Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, 142432, Russia.
Institute of Solid State Physics RAS, Chernogolovka, Moscow region, 142432, Russia.
Chem Asian J. 2018 Jun 18;13(12):1552-1560. doi: 10.1002/asia.201701754. Epub 2018 May 17.
In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu N ) [M O(Pc )] (M=Ti, V) and (Bu MeP ) [M O(Pc )] (M=Ti, V) with [M O(Pc )] dianions were synthesized and characterized. Reduction of M O(Pc ) carried out with an excess of sodium fluorenone ketyl in the presence of Bu N or Bu MeP is exclusive to the phthalocyanine centers, forming Pc species. During reduction, the metal +4 charge did not change, implying that Pc is an non-innocent ligand. The Pc negative charge increase caused the C-N(pyr) bonds to elongate and the C-N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn-Teller effects are significant in the [eg(π*)] dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q-bands were observed in the UV/Vis/NIR when M O(Pc ) was reduced to [M O(Pc )] and [M O(Pc )] . From magnetic measurements, [Ti O(Pc )] was found to be diamagnetic and (Bu N ) [V O(Pc )] and (Bu MeP ) [V O(Pc )] were found to have magnetic moments of 1.72-1.78 μ corresponding to an S=1/2 spin state owing to V electron spin. As a result, two latter salts show EPR signals with V hyperfine coupling.
在这项研究中，合成并表征了钛酰和钒酰酞菁（Pc）盐（Bu N ）[M O(Pc )]（M=Ti、V）和（Bu MeP ）[M O(Pc )]（M=Ti、V），其中[M O(Pc )]为二阴离子。在 Bu N 或 Bu MeP 的存在下，用过量的氟蒽酮钠自由基还原 M O(Pc )，仅在酞菁中心进行，形成 Pc 物种。在还原过程中，金属+4 电荷没有变化，这意味着 Pc 是一个非惰性配体。Pc 负电荷的增加导致 C-N(pyr)键伸长，C-N(imine)键交替，从而增加 Pc 的变形。Jahn-Teller 效应在[eg(π*)]二阴离子基态中非常显著，并且可以进一步扭曲 Pc 大环。当 M O(Pc )还原为[M O(Pc )]和[M O(Pc )]时，在 UV/Vis/NIR 中观察到 Soret 和 Q 带的蓝移。从磁性测量结果可知，[Ti O(Pc )]为抗磁性，（Bu N ）[V O(Pc )]和（Bu MeP ）[V O(Pc )]的磁矩分别为 1.72-1.78 μ，对应于 V 电子自旋的 S=1/2 自旋态。因此，后两种盐表现出 EPR 信号，其中 V 超精细耦合。
