Spin Alignment in Singly Oxidized Spin-Polarized Diradical Donor:  Thianthrene Bis(nitronyl nitroxide)

Izuoka, Akira; Hiraishi, Mayumi; Abe, Takehiro; Sugawara, Tadashi; Sato, Kazunobu; Takui, Takeji

doi:10.1021/ja9916759

Cited by 60 publications

(59 citation statements)

References 23 publications

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“…[17] However, spin manipulation at the intramolecular level benefits from the greater versatility inherent to molecules. This is exemplified by the following recently proposed chemo- [18] (e.g., proton-), [19] redox-, [20][21][22] and light-responsive [23][24][25][26][27] molecular spin systems, whether purely organic or hybrid inorganic compounds. With regards to optical control, we have reported the first spin manipulation that relies on the intramolecular field of a locally excited state (LES) in purely organic p-conjugated multicomponent spin systems.…”

Section: Introductionmentioning

confidence: 96%

Intramolecular Spin Alignment within Mono‐Oxidized and Photoexcited Anthracene‐Based π Radicals as Prototypical Photomagnetic Molecular Devices: Relationships Between Electrochemical, Photophysical, and Photochemical Control Pathways

Matsumoto

Ciofini

Lainé

et al. 2009

Chemistry A European J

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AnOV is a pi-conjugated radical built from an anthracene (An) unit linked by a p-phenylene to an oxoverdazyl (OV) moiety. The mono-oxidized (cationic) form of AnOV was generated both electrochemically and photochemically (in the presence of an electron acceptor). The triplet nature (S=1) of the electronic ground state of AnOV(+) was demonstrated by combining spectroelectrochemistry, electron-spin resonance (ESR) experiments, and ab initio molecular orbital (MO) calculations. The intramolecular spin alignment (ISA) within AnOV(+) results from the ferromagnetic coupling (J(electrochem)>0) of the two unpaired electrons located on the oxidized electron donor (An(+)) and on the pendant OV radical. The spin-density distribution pattern of AnOV(+) is akin to that of AnOV when photopromoted (AnOV*) to its high-spin (HS) lowest excited quartet (S=3/2) state. This high-spin state results from the ferromagnetic coupling (J(photophys)>0) of the triplet locally excited state of An ((3)An*) with the doublet ground state of OV. As a shared salient feature, AnOV(+) and AnOV* (HS) show a spin delocalization within the domain of activated An in either An(+) or (3)An* (nexus states) forms. The present study essentially contributes to establish and clarify relationships between electrochemical, photophysical, and photochemical pathways to achieve ISA processes within AnOV. In particular, we discuss the impact of the spin polarization of the unpaired electron of OV on electronic features of the An electron-donating subunit. Close analysis of this polarizing interplay allows one to derive a novel functional paradigm to manipulate electron spins at the intramolecular level with light and under an external magnetic field. Indeed, two original functional elements are identified: light-triggered donors of spin-polarized electrons and spin-selective electron acceptors, which are of potential interest for molecular spintronics.

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Section: Introductionmentioning

confidence: 96%

Intramolecular Spin Alignment within Mono‐Oxidized and Photoexcited Anthracene‐Based π Radicals as Prototypical Photomagnetic Molecular Devices: Relationships Between Electrochemical, Photophysical, and Photochemical Control Pathways

Matsumoto

Ciofini

Lainé

et al. 2009

Chemistry A European J

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“…[1] Manipulation of the magnetic properties of organic molecules in the spin ground state has been intensively studied by using electron-hole doping [2] and photochromic molecules. [3] Recently, photoswitching between diamagnetic and paramagnetic phases was realized in a 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) organic crystal.…”

mentioning

confidence: 99%

First Evidence for a Uniquely Spin‐Polarized Quartet Photoexcited State of a π‐Conjugated Spin System Generated via the Ion‐Pair State

et al. 2006

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“…3,4,5,6 A new class of purely organic molecular magnets has received increasing attention as their intramolecular spin alignment is controllable by external stimuli such as charge doping or photoexcitation, 7,8,9,10,11,12,13,14,15,16 as schematically shown in Fig. 1.…”

Section: Introductionmentioning

confidence: 99%

“…7 The molecule is spin singlet (S = 0) in neutral state with very weak antiferromagnetic exchange coupling (−1.4 K) between the nitronyl nitroxide groups. Upon one-electron oxidation, i.e.…”

Section: Introductionmentioning

confidence: 99%

Theory of Doping Induced High-Spin in a Model of Polyene-based Molecular Magnets

2004

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Control of intramolecular spin alignment is studied theoretically in a model of polyene-based molecular magnets in which delocalized π electrons are coupled with localized radical spins. In a previous paper [Phys. Rev. Lett. 90 (2003) 207203], we have demonstrated that charge doping is an effective way to realize controllable high-spin in the π-conjugated molecular magnets. In this paper, we clarify the dependence of spin-alignment on the exchange interaction between the localized spin and π electron and the electron-electron interactions. The antiferromagnetic exchange interaction plays a role different from the ferromagnetic counterpart in doped molecules. To understand complex interplay of charge and spin degrees of freedom in the doped systems, we carry out a systematic study on the phase diagram of spin alignment in the parameter space. The mechanism of the spin alignment is discussed based on the spin densities of π electrons. The calculated results are consistent with experiments, providing a theoretical basis for the control of spin alignment.

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Spin Alignment in Singly Oxidized Spin-Polarized Diradical Donor: Thianthrene Bis(nitronyl nitroxide)

Cited by 60 publications

References 23 publications

Intramolecular Spin Alignment within Mono‐Oxidized and Photoexcited Anthracene‐Based π Radicals as Prototypical Photomagnetic Molecular Devices: Relationships Between Electrochemical, Photophysical, and Photochemical Control Pathways

Intramolecular Spin Alignment within Mono‐Oxidized and Photoexcited Anthracene‐Based π Radicals as Prototypical Photomagnetic Molecular Devices: Relationships Between Electrochemical, Photophysical, and Photochemical Control Pathways

First Evidence for a Uniquely Spin‐Polarized Quartet Photoexcited State of a π‐Conjugated Spin System Generated via the Ion‐Pair State

Theory of Doping Induced High-Spin in a Model of Polyene-based Molecular Magnets

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