Light-induced excited spin state trapping (LIESST) in [Fe(2-mephen)3]2+ embedded in polymer matrices

Hauser, Andreas; Adler, J. C.; Gütlich, Philipp

doi:10.1016/0009-2614(88)80443-3

Cited by 123 publications

(96 citation statements)

References 14 publications

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“…For the system of non-interacting complexes, an inhomogeneous distribution results in deviation from single exponential with a characteristic fast initial decay and a long tail with a much slower decay. This behaviour is, in fact, observable for iron(II) spin-crossover complexes embedded in polymer matrices [30]. For the concentrated system, the effect of an inhomogeneous distribution is to reduce the self-acceleration quite dramatically.…”

Section: Inhomogeneous Distributionsmentioning

confidence: 89%

Cooperative phenomena and light-induced bistability in iron(II) spin-crossover compounds

Hauser

Jeftić

Romstedt

et al. 1999

Coordination Chemistry Reviews

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301

239

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Section: Inhomogeneous Distributionsmentioning

confidence: 89%

Cooperative phenomena and light-induced bistability in iron(II) spin-crossover compounds

Hauser

Jeftić

Romstedt

et al. 1999

Coordination Chemistry Reviews

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301

239

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“…In the absence of cooperative effects this results in gradual spin transitions with a well defined transition temperature, single exponential decay curves rather than the self-accelerated curves often observed for neat crystalline materials [11] and no interference from crystallographic phase transitions [35] nor deviations from single exponential decay due to inhomogeneous distributions in amorphous matrices [36].…”

Section: Experimental Methodsmentioning

confidence: 99%

Low-temperature lifetimes of metastable high-spin states in spin-crossover and in low-spin iron(II) compounds: The rule and exceptions to the rule

Hauser

Enachescu

Daku

et al. 2006

Coordination Chemistry Reviews

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193

255

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The high-spin → low-spin relaxation in spin-crossover compounds can be described as non-adiabatic multi-phonon process in the strong coupling limit, in which the low-temperature tunnelling rate increases exponentially with the zero-point energy difference between the two states. Based on the hypothesis that the experimental bond length difference between the high-spin and the low-spin state of not, vert, similar0.2 Å is also valid for low-spin iron(II) complexes, extrapolation of the single configurational coordinate model allows an estimate of the zero-point energy difference for low-spin complexes from kinetic data. DFT calculations on low-spin [Fe(bpy)3]2+ support the structural assumption. However, for low-spin [Fe(terpy)2]2+ the relaxation rate constant shows an anomalous behaviour in so far as it is more in line with spin-crossover systems. This is attributed to very anisotropic bond length changes associated with the spin state change, and the subsequent breakdown of the single mode model

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“…, which is several orders of magnitude larger than that for iron(II) SCO compounds, because Dr HL is smaller for the ironA C H T U N G T R E N N U N G (III) compounds. [57] In 1, the k HL A C H T U N G T R E N N U N G (T!0) value, 2.4 10 À8 s…”

Section: ]Ncs (4) and [Fea C H T U N G T R E N N U N G (Qsal)mentioning

confidence: 99%

Photo‐Induced Spin Transition of Iron(III) Compounds with π–π Intermolecular Interactions

Hayami

Hiki

Kawahara

et al. 2009

Chemistry A European J

156

165

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Iron(III) spin-crossover compounds [Fe(pap)(2)]ClO(4) (1), [Fe(pap)(2)]BF(4) (2), [Fe(pap)(2)]PF(6) (3), [Fe(qsal)(2)]NCS (4), and [Fe(qsal)(2)]NCSe (5) (Hpap=2-(2-pyridylmethyleneamino)phenol and Hqsal=2-[(8-quinolinylimino)methyl]phenol) were prepared and their spin-transition properties investigated by magnetic susceptibility and Mössbauer spectroscopy measurements. The iron(III) compounds exhibited spin transition with thermal hysteresis. Single crystals of the iron(III) compounds were obtained as suitable solvent adducts for X-ray analysis, and structures in high-spin (HS) and low-spin (LS) states were revealed. Light-induced excited-spin-state trapping (LIESST) effects of the iron(III) compounds were induced by light irradiation at 532 nm for 1-3 and at 800 nm for 4 and 5. The activation energy E(a) and the low-temperature tunneling rate k(HL)(T-->0) of iron(III) LIESST compound 1 were estimated to be 1079 cm(-1) and 2.4x10(-8) s(-1), respectively, by HS-->LS relaxation experiments. The Huang-Rhys factor S of 1 was also estimated to be 50, which was similar to that expected for iron(II) complexes. It is thought that the slow relaxation in iron(III) systems is achieved by the large structural distortion between HS and LS states. Introduction of strong intermolecular interactions, such as pi-pi stacking, can also play an important role in the relaxation behavior, because it can enhance the structural distortion of the LIESST complex.

show abstract

Light-induced excited spin state trapping (LIESST) in [Fe(2-mephen)3]2+ embedded in polymer matrices

Cited by 123 publications

References 14 publications

Cooperative phenomena and light-induced bistability in iron(II) spin-crossover compounds

Cooperative phenomena and light-induced bistability in iron(II) spin-crossover compounds

Low-temperature lifetimes of metastable high-spin states in spin-crossover and in low-spin iron(II) compounds: The rule and exceptions to the rule

Photo‐Induced Spin Transition of Iron(III) Compounds with π–π Intermolecular Interactions

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