Metallocene‐Based Magnets

Yee, Gordon T.; Miller, Joel S.

doi:10.1002/3527604383.ch7

Cited by 7 publications

(3 citation statements)

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“…In some of these crystals, diamagnetic dianionic dimers, [A] 2 2− (A = TCNE, TCNQ), have been reported. Whereas many examples of electron transfer salts possessing [TCNE] •− exhibit bulk magnetic ordering, and many examples of electron transfer salts possessing [TCNQ] •− exhibit high metal-like dc electrical conductivity, these properties are not manifested when [A] 2 2− is present. Therefore, to obtain new [TCNE] •− and [TCNQ] •− electron transfer salts with technologically interesting properties, it is necessary to understand the factors that control the existence of [TCNE] 2 2− and [TCNQ] 2 2− dimers.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Electronic Structure of [TCNQ]₂²⁻(TCNQ = 7,7,8,8-Tetracyano-p-quinodimethane) Dimers and Their Intradimer, Long, Multicenter Bond in Solution and the Solid State

2009

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The long, multicenter bonding in 7,7,8,8-tetracyano-p-quinodimethane anion radical dimers, [TCNQ](2)(2-), observed in both the solid state and in solution, was computationally investigated via B3LYP, CASSCF(2,2), and MCQDPT/CASSCF(2,2) methods. Isolated [TCNQ](*-)...[TCNQ](*-) interactions are repulsive by all three methods, although a metastable minimum is found at the MCQDPT/CASSCF(2,2) level. In the solid state, the stability of [TCNQ](2)(2-) dimers primarily originates from [TCNQ](*-)...cation(+) electrostatic interactions, whose sum exceeds the sum of the [TCNQ](*-)...[TCNQ](*-) and cation(+)...anion(+) repulsive interactions. In the solid state, as observed for K(2)[TCNQ](2) aggregates, [TCNQ](2)(2-) has a long, two-electron bond with contributions from 20 centers (4 N...N and 6 C...C). In solution, their stability originates from the [TCNQ](*-)solvent attractive interactions, as calculated for {[TCNQ](2)(S)(4)}(2-) (S = CH(2)Cl(2), H(2)O), and these have contributions from 16 C centers as the N atoms do not contribute because the nitriles bend away from the nominal plane of the fragment. MCQDPT/CASSCF(2,2) calculations indicate that the electronic ground state of these [TCNQ](2)(2-) dimers is a closed-shell singlet with a non-negligible contribution from the open-shell singlet, as is experimentally observed. This ground-state electronic structure is well described from B3LYP calculations.

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Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Electronic Structure of [TCNQ]₂²⁻(TCNQ = 7,7,8,8-Tetracyano-p-quinodimethane) Dimers and Their Intradimer, Long, Multicenter Bond in Solution and the Solid State

2009

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“…Currently, metallocenes are of ever-increasing interest among researchers in fundamental and applied science, since they are relevant to the modern theories of metal–ligand bonding [ 3 , 4 , 5 , 6 ], electro- and magnetochemistry [ 7 , 8 , 9 , 10 , 11 , 12 , 13 ], metallopolymers [ 14 , 15 , 16 , 17 , 18 ], biomedicine [ 19 , 20 , 21 , 22 ], catalysis [ 23 , 24 , 25 ], nanoelectronics [ 26 , 27 , 28 , 29 , 30 , 31 , 32 ] and molecular machines [ 33 , 34 , 35 ]. Many applications of metallocenes take advantage of their pronounced reducing properties, which allow for the easy formation of stable or reactive sandwich ions [ 7 , 8 , 9 , 10 , 14 , 15 , 16 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 33 , 34 , …”

Section: Introductionmentioning

confidence: 99%

Ionization of Decamethylmanganocene: Insights from the DFT-Assisted Laser Spectroscopy

et al. 2022

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Metallocenes represent one of the most important classes of organometallics with wide prospects for practical use in various fields of chemistry, materials science, molecular electronics, and biomedicine. Many applications of these metal complexes are based on their ability to form molecular ions. We report the first results concerning the changes in the molecular and electronic structure of decamethylmanganocene, Cp*2Mn, upon ionization provided by the high-resolution mass-analyzed threshold ionization (MATI) spectroscopy supported by DFT calculations. The precise ionization energy of Cp*2Mn is determined as 5.349 ± 0.001 eV. The DFT modeling of the MATI spectrum shows that the main structural deformations accompanying the detachment of an electron consist in the elongation of the Mn-C bonds and a change in the Me out-of-plane bending angles. Surprisingly, the DFT calculations predict that most of the reduction in electron density (ED) upon ionization is associated with the hydrogen atoms of the substituents, despite the metal character of the ionized orbital. However, the ED difference isosurfaces reveal a complex mechanism of the charge redistribution involving also the carbon atoms of the molecule.

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“…The charge-transfer (CT) salt approach has been one of the most successful strategies for producing magnetically ordered compounds based on molecular building blocks …”

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confidence: 99%

Bis(1,2,3-trimethylindenyl)iron(III) 2,3-Dicyanonaphtho-1,4-quinonide, a Non-Metallocene, Charge-Transfer Salt Metamagnet with Complementary Donor−Acceptor Geometries

et al. 2004

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Bis(1,2,3-trimethylindenyl)iron(III) can be paired with 2,3-dicyanonaphtho-1,4-quinone to give an air-stable pi-stacked metamagnet with T(c) = 4.1 K, the first example of a non-metallocene CT salt magnet in this class. A single crystal X-ray structure of the Fe(1,2,3-Me(3)C(9)H(4))(2)[DCNQ] salt indicates that it consists of stacks of alternating donors and acceptors, in which the DCNQ ring systems are aligned with indenyl groups above and below, and the long axes of the DCNQ and the indenyl ligand are parallel to each other. This arrangement suggests that the magnetic properties arise from favorable interactions due to geometric similarities between the donor and acceptor, and not from a unique property of the donor itself.

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Metallocene‐Based Magnets

Cited by 7 publications

References 61 publications

Theoretical Study of the Electronic Structure of [TCNQ]₂²⁻(TCNQ = 7,7,8,8-Tetracyano-p-quinodimethane) Dimers and Their Intradimer, Long, Multicenter Bond in Solution and the Solid State

Theoretical Study of the Electronic Structure of [TCNQ]₂²⁻(TCNQ = 7,7,8,8-Tetracyano-p-quinodimethane) Dimers and Their Intradimer, Long, Multicenter Bond in Solution and the Solid State

Ionization of Decamethylmanganocene: Insights from the DFT-Assisted Laser Spectroscopy

Bis(1,2,3-trimethylindenyl)iron(III) 2,3-Dicyanonaphtho-1,4-quinonide, a Non-Metallocene, Charge-Transfer Salt Metamagnet with Complementary Donor−Acceptor Geometries

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Metallocene‐Based Magnets

Cited by 7 publications

References 61 publications

Theoretical Study of the Electronic Structure of [TCNQ]22−(TCNQ = 7,7,8,8-Tetracyano-p-quinodimethane) Dimers and Their Intradimer, Long, Multicenter Bond in Solution and the Solid State

Theoretical Study of the Electronic Structure of [TCNQ]22−(TCNQ = 7,7,8,8-Tetracyano-p-quinodimethane) Dimers and Their Intradimer, Long, Multicenter Bond in Solution and the Solid State

Ionization of Decamethylmanganocene: Insights from the DFT-Assisted Laser Spectroscopy

Bis(1,2,3-trimethylindenyl)iron(III) 2,3-Dicyanonaphtho-1,4-quinonide, a Non-Metallocene, Charge-Transfer Salt Metamagnet with Complementary Donor−Acceptor Geometries

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Theoretical Study of the Electronic Structure of [TCNQ]₂²⁻(TCNQ = 7,7,8,8-Tetracyano-p-quinodimethane) Dimers and Their Intradimer, Long, Multicenter Bond in Solution and the Solid State

Theoretical Study of the Electronic Structure of [TCNQ]₂²⁻(TCNQ = 7,7,8,8-Tetracyano-p-quinodimethane) Dimers and Their Intradimer, Long, Multicenter Bond in Solution and the Solid State