Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M<sup>II</sup><sub>3</sub>O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet?Quartet Transitions in the Dianions
Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M<sup>II</sup><sub>3</sub>O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet?Quartet Transitions in the Dianions
复制标题
具有同三核 M<sup>II</sup><sub>3</sub>O 簇（M = Ni 和 Cu）的三硫十二氮杂六菲林配合物的双阴离子态：晶体结构、金属或大环中心还原和双峰？四重态跃迁
DOI：
10.1021/acs.inorgchem.1c01132
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发表时间：
2021
影响因子：
4.6
通讯作者：
Kitagawa Hiro
中科院分区：
文献类型：
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作者：
Nazarov Dmitry I.;Islyaikin Mikhail K.;Ivanov Evgenii N.;Koifman Oskar I.;Batov Mikhail S.;Zorina Leokadiya V.;Khasanov Salavat S.;Shestakov Alexander F.;Yudanova Evgeniya I.;Zhabanov Yuriy A.;Vyalkin Dmitriy A.;Otsuka Akihiro;Yamochi Hideki;Kitagawa Hiro
合成了三硫代十氮杂六氢叶酸(HHP)的金属配合物，它们在π扩展的三阴离子(HHP-)大环中含有MII3O簇合物。对NiII3O(HHP)和CuII3O(HHP)的磁性研究揭示了抗磁和EPR沉默的三阴离子(Hhp3-)大循环以及抗磁NiII3(O2-)或顺磁CuII3(O2-)四元反应。MII3O(HHP)的正电荷由一个醋酸盐阴离子{MII3O(HHP)}+(CH3CO2-)补偿。{MII3O(HHP)}+的三电子还原反应生成{Cryptand(Cs+)}2{NiII2NiIO(Hhp5-)}2-·2C7H8(1)和{Cryptand(Cs+)}2{CuII3O(HHP·6-)}2-·C7H8(2)结晶盐。1的磁性揭示了HHP5-的形成和镍(II)还原成顺磁性Ni离子(S=1/2)，并伴随着{NiII2NiIO(HHP5-)}2-阴离子的形成。结果表明，在20-220K范围内，1的磁矩为1.68μBin，并观察到NiI的宽的电子顺磁共振信号。Hhp5-大环单重态基态，但在220K以上磁矩的大小增加归因于Hhp5-中三重态激发态的布居。{NiII2NiIO(Hhp5-)}2-阴离子从二重态激发态转变为四重态激发态，能隙为1420±50K。Salt1在1000-2200 nm处表现出异常强的低能近红外吸收。在In_2中，高度还原的HHP·6-自由基六阴离子(S=1/2)与CuII3(O2-)团簇(S=1/2)共存于{CuII3(HHP·6-)}2-阴离子中。双阴离子具有三重基态，两个自旋之间有反铁磁交换，j=−6.4 cm-1。HHP在两种盐中的还原平衡了初始交替的C-N键，支持了HHP大循环电子离域的增加。
Metal complexes of trithiadodecaazahexaphyrin (Hhp) that contain MII3O clusters inside a π-extended trianionic (Hhp3–) macrocycle have been prepared. Studies of the magnetic properties of NiII3O(Hhp) and CuII3O(Hhp) reveal a diamagnetic and EPR-silent trianionic (Hhp3–) macrocycle and diamagnetic NiII3(O2–) or paramagnetic CuII3(O2–) tetracations. The positive charge of MII3O(Hhp) is compensated by one acetate anion {MII3O(Hhp)}+(CH3CO2–). The three-electron reduction of {MII3O(Hhp)}+yields {cryptand(Cs+)}2{NiII2NiIO(Hhp5–)}2–·2C7H8(1) and {cryptand(Cs+)}2{CuII3O(Hhp•6–)}2–·C7H8(2) crystalline salts. The magnetic properties of1reveal the formation of Hhp5–and the reduction of nickel(II) to the paramagnetic NiIion (S= 1/2), which is accompanied by the formation of the {NiII2NiIO(Hhp5–)}2–dianion. As a result, the magnetic moment of1is 1.68 μBin the 20–220 K range, and a broad EPR signal of NiIwas observed. The Hhp5–macrocycle has a singlet ground state, but the increase in the magnitude of the magnetic moment of1above 220 K is attributed to the population of the triplet excited state in Hhp5–. The {NiII2NiIO(Hhp5–)}2–dianion is transferred from the doublet excited state to the quartet excited state with an energy gap of 1420 ± 50 K. Salt1also shows an unusually strong low-energy NIR absorption, which was observed at 1000–2200 nm. In2, a highly reduced Hhp•6–radical hexaanion (S= 1/2) coexists with a CuII3(O2–) cluster (S= 1/2) in the {CuII3O(Hhp•6–)}2–dianions. The dianions have a triplet ground state with antiferromagnetic exchange between twoS= 1/2 spins withJ= −6.4 cm–1. The reduction of Hhp in both salts equalizes the initially alternated C–N bonds, supporting the increase in the Hhp macrocycle electron delocalization.