Dual-radical-based molecular anisotropy and synergy effect of semi-conductivity and valence tautomerization in a photoswitchable coordination polymer.
Dual-radical-based molecular anisotropy and synergy effect of semi-conductivity and valence tautomerization in a photoswitchable coordination polymer.
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DOI：
10.1093/nsr/nwad047
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发表时间：
2023-06
影响因子：
20.6
通讯作者：
中科院分区：
文献类型：
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有机自由基作为连接基或配体被广泛用于合成分子磁性材料。然而，关于自由基磁性材料的分子各向异性及其多功能性的研究却很少。本文中，可光异构化的二芳基乙烯配体用于形成{[CoIII（3，5-DTSQ·-）（3，5-DTCat 2-）]2（6 F-DAE-py 2）}·3CH 3CN·H2O（o-1·3CH 3CN·H2O，6 F-DAE-py 2 = 1，2-双（2-甲基-5-（4-吡啶基）-3-噻吩基）全氟环戊烯），一种价互变异构（VT）配位聚合物。我们直接观察到双自由基的单晶使用高场/频率（13.3 T和1360 GHz）电子顺磁共振（EPR）谱沿着c轴，这是进一步证实了角度依赖的Q带EPR谱。此外，只有当探针连接在单晶的ab平面时，才观察到接近VT转变温度的导电异常，这表明价态互变异构和导电性之间的协同作用。结构各向异性研究和密度泛函理论（DFT）计算表明，这种协同作用是由于电子转移与价态互变异构。本研究提出了第一个基于双自由基的分子各向异性和电荷转移诱导的导电各向异性的光开关配位聚合物的例子。合成了一种具有光开关和价态互变异构的配位聚合物，并显示出明显的分子各向异性，有助于直接观察双有机自由基。实现了磁双稳态与电导率的协同效应。
Organic radicals are widely used as linkers or ligands to synthesize molecular magnetic materials. However, studies regarding the molecular anisotropies of radical-based magnetic materials and their multifunctionalities are rare. Herein, a photoisomerizable diarylethene ligand was used to form {[CoIII(3,5-DTSQ·–)(3,5-DTCat2–)]2(6F-DAE-py2)}·3CH3CN·H2O (o-1·3CH3CN·H2O, 6F-DAE-py2 = 1,2-bis(2-methyl-5-(4-pyridyl)-3-thienyl)perfluorocyclopentene), a valence-tautomeric (VT) coordination polymer. We directly observed dual radicals for a single crystal using high-field/-frequency (∼13.3 T and ∼360 GHz) electron paramagnetic resonance (EPR) spectroscopy along the c-axis, which was further confirmed by angle-dependent Q-band EPR spectroscopy. Moreover, a conductive anomaly close to the VT transition temperature was observed only when probes were attached at the ab plane of the single crystal, indicative of synergy between valence tautomerism and conductivity. Structural anisotropy studies and density functional theory (DFT) calculations revealed that this synergy is due to electron transfer associated with valence tautomerism. This study presents the first example of dual-radical-based molecular anisotropy and charge-transfer-induced conductive anisotropy in a photoswitchable coordination polymer. A photoswitchable and valence tautomeric coordination polymer was synthesized and displayed significant molecular anisotropy that helped directly observing dual organic radicals. Synergy effect between magnetic bistability and conductivity was realized.
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影响因子：
15
作者：
Hojorat, Maher;Al Sabea, Hassan;Rigaut, Stephane
通讯作者：
Rigaut, Stephane
影响因子：
15
作者：
Demir, Selvan;Zadrozny, Joseph M.;Long, Jeffrey R.
通讯作者：
Long, Jeffrey R.
影响因子：
15
作者：
BUCHANAN, RM;PIERPONT, CG
通讯作者：
PIERPONT, CG
影响因子：
15
作者：
Lannes, Anthony;Suffren, Yan;Luneau, Dominique
通讯作者：
Luneau, Dominique
DOI：
10.1039/c39930001439
发表时间：
1993-09-21
影响因子：
--
作者：
GILAT, SL;KAWAI, SH;LEHN, JM
通讯作者：
LEHN, JM