII}2(µ-L2-)]2+ [1](ClO4)2/[2](ClO4)2 and diosmium [{(AL1/AL2)2OsII}2(µ-L2-)]2+ [3](PF6)2/[4](ClO4)2 complexes as a function of moderate-to-strongly π-accepting ancillary ligands: AL1 = 2,2'-bipyridine (bpy) and AL2 = 2-phenylazopyridine (pap). Structural elucidation of the complexes established an anti-oriented bridge (L2-) linked to the metal units through its N,O-/O-,N-donor sets, which led to two six-membered chelates in each case. It also highlighted the twisting of the phenolato functions of L2- with respect to the central thiazolothiazole (TzTz) unit and the unreduced state of the azo function of AL2 and multiple non-covalent π⋯π/CH⋯π interactions within the molecules in the nearby asymmetric units. The potential of the multiple redox steps of the complexes varied as a function of Ru versus Os and AL1 versus AL2. A collective consideration of experimental and DFT calculations revealed largely bridge- and metal-based first and second oxidative steps, which could be attributed to the electronic forms [(AL1/AL2)2MII(µ-L˙-)MII(AL1/AL2)2]3+ ↔ [(AL1/AL2)2MII(µ-L2-) MIII(AL1/AL2)2]3+ and [(AL1/AL2)2M2.5(µ-L˙-) M2.5(AL1/AL2)2]4+ for 13+-43+ and 14+-44+, respectively, implying the noninnocence of L2-, which was enhanced on moving from bpy to pap and from Os to Ru. Reductions of 12+-42+ were, however, centred around the ancillary ligand (AL1/AL2), in spite of the π-accepting feature of the TzTz core of L, implying the weaker π-acceptor form of the latter with special reference to the former. Involvement of the primarily metal (with minor contribution of the bridge, L) and ancillary ligand (AL) based orbitals in the second oxidised and first reduced steps could also be corroborated by the metal-based anisotropic and free radical EPR spectral signatures, respectively. 12+-42+ displayed multiple moderately-intense-to-intense charge-transfer absorption bands in the visible-to-UV region, which originated from mixed metal/ligand and intra/inter-ligand charge-transfer transitions.