Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region 142432, Russia.
Inorg Chem. 2010 Apr 19;49(8):3881-7. doi: 10.1021/ic100061e.
Ionic complexes containing C(60)(-) radical anions and metalloporphyrins coordinatively bound to N,N',N'-trimethylpiperazinium cations {(TMP(+))(2).M(II)TPP}.(C(60)(-))(2).(C(6)H(4)Cl(2))(2).(C(6)H(5)CN)(2) [M = Zn (1) and Mn (2)] have been obtained. The crystal structures of 1 and 2 solved at 250 and 270 K, respectively, show layered packing in which fullerene layers alternate with the (TMP(+))(2).M(II)TPP ones. Fullerenes form pairs in the layer with short center-to-center distances of 10.044 and 10.077 A, respectively. The structures of 1 and 2 solved at 100 K indicate the formation of singly bonded (C(60)(-))(2) dimers. That results in the transition of 1 from the paramagnetic to diamagnetic state accompanied by the disappearance of the electron paramagnetic resonance (EPR) signal of C(60)(-) at 220-150 K. Dimerization in 2 results in a decrease in the magnetic moment from 6.36 to 6.00 mu(B) at 200-150 K and a change in the shape of EPR signal. The room-temperature EPR signal shows a major broad component at g = 2.0678 (DeltaH = 111.6 mT) attributed to both paramagnetic C(60)(*-) and high-spin (TMP(+))(2).Mn(II)TPP species having strong exchange interaction. After dimerization, the signal is characteristic of isolated high-spin Mn(II)TPP (g( perpendicular) = 6 with |A| = 7.3 mT and g(||) approximately 2). Two TMP(+) cations can coordinate to M(II) in (TMP(+))(2).M(II)TPP. However, a weak coordination bond is formed only with one cation with the M(II)...N(TMP(+)) distances of 2.489(2)-2.688(3) A. As a result, metal atoms displace by +/-0.232(3) A (1, 250 K), +/-0.231(1) A (1, 100 K) and +/-0.4684(7) A (2, 270 K) out of the porphyrin plane to be located above and below the porphyrin plane with equal occupancies for both positions. The symmetry of the crystal structure of 2 decreases from monoclinic to triclinic under cooling. That results in unequal 0.85/0.15 occupation of the Mn(II) positions at 100 K with displacement of the metal by 0.391(2) and 0.554(4) A, respectively.
含有 C(60)(-)自由基阴离子和金属卟啉配位结合到 N,N',N'-三甲基哌嗪阳离子{(TMP(+))(2).M(II)TPP}的离子配合物。{(C(60)(-))(2).(C(6)H(4)Cl(2))(2).(C(6)H(5)CN)(2)} [M = Zn (1) 和 Mn (2)] 已被获得。在 250 和 270 K 下分别解决了 1 和 2 的晶体结构，显示出富勒烯层与（TMP(+))(2).M(II)TPP 交替的层状堆积。富勒烯在层中形成对，其中心到中心的距离分别为 10.044 和 10.077 A。在 100 K 下解决的 1 和 2 的结构表明形成了单键合的(C(60)(-))(2)二聚体。这导致 1 从顺磁态向抗磁态转变，伴随着 C(60)(-)的电子顺磁共振（EPR）信号在 220-150 K 之间消失。在 2 中二聚化导致磁矩从 200-150 K 时的 6.36 降至 6.00 mu(B)，并且 EPR 信号的形状发生变化。室温 EPR 信号显示出主要的宽成分，g = 2.0678（DeltaH = 111.6 mT）归因于具有强交换相互作用的顺磁 C(60)(*-)和高自旋（TMP(+))(2).Mn(II)TPP 物质。二聚化后，信号特征为孤立的高自旋 Mn(II)TPP（g(perpendicular) = 6，|A| = 7.3 mT，g(||)约为 2）。两个 TMP(+)阳离子可以配位到（TMP(+))(2).M(II)TPP 中的 M(II)。然而，只有一个阳离子形成弱配位键，其 M(II)...N(TMP(+))距离为 2.489(2)-2.688(3) A。结果，金属原子位移为 +/-0.232(3) A（1，250 K），+/-0.231(1) A（1，100 K）和 +/-0.4684(7) A（2，270 K）超出卟啉平面，位于卟啉平面的上方和下方，两个位置的占有率相等。2 的晶体结构的对称性在冷却过程中从单斜晶系降低到三斜晶系。这导致 100 K 时 Mn(II)位置的 0.85/0.15 不等占有率，金属分别位移 0.391(2)和 0.554(4) A。
