Matrix effects on the high-spin→low-spin relaxation in [M1−Fe (bpy)3](PF6)2 (M=Cd, Mn and Zn, bpy=2,2′-bipyridine)

Schenker, Sabine; Hauser, Andreas; Wang, Wei; Chan, I. Y.

doi:10.1016/s0009-2614(98)01136-1

Cited by 20 publications

(14 citation statements)

References 19 publications

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“…For [Fe(bpy) 3 ] 2 + (Figure 2), for instance, they vary between % 10 4 s À1 and % 10 8 s À1 , depending on the complex environment. [29][30][31] As proposed by Buhks et al, [20] the HS!LS relaxation in spin-crossover compounds of first-row transition metal ions is Figure 1. Configurational coordinate diagram along the totally symmetric breathing mode for an iron(II) complex with an LS 1 A 1g (t 6 2g ) ground state.…”

Section: The Hs!ls Relaxation and The Zero-point Energy Differencementioning

confidence: 70%

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Assessment of Density Functionals for the High‐Spin/Low‐Spin Energy Difference in the Low‐Spin Iron(II) Tris(2,2′‐bipyridine) Complex

et al. 2005

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In the iron(II) low‐spin complex [Fe(bpy)3]2+, the zero‐point energy difference between the 5T2g(t${{{4\hfill \atop 2g\hfill}}}$${e{{2\hfill \atop g\hfill}}}$) high‐spin and the 1A1g(t${{{6\hfill \atop 2g\hfill}}}$) low‐spin states, ΔE${{{0\hfill \atop HL\hfill}}}$, is estimated to lie in the range of 2500–5000 cm−1. This estimate is based on the low‐temperature dynamics of the high‐spin→low‐spin relaxation following the light‐induced population of the high‐spin state and on the assumption that the bond‐length difference between the two states ΔrHL is equal to the average value of ≈0.2 Å, as found experimentally for the spin‐crossover system. Calculations based on density functional theory (DFT) validate the structural assumption insofar as the low‐spin‐state optimised geometries are found to be in very good agreement with the experimental X‐ray structure of the complex and the predicted high‐spin geometries are all very close to one another for a whole series of common GGA (PB86, PW91, PBE, RPBE) and hybrid (B3LYP, B3LYP*, PBE1PBE) functionals. This confirmation of the structural assumption underlying the estimation of ΔE${{{0\hfill \atop HL\hfill}}}$ from experimental relaxation rate constants permits us to use this value to assess the ability of the density functionals for the calculation of the energy difference between the HS and LS states. Since the different functionals give values from −1000 to 12000 cm−1, the comparison of the calculated values with the experimental estimate thus provides a stringent criterion for the performance of a given functional. Based on this comparison the RPBE and B3LYP* functionals give the best agreement with experiment.

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Section: The Hs!ls Relaxation and The Zero-point Energy Differencementioning

confidence: 70%

“…For the title complex [Fe(bpy) 3 ] 2 + , an acceleration of a factor of two at 10 K has been reported. [31] At comparatively low pressure, the lowtemperature tunnelling rate constant as a function of pressure can be expressed as Equation (4):…”

Section: The Hs!ls Relaxation and The Zero-point Energy Differencementioning

confidence: 99%

Assessment of Density Functionals for the High‐Spin/Low‐Spin Energy Difference in the Low‐Spin Iron(II) Tris(2,2′‐bipyridine) Complex

et al. 2005

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“…In 1983, Netzel and co-workers published a picosecond time-resolved absorption study of the excited-state dynamics of [Fe(bpy) 3 ] 2+ [22]. Although not a SCO compound, the lowest-energy excited state of [Fe(bpy) 3 ] 2+ is also the 5 T 2 state and therefore presents in electronic terms a strict analogy to the SCO systems we are considering here [23]. In addition to some dynamic information, Netzel reported a quantum yield for formation of the lowest-energy excited state of 1.0€0.05, i.e., the 5 T 2 state is formed with unit efficiency following 1 A 1 !…”

Section: Probing the Mechanism Of Photoconversionmentioning

confidence: 99%

Time-Resolved Relaxation Studies of Spin Crossover Systems in Solution

Brady

McGarvey

McCusker

et al.

Topics in Current Chemistry

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“…This effect could be compensated by the application of a positive external pressure that favors the LS state (the smaller state). [11d], However, as metal dilution changes the transition temperature, according to the inverse energy‐gap law, the relaxation kinetics should be slower. This point is difficult to disentangle from a cooperativity decrease that also slows down the relaxation.…”

Section: Introductionmentioning

confidence: 99%

On the Effect of the Internal Pressure on the Photoinduced Spin‐Crossover Behavior of [Fe_xM_1–x(1,10‐phenanthroline)₂(NCS)₂] Solid Solutions (M = Ni^II, Zn^II, and Cd^II)

et al. 2017

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Abstract:The thermal and light-induced magnetic properties of a family of metal-diluted spin-crossover complexes, [Fe x M 1-x -(phen) 2 (NCS) 2 ] (phen = 1,10-phenantholine and M = Ni II , Cd II ), are reported and compared to previous results obtained for the same series but with Zn II ions used to substitute Fe II ions; the ultimate goal was to validate the influence of the size and nature of the inert metal ion on the light-induced properties of spin-crossover compounds. For all of the materials, we measured the thermally induced spin-crossover temperature (T 1/2 )

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Matrix effects on the high-spin→low-spin relaxation in [M1−Fe (bpy)3](PF6)2 (M=Cd, Mn and Zn, bpy=2,2′-bipyridine)

Cited by 20 publications

References 19 publications

Assessment of Density Functionals for the High‐Spin/Low‐Spin Energy Difference in the Low‐Spin Iron(II) Tris(2,2′‐bipyridine) Complex

Assessment of Density Functionals for the High‐Spin/Low‐Spin Energy Difference in the Low‐Spin Iron(II) Tris(2,2′‐bipyridine) Complex

Time-Resolved Relaxation Studies of Spin Crossover Systems in Solution

On the Effect of the Internal Pressure on the Photoinduced Spin‐Crossover Behavior of [Fe_xM_1–x(1,10‐phenanthroline)₂(NCS)₂] Solid Solutions (M = Ni^II, Zn^II, and Cd^II)

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Matrix effects on the high-spin→low-spin relaxation in [M1−Fe (bpy)3](PF6)2 (M=Cd, Mn and Zn, bpy=2,2′-bipyridine)

Cited by 20 publications

References 19 publications

Assessment of Density Functionals for the High‐Spin/Low‐Spin Energy Difference in the Low‐Spin Iron(II) Tris(2,2′‐bipyridine) Complex

Assessment of Density Functionals for the High‐Spin/Low‐Spin Energy Difference in the Low‐Spin Iron(II) Tris(2,2′‐bipyridine) Complex

Time-Resolved Relaxation Studies of Spin Crossover Systems in Solution

On the Effect of the Internal Pressure on the Photoinduced Spin‐Crossover Behavior of [FexM1–x(1,10‐phenanthroline)2(NCS)2] Solid Solutions (M = NiII, ZnII, and CdII)

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On the Effect of the Internal Pressure on the Photoinduced Spin‐Crossover Behavior of [Fe_xM_1–x(1,10‐phenanthroline)₂(NCS)₂] Solid Solutions (M = Ni^II, Zn^II, and Cd^II)