Tuning of Stepwise Neutral-Ionic Transitions by Acceptor Site-Doping in Alternating Donor/Acceptor Chains
Tuning of Stepwise Neutral-Ionic Transitions by Acceptor Site-Doping in Alternating Donor/Acceptor Chains
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通过交替供体/受体链中的受体位点掺杂来调节逐步中性离子跃迁
DOI：
10.1021/acs.inorgchem.5b02858
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发表时间：
2016
期刊：
影响因子：
4.6
通讯作者：
Keita Nakabayashi et al.
中科院分区：
文献类型：
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作者：
Tomoaki Fukushima;Shin-ichiro Kawano;Kentaro Tanaka;Keita Nakabayashi et al.
通过用2，5-二甲氧基-N，N‘-二氰基苯二亚胺(DMeODCNQI)部分取代受体DMDCNQI(2，5-二甲氧基-N，N’-二氰基苯二亚胺(DMeODCNQI))，调节了交替的供体/受体链[RU2(2，3，5，6-F4PhCO2)4(DMDCNQI)]·2(对二甲苯)(0；2，3，5，6-F4PhCO2-=2，3，5，6-四氟苯甲酸酯；DMDCNQI=2，5-二甲基-N，N‘-二氰基苯二亚胺(DMeODCNQI))中的分步中性离子(N-I)相变。位置掺杂系列包括掺杂率(X)=0.05(0.05MeO)、0.10(0.10-MeO)、0.15(0.15-MeO)和0.20(0.20-MeO)的[Ru2(2，3，5，6-F4PhCO2)4(DMDCNQI)1–x(DMeODCNQI)x]·2(p-xylene)。还鉴定了中性链[Ru2(2，3，5，6-F4PhCO2)4(DMeODCNQI)]·4(p-xylene)(1)，它只含有DMeODCNQI。除1外，所有的位掺杂化合物都是等结构的，尽管它们的DA链基序相同。除了X值为0.20时，它们都表现出包含中间相的两步N-I转变。这种转变是在高温下发生的，但随着掺杂率的增加而平行向低温方向移动。同时，每个跃迁都随着掺杂率的增加而展宽，导致两个跃迁在X值接近0.2处收敛。施主/受主位置掺杂技术对链间库仑效应的影响略有不同。
The stepwise neutral–ionic (N–I) phase transition found in the alternating donor/acceptor (DA) chain [Ru2(2,3,5,6-F4PhCO2)4(DMDCNQI)]·2(p-xylene) (0; 2,3,5,6-F4PhCO2–= 2,3,5,6-tetrafluorobenzoate; DMDCNQI = 2,5-dimethyl-N,N′-dicyanoquinonediimine) was tuned by partly substituting the acceptor DMDCNQI with 2,5-dimethoxy-N,N′-dicyanoquinonediimine (DMeODCNQI), which displays a poorer electron affinity in an isostructural series. The site-doped series comprised [Ru2(2,3,5,6-F4PhCO2)4(DMDCNQI)1–x(DMeODCNQI)x]·2(p-xylene) for doping rates (x) = 0.05 (0.05-MeO), 0.10 (0.10-MeO), 0.15 (0.15-MeO), and 0.20 (0.20-MeO). The neutral chain [Ru2(2,3,5,6-F4PhCO2)4(DMeODCNQI)]·4(p-xylene) (1), which only contained DMeODCNQI, was also characterized. All site-doped compounds were isostructural to0except1despite their identical DA chain motif. Except at anxvalue of 0.20, they displayed a two-step N–I transition involving an intermediate phase. This transition occurred at high temperatures in0but shifted to lower temperatures in a parallel manner with increasing doping rate. Simultaneously, each transition broadened with increasing doping rate, leading to a convergence of two transitions at anxvalue approximating 0.2. Donor/acceptor-site-doping techniques present somewhat different impacts in terms of interchain Coulomb effects.