Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, 142432, Russia.
Dalton Trans. 2012 Aug 14;41(30):9170-5. doi: 10.1039/c2dt30701d. Epub 2012 May 31.
Ionic complexes containing μ(2)-hydroxo-bonded (MgPc)(2)OH(-) phthalocyanine assemblies and C(60)(-) anions: {(MgPc)(2)OH(-)}(2)·(C(60)(-))(2)·(PMDAE(+))(4)·(C(6)H(5)CN)(4) (1); {(MgPc)(2)OH(-)}(2)·(C(60)(-))(2)·(TMP(+))(4)·(C(6)H(5)CN)(3)·(C(6)H(4)Cl(2))(2.5) (2) (where PMDAE(+) is the cation of N,N,N',N',N'-pentamethyldiaminoethane and TMP(+) is the N,N'N'-trimethylpiperazinium cation) have been obtained as single crystals. The ionic ground state of the complexes is justified by the EPR spectra and the spectra in the IR and NIR ranges. The C(60)˙(-) radical anions are dimerized both in 1 and 2 in the 240-220 K range. Dimerization is accompanied by the reversible transition of the complexes from paramagnetic to diamagnetic state. MgPc forms unusual (MgPc)(2)OH(-) assemblies, in which the hydroxo-anion coordinates to two MgPc molecules by a μ(2)-fashion. The length of the Mg-O bonds is 1.936-1.955(2) Å, the Mg-O-Mg angle is 133.37-135.27(4)° and the displacement of the Mg atoms out of the mean 24-atom phthalocyanine plane is 0.77-0.86 Å. The packing of spherical fullerene and planar phthalocyanine molecules is attained in a crystal by the insertion of fullerenes between phenylene groups of phthalocyanines. It has been shown that metal phthalocyanines in ionic complexes with C(60) form M(II)Pc·(L(-)) assemblies, whereas metalloporphyrins form M(II)porphyrin·(C(+)) assemblies.
含有 μ(2)-羟桥联（MgPc）（2）OH(-) 酞菁组装体和 C(60)(-) 阴离子的离子配合物：{(MgPc)(2)OH(-)}(2)·(C(60)(-))(2)·(PMDAE(+))(4)·(C(6H(5)CN)(4) (1); {(MgPc)(2)OH(-)}(2)·(C(60)(-))(2)·(TMP(+))(4)·(C(6H(5)CN)(3)·(C(6H(4)Cl(2))(2.5) (2)（其中 PMDAE(+) 是 N,N,N',N',N'- 五甲基二乙胺阳离子，TMP(+) 是 N,N'N'- 三甲基哌嗪阳离子）已被获得为单晶。配合物的离子基态由 EPR 光谱和 IR 和 NIR 范围内的光谱证明。在 240-220 K 范围内，C(60)˙(-) 自由基阴离子在 1 和 2 中都发生二聚化。二聚化伴随着配合物从顺磁态到抗磁态的可逆转变。MgPc 形成不寻常的（MgPc）（2）OH(-) 组装体，其中羟阴离子通过 μ(2)-方式与两个 MgPc 分子配位。Mg-O 键的长度为 1.936-1.955(2) Å，Mg-O-Mg 角为 133.37-135.27(4)°，并且 Mg 原子偏离平均 24 原子酞菁平面的位移为 0.77-0.86 Å。通过将富勒烯插入酞菁的亚苯基基团之间，在晶体中实现了球形富勒烯和平面酞菁分子的堆积。已经表明，与 C(60) 形成离子配合物的金属酞菁形成 M(II)Pc·(L(-)) 组装体，而金属卟啉形成 M(II)卟啉·(C(+)) 组装体。
