[TDNQ][CoCp*_2] and [TDNQ]_3[CoCp _2]_2; Radical anions of a 1,2,5-thiadiazolo-naphthoquinone

Morgan I.S.; Jennings M.; Vindigni A.; Clérac R.; Preuss K.E.

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[TDNQ][CoCp*_2] and [TDNQ]_3[CoCp _2]_2; Radical anions of a 1,2,5-thiadiazolo-naphthoquinone

机译：[TDNQ] [CoCp * _2]和[TDNQ] _3 [CoCp _2] _2; 1,2,5-噻二唑并萘醌的自由基阴离子

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The first crystal structure of a quinone[1,2,5]thiadiazole radical anion is presented. Reduction of naphtha[2,3-c][1,2,5]thiadiazole-4,9-dione (TDNQ) with outersphere electron transfer agents, decamethylcobaltocene (CoCp* _2) and cobaltocene (CoCp_2), by slow mixing of solutions, generates two species: [TDNQ][CoCp*_2] and [TDNQ] _3[CoCp_2]_2, respectively. The [TDNQ][CoCp*_2] is soluble in a wide variety of organic solvents, whereas [TDNQ]_3[CoCp_2]_2 is generally insoluble. The radical anion oxidation state, TDNQ~(?-), in [TDNQ][CoCp*_2] is confirmed by lengthened C-O bond distances in the (solvated) crystal structure, as compared to neutral TDNQ, shifting of the ν(C-O) stretch in the IR absorption spectrum, and the presence of a solution electron paramagnetic resonance (EPR) signal. In the [TDNQ] _3[CoCp_2]_2 species, copacking of single-molecule radical anions, TDNQ~(?-), and bimolecular radical anion units, (TDNQ)_2~(?-), with cobaltocenium cations is observed. The magnetic measurements highlight the presence of dominating antiferromagnetic interactions between TDNQ?- and (TDNQ)_2~(?-) spins in this cobaltocene salt.

机译：给出了醌[1,2,5]噻二唑自由基阴离子的第一晶体结构。通过缓慢混合溶液，用外层电子转移剂，十甲基钴茂（CoCp * _2）和钴茂（CoCp_2）还原石脑油[2,3-c] [1,2,5]噻二唑-4,9-二酮（TDNQ）分别产生两种：[TDNQ] [CoCp * _2]和[TDNQ] _3 [CoCp_2] _2。 [TDNQ] [CoCp * _2]可溶于多种有机溶剂，而[TDNQ] _3 [CoCp_2] _2通常不溶。 [TDNQ] [CoCp * _2]中的自由基阴离子氧化态TDNQ〜（α-）通过（溶剂化）晶体结构中与中性TDNQ相比延长的（溶剂化）晶体结构中的CO键距离来确定，ν（CO）的移动在红外吸收光谱中伸展，并存在溶液电子顺磁共振（EPR）信号。在[TDNQ] _3 [CoCp_2] _2物种中，观察到单分子自由基阴离子TDNQ _（？-）和双分子自由基阴离子单元（TDNQ）_2〜（？-）与钴to阳离子共填充。磁性测量结果表明该钴茂盐中TDNQβ-和（TDNQ）_2〜（β-）自旋之间存在着主要的反铁磁相互作用。

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《Crystal growth & design》 |2011年第6期|共8页
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Morgan I.S.; Jennings M.; Vindigni A.; Clérac R.; Preuss K.E.;
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1. [TDNQ][CoCp*_2] and [TDNQ]_3[CoCp _2]_2; Radical anions of a 1,2,5-thiadiazolo-naphthoquinone [J] . Morgan I.S., Jennings M., Vindigni A., Crystal growth & design . 2011,第6期

机译：[TDNQ] [CoCp * _2]和[TDNQ] _3 [CoCp _2] _2; 1,2,5-噻二唑并萘醌的自由基阴离子
2. Hydrolysis product of the [Na(15-crown-5)] salt of the [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl radical anion [J] . Lork E, Mews R, Zibarev AV Mendeleev Communications . 2009,第3期

机译：[1,2,5]噻二唑[3,4-c] [1,2,5]噻二唑烷基自由基阴离子的[Na（15-crown-5）]盐的水解产物
3. Diamagnetic pi-dimers of the [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl radical anion in the crystalline state: Preparation and X-ray crystal structure of a [(Me2N)(2)CC(NMe2)(2)](2+)[(C2N4S2)(2)](2-) salt [J] . Gritsan NP, Lonchakov AV, Lork E, European journal of inorganic chemistry . 2008,第12期

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4. Bis(1,2,5-thiadiazolo)-p-quinobis(1,3-dithiole) (BTQBT) Templating Effect on Structure and Performance of Organic Solar Cells [C] . Yasuhiro Iwasawa, Yukio Furukawa Padjadjaran International Physics Symposium . 2014

机译：BIS（1,2,5-噻唑罗）-p-喹诺比斯（1,3-二孔）（BTQBT）模板对有机太阳能电池结构和性能的影响
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[TDNQ][CoCp*_2] and [TDNQ]_3[CoCp _2]_2; Radical anions of a 1,2,5-thiadiazolo-naphthoquinone

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