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Coexistence of Metal Phthalocyanine and Fullerene C60 Anions in Mixed {cryptand[2.2.2](Na+)}x(MPc)–x‐1·(C60) – Salts (M = CoI, VIVO, x = 2 and 1.5)
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-01-09 , DOI: 10.1002/ejic.201901229 Dmitri V. Konarev 1 , Mikhail G. Andronov 1, 2 , Alexey V. Kuzmin 3 , Salavat S. Khasanov 3 , Rimma N. Lyubovskaya 1
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-01-09 , DOI: 10.1002/ejic.201901229 Dmitri V. Konarev 1 , Mikhail G. Andronov 1, 2 , Alexey V. Kuzmin 3 , Salavat S. Khasanov 3 , Rimma N. Lyubovskaya 1
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Salts containing metal phthalocyanine and fullerene anions: {cryptand[2.2.2](Na+)}1.5{CoI(Pc2–)}–0.5(C60·–)·2C6H4Cl2 (1) and {cryptand[2.2.2](Na+)}2{VIVO(Pc·3–)}–(C60–)·C6H4Cl2 (2) were obtained. The {CoI(Pc2–)}–anions are formed by metal centered reduction whereas the Pc2– macrocycles are reduced at the formation of {VIVO(Pc·3–)}–. Fullerenes form zigzag chains in 1 in which they are positionally disordered showing different degree of dimerization [loose packed or π‐stacked pairs from the monomers and singly bonded (C60–)2 dimers]. Singly bonded (C60–)2 dimers in 2 also coexist with pairs of π‐stacked C60·–monomers. The (MPc)– anions are isolated in the salts alternating with the {cryptand(Na+)} cations. Magnetic measurements by EPR technique show the presence of spins in 1 both on C60·–(S = 1/2) and the CoI atoms having S = 1 spin state. These spins are weakly antiferromagnetically coupled in the fullerene chains (Θ = –6 K) but show nearly paramagnetic behaviour for isolated {CoI(Pc2–)}– anions. Both S = 1/2 spins in 2 are mainly localized on VIV and delocalized over Pc·3– since only about 10 % of C60·– from total amount of fullerene is preserved. Spins in 2 show only weak antiferromagnetic coupling with Θ = –2 K within one {VIVO(Pc·3–)}– unit.
中文翻译：
在混合的{cryptand [2.2.2]（Na +）} x（MPc）–x-1·（C60）–盐中，金属酞菁和富勒烯C60阴离子共存（M = CoI，VIVO，x = 2和1.5）
含有金属酞菁和富勒烯阴离子的盐：{cryptand [2.2.2]（Na +）} 1.5 {Co I（Pc 2–）} – 0.5（C 60 · –）· 2C 6 H 4 Cl 2（1）和{获得了cryptand [2.2.2]（Na +）} 2 {V IV O（Pc · 3–）} –（C 60 –）· C 6 H 4 Cl 2（2）。{CoI（Pc 2–）} –阴离子通过金属中心还原而形成，而Pc 2–大环在{V IV O（Pc · 3–）} –形成时被还原。富勒烯在1中形成之字形链，它们在位置上无序，显示出不同的二聚度（来自单体的松散堆积或π堆积对，单键结合（C 60 –）2个二聚体）。单键键合（C 60 - ）2个二聚体2还与对π堆叠的C共存60 · -的单体。（MPc）–分离出与{cryptand（Na +）}阳离子交替存在的盐中的阴离子。磁测量通过EPR技术显示出自旋的存在1都基于C 60 · - （小号= 1/2）和联合我具有原子小号= 1自旋态。这些自旋在富勒烯链中弱反铁磁耦合（Θ= –6 K），但对于孤立的{Co I（Pc 2–）} –阴离子显示几乎顺磁行为。两个小号= 1/2自旋2主要位于开V IV和离域在PC · 3-因为仅保留了富勒烯总量中C 60 · –的大约10％。自旋2仅显示在一个{V IV O（Pc · 3–）} –单位内，Θ= –2 K的弱反铁磁耦合。
更新日期：2020-01-09
中文翻译：
在混合的{cryptand [2.2.2]（Na +）} x（MPc）–x-1·（C60）–盐中，金属酞菁和富勒烯C60阴离子共存（M = CoI，VIVO，x = 2和1.5）
含有金属酞菁和富勒烯阴离子的盐：{cryptand [2.2.2]（Na +）} 1.5 {Co I（Pc 2–）} – 0.5（C 60 · –）· 2C 6 H 4 Cl 2（1）和{获得了cryptand [2.2.2]（Na +）} 2 {V IV O（Pc · 3–）} –（C 60 –）· C 6 H 4 Cl 2（2）。{CoI（Pc 2–）} –阴离子通过金属中心还原而形成，而Pc 2–大环在{V IV O（Pc · 3–）} –形成时被还原。富勒烯在1中形成之字形链，它们在位置上无序，显示出不同的二聚度（来自单体的松散堆积或π堆积对，单键结合（C 60 –）2个二聚体）。单键键合（C 60 - ）2个二聚体2还与对π堆叠的C共存60 · -的单体。（MPc）–分离出与{cryptand（Na +）}阳离子交替存在的盐中的阴离子。磁测量通过EPR技术显示出自旋的存在1都基于C 60 · - （小号= 1/2）和联合我具有原子小号= 1自旋态。这些自旋在富勒烯链中弱反铁磁耦合（Θ= –6 K），但对于孤立的{Co I（Pc 2–）} –阴离子显示几乎顺磁行为。两个小号= 1/2自旋2主要位于开V IV和离域在PC · 3-因为仅保留了富勒烯总量中C 60 · –的大约10％。自旋2仅显示在一个{V IV O（Pc · 3–）} –单位内，Θ= –2 K的弱反铁磁耦合。
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