Trinuclear Early/Late‐Transition‐Metal Thiolate Complexes

Eichhöfer, Andreas; Andrushko, Vasyl; Bodenstein, Tilmann; Fink, Karin

doi:10.1002/ejic.201402069

Cited by 7 publications

(5 citation statements)

References 69 publications

(97 reference statements)

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“…These values are in the order of the sum of the covalent radii of vanadium and nickel (2.77 Å), with covalent ratios ( r ) of 1.00 and 1.01. 42 , 43 Although there is a paucity of vanadium–nickel metal–metal bonds in the literature, 44 − 46 these distances are consistent with a formal bonding interaction between the metal centers. The bridging nature of the thiolates results in a slight elongation of the vanadium–sulfur distance from V–S avg = 2.36 Å in the free [V(SNS) 2 ] 1– anion to V–S avg = 2.43 Å in the [V(SNS) 2 {Ni(dppe)} 2 ] 1– trimetallic cluster.…”

Section: Resultsmentioning

confidence: 66%

Two-Electron Mixed Valency in a Heterotrimetallic Nickel–Vanadium–Nickel Complex

Wojnar

Heyduk

2023

Inorg. Chem.

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Mixed-valence complexes represent an enticing class of coordination compounds to interrogate electron transfer confined within a molecular framework. The diamagnetic heterotrimetallic anion, [V(SNS)2{Ni(dppe)}2]−, was prepared by reducing (dppe)NiCl2 in the presence of the chelating metalloligand [V(SNS)2]− [dppe = bis(diphenylphosphino)ethane; (SNS)3– = bis(2-thiolato-4-methylphenyl)amide]. Vanadium–nickel bonds span the heterotrimetallic core in the structure of [V(SNS)2{Ni(dppe)}2]−, with V–Ni bond lengths of 2.78 and 2.79 Å. One-electron oxidation of monoanionic [V(SNS)2{Ni(dppe)}2]− yielded neutral, paramagnetic V(SNS)2{Ni(dppe)}2. The solid-state structure of V(SNS)2{Ni(dppe)}2 revealed that the two nickel ions occupy unique coordination environments: one nickel is in a square-planar S2P2 coordination environment (τ4 = 0.19), with a long Ni···V distance of 3.45 Å; the other nickel is in a tetrahedral S2P2 coordination environment (τ4 = 0.84) with a short Ni–V distance of 2.60 Å, consistent with a formal metal–metal bond. Continuous-wave X-band electron paramagnetic resonance spectroscopy, electrochemical investigations, and density functional theory computations indicated that the unpaired electron in the neutral V(SNS)2{Ni(dppe)}2 cluster is localized on the bridging [V(SNS)2] metalloligand, and as a result, V(SNS)2{Ni(dppe)}2 is best described as a two-electron mixed-valence complex. These results demonstrate the important role that metal–metal interactions and flexible coordination geometries play in enabling multiple, reversible electron transfer processes in small cluster complexes.

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Section: Resultsmentioning

confidence: 66%

Two-Electron Mixed Valency in a Heterotrimetallic Nickel–Vanadium–Nickel Complex

Wojnar

Heyduk

2023

Inorg. Chem.

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“…Assuming the phenyl-chalcogenolato ligands −SPh and −SePh to be singly negatively charged, we assign, in agreement with previous reports, the formal oxidation states of +IV to the titanium atoms and +I to the coinage metal as well as sodium atoms. , In the literature, several other heterobimetallic trinuclear complexes can be found, which comprise a similar linear metal skeleton, including [Cu 2 Sn(EPh) 6 (PPh 3 ) 2 ] (E = S, Se), , [Ag 2 Sn(SPh) 6 (PPh 3 ) 2 ], [Cu 2 Nb(SePh) 6 (PR 3 ) 2 ] (R = org. group), [Co 2 V(SPh) 8 ] 2– , [Ni 2 V(SPh) 8 ] 2– , [Cu 2 M(SAr) 6 (PPh 3 ) 2 ] (M = W, Mo, U; Ar = Ph, p -C 6 H 4 Me, p -C 6 H 4 F, p -C 6 H 4 Cl, p -C 6 H 4 Br), − and [LFeMFeL] n + (M = Ge, Sn; n = 2, 3; L = 1,4,7-(4- tert -butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane) …”

Section: Results and Discussionmentioning

confidence: 99%

Near-Infrared Luminescence in Trinuclear Mixed-Metal Chalcogenolate Complexes of the Types [M₂Ti(EPh)₆(PPh₃)₂] (M = Cu, Ag; E = S, Se) and [Na(thf)₃]₂[Ti(SPh)₆]

2021

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The optical properties of four new trinuclear chalcogenolato bridged metal complexes [Ag 2 Ti(SPh) , and [Ag 2 Ti-(SePh) 6 (PPh 3 ) 2 ] have been investigated by absorption and photoluminescence spectroscopy as well as time-dependent density functional theory (TDDFT) calculations and compared to the results published recently for [Cu 2 Ti(SPh) 6 (PPh 3 ) 2 ]. All of these compounds are distinguished by efficient near-infrared luminescence at ∼880−1200 nm in the solid state at low temperatures, which remains quite intense for the copper−titanium complexes at ambient temperature with PL quantum yields of 9.5 and 4.8% at λ PL = 1090 and 1240 nm for [Cu 2 Ti(EPh) 6 (PPh 3 ) 2 ], E = S, Se, respectively. According to the calculations, a peculiar feature of the lowest-energy electronic transitions in these complexes is their high localization on the metal and chalcogen atoms, with negligible contributions of the "external" ligand groups. Correspondingly, the type of atoms in the M 2 TiE 6 (M = Cu, Ag, Na) core structure determines optical properties such as the absorption and emission wavelengths and PL lifetime.

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“…The CASOCI program only needs these matrix elements, whose number is very small since only active orbital indices are involved. So far the program has been used with CASSCF orbitals obtained either with MOLPRO [30] or with the program of Meier and Staemmler [31] , where we have programmed an interface to store orbitals and basis set data in TURBOMOLE format.…”

Section: Methodsmentioning

confidence: 99%

“…In Ref. [31], a scaled nucleus approach with a scaling factor of 0.61 was used for the spin-orbit integrals. S4).…”

Section: Zero-field Splitting In a Sulfur-bridged Co-v-co Complexmentioning

confidence: 99%

Development and Application of a Complete Active Space Spin‐Orbit Configuration Interaction Program Designed for Single Molecule Magnets

et al. 2021

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We present a spin-orbit configuration interaction program which has been tailored for the description of the magnetic properties of polynuclear metal complexes with partially filled d-and f-shells. The spin-orbit operators are directly included in the configuration interaction program based on Slater-determinants. The lowest states are obtained by a Block-Davidson-type diagonalisation. The usage of localised active orbitals enables the construction of start vectors from tensor products of singlecenter wave functions that already include spin-orbit interaction. This allows for an analysis of the role and the interplay of the different metal centres. Furthermore, in case of weak coupling of the metal centres these tensor products are already close to the final wave functions ensuring fast convergence. In combination with a two-layer hybrid parallelisation, this makes the program highly efficient. Based on the spin-orbit coupled wave functions, magnetic D-tensors, g-tensors and temperature-dependent susceptibilities can be calculated. The applicability and performance of the program is shown exemplarily on a trinuclear transition metal (Co II V II Co II ) complex.

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Trinuclear Early/Late‐Transition‐Metal Thiolate Complexes

Abstract: The thiolato-bridged cobalt(II)/vanadium(II) complexes [Li(thf)

Cited by 7 publications

References 69 publications

Two-Electron Mixed Valency in a Heterotrimetallic Nickel–Vanadium–Nickel Complex

Two-Electron Mixed Valency in a Heterotrimetallic Nickel–Vanadium–Nickel Complex

Near-Infrared Luminescence in Trinuclear Mixed-Metal Chalcogenolate Complexes of the Types [M₂Ti(EPh)₆(PPh₃)₂] (M = Cu, Ag; E = S, Se) and [Na(thf)₃]₂[Ti(SPh)₆]

Development and Application of a Complete Active Space Spin‐Orbit Configuration Interaction Program Designed for Single Molecule Magnets

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Trinuclear Early/Late‐Transition‐Metal Thiolate Complexes

Abstract: The thiolato-bridged cobalt(II)/vanadium(II) complexes [Li(thf)

Cited by 7 publications

References 69 publications

Two-Electron Mixed Valency in a Heterotrimetallic Nickel–Vanadium–Nickel Complex

Two-Electron Mixed Valency in a Heterotrimetallic Nickel–Vanadium–Nickel Complex

Near-Infrared Luminescence in Trinuclear Mixed-Metal Chalcogenolate Complexes of the Types [M2Ti(EPh)6(PPh3)2] (M = Cu, Ag; E = S, Se) and [Na(thf)3]2[Ti(SPh)6]

Development and Application of a Complete Active Space Spin‐Orbit Configuration Interaction Program Designed for Single Molecule Magnets

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Near-Infrared Luminescence in Trinuclear Mixed-Metal Chalcogenolate Complexes of the Types [M₂Ti(EPh)₆(PPh₃)₂] (M = Cu, Ag; E = S, Se) and [Na(thf)₃]₂[Ti(SPh)₆]