期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 132, 期 5, 页码 1532-1544出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja909489s
关键词
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资金
- Ministry of Education, Culture, Sports, Science, and Technology, Japan [21350032]
- Asahi Glass Foundation
- JSPS
- Department of Energy [DE-FG02-02ER45999]
- National Science Foundation
- Welch Foundation [A-1449]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0957840] Funding Source: National Science Foundation
- Grants-in-Aid for Scientific Research [20225003] Funding Source: KAKEN
The isostructural series of two-dimensional (2-D) fishnet-type network compounds, [{Ru-2(O2CCF3)(4)}(2)-(TCNQR(x))]center dot n(solv) (R-x = H-4, 1; Br-2, 2; Cl-2, 3; F-2, 4; F-4, 5), has been synthesized from the reactions of a paddlewheel diruthenium(II, II) complex, [Ru-2(II,II)(O2CCF3)(4)], and neutral TCNQ derivatives (TCNQR(x) = 2,3,5,6- or 2,5-halogen-substituted 7,7,8,8-tetracyanoquinodimethane) under anaerobic conditions. Corresponding Rh compounds 1-Rh-5-Rh, which are diamagnetic and redox-inactive, were also synthesized for the purpose of comparison with 1-5. According to the electron affinity of TCNQR(x), which is related to its first reduction potential, the Ru-2 series (1-5) has the requisite driving force for charge transfer from [Ru-2(II,II)(O2CCF3)(4)] to TCNQR(x), which can lead to a mixed-valence state of [{Ru-2(4.5+)}-(TCNQR(x)(center dot-))-{Ru-2(4.5+)}] for the 2-D network Such a charge (or electron) transfer results in magnetic exchange interactions between [Ru-2] units (S = 1 for [Ru-2(II,II)] and S = 3/2 for [Ru-2(II,III)](+)) via TCNQR(x)(center dot-) S = 1/2 radicals that lead to long-range magnetic ordering in the layer. In the present series, only 5 demonstrated the full electron transfer (1-e(-) transfer) to the mixed-valence state, whereas other members are essentially in the state [{Ru-2(4+)}- (TCNQR(x)(0)){Ru-2(4+)}]. Whereas 1-4 are paramagnetic, 5 is a metamagnet undergoing 3-D long-range antiferromagnetic ordering at 95 K (= T-N) and reverts to a magnetic-field-induced ferromagnetic state exhibiting coercivity up to 60 K. This result is consistent with the fact that TCNQF(4) has the strongest electron affinity among the TCNQR(x) molecules. Even in neutral forms, however, 1-4 can be observed to undergo thermally and/or field-activated charge transfers from [Ru-2(II,II)] to TCNQR(x) to give semiconductors with an activation energy of 200-300 meV, which is a driving force to transport electrons over the lattice. As determined by their conducting properties, the ease of thermally and/or field-activated charge transfers is on the order of 1 < 4 < 2 approximate to 3 << 5, which is in agreement with the order of electron affinity of TCNQR(x). Indeed, a magnetic anomaly with short-range order associated with the localization of charge-transferred electrons was revealed in the low-temperature susceptibility data for 2 and 3. Finally, 5 was subjected to terahertz time-domain spectroscopy, the data from which revealed that transport hopping electrons scattered at high temperatures interact with magnetically ordered spins with the scattering being suppressed at T-N, at which temperature the real part of the complex electronic Conductivity (sigma(1)) and dielectric permeability (epsilon(1)) are dramatically altered. From these collective data, we conclude that molecular design based on an interunit charge transfer in a paramagnetic lattice is an efficient route to the design of materials with synergism between magnetic and conducting properties.
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