The first crystal structure of a one-dimensional chain of linked RuIIRuII units

Miyasaka, Hitoshi; Clérac, Rodolphe; Campos-Fernández, Cristian S.; Dunbar, Kim R.

doi:10.1039/b007079n

Cited by 69 publications

(54 citation statements)

References 29 publications

(15 reference statements)

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“…ORTEP drawings of the formula units of 1 and 2 with atomic numbering scheme are depicted in Figure 1 (selected bond distances and angles are given in Supporting Information Table S14). The chain feature is similar to that in [Ru 2 II,II (CF 3 CO 2 ) 4 (phz)] 25 Table S14 and the related description in the Supporting Information). The asymmetric unit contains two crystallographically unique anisate moieties, which are distinguished hereafter as anis-A and anis-B, located nearly along the c-and b-axes, respectively (see Figures 2 and S10 in the Supporting Information).…”

Section: ■ Introductionsupporting

confidence: 56%

“…This study proposes a simple strategy for the design of PCPs/MOFs for selective gas adsorption. 25 and some of them provide good porous materials, as demonstrated by CO 2 adsorption. 26 The choice of phz linkage is due to an idea: because N-substituted phz derivatives with electronreleasing substituents such as methyl group (e.g., 5,10-dihydro-5,10-dimethylphenazine) act as good electron donors, 27 the phz moiety capped by donor [Ru 2 II,II ] units would also have a donor character advantageous for the design of donor-type PCPs.…”

Section: ■ Introductionmentioning

confidence: 99%

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Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru₂^II,II]/[Rh₂^II,II] Dimers

et al. 2013

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The design of porous materials that undergo selective adsorption of a specific molecule is a critical issue in research on porous coordination polymers or metal-organic frameworks. For the purpose of the selective capture of molecules possessing an electron-acceptor character such as nitric oxide (NO), one-dimensional chain compounds possessing a high donor character have been synthesized using 4-chloroanisate-bridged paddlewheel-type dimetal(II, II) complexes with M = Ru and Rh and phenazine (phz) as the chain linker: [M2(4-Cl-2-OMePhCO2)4(phz)]·n(CH2Cl2) (M = Ru, 1; Rh, 2). These compounds are isostructural and are composed of chains with a [-{M2}-phz-] repeating unit and CH2Cl2 occupying the void space between the chains. Compounds 1 and 2 change to a new phase (1-dry and 2-dry) upon evacuating the crystallization solvent (CH2Cl2) and almost lose their pores in the drying process: no void space in 1-dry and 31.8 Å(3), corresponding to 2.9% of the cell volume, in 2-dry. Nevertheless, the compounds show a unique gas accommodation ability. Accompanied by a structural transformation (i.e., the first gate-opening) at low pressures of <10 kPa, both compounds show a typical physisorption isotherm for O2 (90 K) and CO2 (195 K), with the adsorption amount of ca. 2-4 gas molecules per [M2] unit. In addition, the adsorption isotherm for NO (121 K) involves the first gate-opening followed by a second gate-opening anomaly at NO pressures of ≈52 kPa for 1-dry and ≈21 kPa for 2-dry. At the first gate-opening, the absorbed amount of NO is ca. 4 molecules per [M2] unit, and then it reaches 8.4 and 6.3 for 1-dry and 2-dry, respectively, at 95 kPa. Only the isotherm for NO exhibits hysteresis in the desorption process, and some of the NO molecules are trapped in pores even after evacuating at 121 K, although it recovers to the original dried sample on heating to room temperature. The adsorbed NO molecules accrue a significant electron donation from the host framework even in the [Rh2] derivative, indicating that such simple porous compounds with electron-donor characteristics are useful for the selective adsorption of NO.

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Section: ■ Introductionsupporting

confidence: 56%

Section: ■ Introductionmentioning

confidence: 99%

Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru₂^II,II]/[Rh₂^II,II] Dimers

et al. 2013

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“…In addition, a moderate or important interdimer magnetic interaction, depending on the structure of the complex, has been observed in Ru 2 5 + compounds. Also a moderate interdimer magnetic interaction in the molecular Ru 2 4 + complexes has been observed although a stronger magnetic interaction in some polymeric species [10,11] …”

Section: -A C H T U N G T R E N N U N G (O 2 Cme)a C H T U N G T R E mentioning

confidence: 96%

Tuning the Magnetic Moment of [Ru₂(DPhF)₃(O₂CMe)L]⁺ Complexes (DPhF=N,N′‐Diphenylformamidinate): A Theoretical Explanation of the Axial Ligand Influence

Barral

Casanova

Herrero

et al. 2010

Chemistry A European J

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The magnetic behaviour of the compounds containing the [Ru(2)(DPhF)(3)(O(2)CMe)](+) ion (DPhF(-)=N,N'-diphenylformamidinate) shows a strong dependence on the nature of the ligand bonded to the axial position. The new complexes [Ru(2)(DPhF)(3)(O(2)CMe)(OPMe(3))][BF(4)]0.5 CH(2)Cl(2) (1 0.5 CH(2)Cl(2)) and [Ru(2)(DPhF)(3)(O(2)CMe)(4-pic)][BF(4)] (2) (4-pic=4-methylpyridine) clearly display this influence. Complex 1.0.5 CH(2)Cl(2) shows a magnetic moment corresponding to a S=3/2 system affected by the common zero-field splitting (ZFS) and a weak antiferromagnetic interaction, whereas complex 2 displays an intermediate behaviour between S=3/2 and S=1/2 systems. The experimental data of complex 1 are fitted with a model that considers the ZFS effect using the Hamiltonian H(D)=S.D.S. The weak antiferromagnetic coupling is introduced as a perturbation, using the molecular field approximation. DFT calculations demonstrate that, in the [Ru(2)(O(2)CMe)(DPhF)(3)(L)](+) complexes, the energy level of the metal-metal molecular orbitals is strongly dependent on the nature of the axial ligand (L). This study reveals that the increase in the pi-acceptor character of L leads to a greater split between the pi* and delta* HOMO orbitals. The influence of the axial ligand in the relative energy between the doublet and quartet states in this type of complexes was also analysed. This study was performed on the new complexes 1.0.5 CH(2)Cl(2) and 2. The previously isolated [Ru(2)(DPhF)(3)(O(2)CMe)(OH(2))][BF(4)].0.5 CH(2)Cl(2) (3.0.5 CH(2)Cl(2)) and [Ru(2)(DPhF)(3)(O(2)CMe)(CO)][BF(4)].CH(2)Cl(2) (4.CH(2)Cl(2)) complexes were also included in this study as representative examples of spin-admixed and low-spin configurations, respectively. The [Ru(2)(DPhF)(3)(O(2)CMe)](+) (5) unit was used as a reference compound. These theoretical studies are in accordance with the different magnetic behaviour experimentally observed.

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“…91 Similarly, Ru 2 4+ complexes with aliphatic carboxylates display g values from 2.05 to 2.12 and D/k B values ranging from +389 to +452 K. 92 However, a small (and suspect 93 ) g value of 1.64 was found for 4,0-Ru 2 (fhp) 4 (thf), a fluorine analogue of the studied molecules, with a comparable D/k B value of +378 K. 44 Most of the other treatments of the magnetic data of Ru 2 4+ compounds fix the g value to 2.00. In this way, a series of Ru 2 (O 2 CAr) 4 compounds, where Ar = fluorine-substituted phenyl, exhibited D/k B values ranging from +333 to +449 K; 10 the one-dimensional compound [Ru 2 (O 2 CCF 3 ) 4 (Phz)] gave D/k B = +399 K, 12 and the trifluoroactete and perfluorobenzoate (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl adducts revealed D/k B = +338 and +350 K, respectively. 94 Thus, 4 and 5 show magnetic features that are similar to known 3 A compounds.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

Electronic Structure of Ru₂(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding

Brown

Dolinar

Hillard³

et al. 2015

Inorg. Chem.

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Reduction of (4,0)-Ru2(chp)4Cl (1) (chp = 6-chloro-2-oxypyridinate) with Zn or FeCl2 yields a series of axial ligand adducts of the Ru2(II,II) species Ru2(chp)4(L), with L = tetrahydrofuran (2), dimethyl sulfoxide (DMSO; 3), PPh3 (4), pyridine (5), or MeCN (6). Zn reduction in noncoordinating solvents such as toluene or CH2Cl2 leads to the dimeric species [Ru2(chp)4]2 (7) or [Ru2(chp)4]2(ZnCl2) (8), whereas addition of strongly σ-donating ligands such as CO causes cleavage of the Ru-Ru bond. Density functional theory (DFT) models of these complexes, the axially free species, and the axial adducts of several other potential ligands (H2O, NH3, CH2Cl2, S-bound DMSO, N2, and CO) indicate that these compounds can be divided into three distinct categories, based on their Ru-Ru bond length and electronic structure. Compounds 2, 3, 5, 6, 7, and 8, the hypothetical axially free species, and adducts of H2O and NH3 fit in Category 1 with a (δ*)(2)(π*)(2) ground state, as indicated by their electronic spectra, magnetic properties, and Ru-Ru bond distances. However, compound 4 and the CH2Cl2 adduct (Category 2) show a pseudo-Jahn-Teller distortion and spectroscopic signs of δ*/π* orbital mixing suggestive of a new electronic ground state intermediate between the (δ*)(2)(π*)(2) and (δ*)(1)(π*)(3) configurations. Category 3 consists of the hypothetical adducts of N2, S-bound DMSO, and CO, all of which are predicted to have a (δ*)(1)(π*)(3) configuration. Electronic spectra were recorded and assigned using time-dependent DFT, allowing assignment of a band in the 10,000-13,000 cm(-1) range as the δ → π* transition. The axial ligand's π-acid character heavily influences the δ*-π* gap, and thereby the ground-state electronic configuration, but not the axial ligand binding strength, which is dictated more by the σ-donor character of the ligands. Thus, this work greatly expands the number of axial ligand adducts known for Ru2(II,II) complexes supported by N,O-donor ligands and provides a predictive theoretical framework for their stability and electronic structures.

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The first crystal structure of a one-dimensional chain of linked RuIIRuII units

Cited by 69 publications

References 29 publications

Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru₂^II,II]/[Rh₂^II,II] Dimers

Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru₂^II,II]/[Rh₂^II,II] Dimers

Tuning the Magnetic Moment of [Ru₂(DPhF)₃(O₂CMe)L]⁺ Complexes (DPhF=N,N′‐Diphenylformamidinate): A Theoretical Explanation of the Axial Ligand Influence

Electronic Structure of Ru₂(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding

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The first crystal structure of a one-dimensional chain of linked RuIIRuII units

Cited by 69 publications

References 29 publications

Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru2II,II]/[Rh2II,II] Dimers

Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru2II,II]/[Rh2II,II] Dimers

Tuning the Magnetic Moment of [Ru2(DPhF)3(O2CMe)L]+ Complexes (DPhF=N,N′‐Diphenylformamidinate): A Theoretical Explanation of the Axial Ligand Influence

Electronic Structure of Ru2(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding

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Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru₂^II,II]/[Rh₂^II,II] Dimers

Selective NO Trapping in the Pores of Chain-Type Complex Assemblies Based on Electronically Activated Paddlewheel-Type [Ru₂^II,II]/[Rh₂^II,II] Dimers

Tuning the Magnetic Moment of [Ru₂(DPhF)₃(O₂CMe)L]⁺ Complexes (DPhF=N,N′‐Diphenylformamidinate): A Theoretical Explanation of the Axial Ligand Influence

Electronic Structure of Ru₂(II,II) Oxypyridinates: Synthetic, Structural, and Theoretical Insights into Axial Ligand Binding