Electron Transfer and Unusual Chemical Transformations of F4‐TCNQ in a Reaction with Mn‐Phthalocyanine

Abstract

The interaction of manganese phthalocyanine with F4-TCNQ is accompanied by the transformation of the acceptor molecule into a new organic ligand, the 4-(dicyanomethanido)tetra-fluorobenzoate dianion, resulting in the formation of a unique Mn III charge-transfer complex, in which two Mn phthalocyanine moieties are bridged by the dianion, with parallel arrangement of all aromatic fragments and an interplanar distance of 3.30 Å. The formation of the complex takes place in a 2:1 ratio, with the two electrons transferring from two donor molecules to an acceptor molecule. Magnetic measurements [a] A. E. ported so far; however, several complexes with structurally similar metal-porphyrin derivatives are known. They involve charge-transfer complexes with π-stacking interactions between the donor and acceptor molecules [12] and those with metal-N≡C coordination bonds between metal-porphyrins and TCNQ derivatives. [13] Similar results should possibly be expected for metal-phthalocyanine complexes.Our attempts to grow mixed single crystals of MnPc and F4-TCNQ from solution resulted in a quite unexpected reaction between the components and a new type of complex. Herewith, we report these new complexes, their structure, and their electrochemical and magnetic properties. Results and Discussion SynthesisThe main problem of growing CT multicomponent single crystals from solution is the poor solubility of phthalocyanines. [14] We chose N-methyl-2-pyrrolidone (NMP) and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidin-7-one (DMPU) as solvents suitable for both the donor and acceptor components.The first step to grow bicomponent crystals was naturally performed in the moisture-free conditions that are most consistent with those used for the preparation of thin films. [10] However, no single crystals suitable for single-crystal X-ray diffraction study could be grown from dry solvents. Instead, the crystallization appeared to be possible by slow diffusion of water into the reaction mixtures. The reaction products obtained in the two solvents NMP and DMPU are quite different.The crystallization from NMP produces two types of crystals, 1 and 2. Their structure was studied by single-crystal X-ray diffraction. The results appear to be quite unexpected (Scheme 1).Both compounds contain the Mn III Pc framework, as well as the aromatic 4-(dicyanomethanido)tetrafluorobenzoate dianion, obviously being transformed from pristine F4-TCNQ. The first compound (1) has a salt-like structure, composed of Mn III Pc, coordinated by the 4-(dicyanomethanido)tetrafluorobenzoate dianion, and the cation of Mn III Pc, coordinated by two water molecules.Scheme 1. Interaction of MnPc with F4-TCNQ in NMP.

Multi-charge transfer from photodoped ITO nanocrystals

“…The formation of F4TCNQ dianion is observed in several polymer-dopant systems. [41][42][43] Recently, doping of bithiophenethienothiophene-based copolymers with F4TCNQ showed an almost complete double ionization of dopant molecules providing a ionization efficiency of 200% which also resulted in an enhancement of charge carrier transport. 41, 44 To the best of our knowledge double reduction of F4TCNQ has never been reported neither for inorganic-dopant systems nor for photodoped MO NCs-dopant mixtures.…”

Ferrocene-Containing Sterically Hindered Phosphonium Salts

“…Di( tert -butyl)ferrocenylphosphine has been prepared by the most common way, namely by lithiation of ferrocene with tert -butyllithium and subsequent reaction with di( tert -butyl)chlorophosphine 1 [ 23 ]. The starting di( tert -butyl)chlorophosphine has been obtained by the procedure described in [ 24 ], i.e., by the reaction of an excess of tert -butylmagnesium chloride with phosphorus trichloride with following separation of the product mixture by distillation under reduced pressure ( Scheme 1 ).…”

“…Design of CPE requires using chemically inert compounds with high viscosity and ionic conductivity. Such electrodes can significantly increase the selectivity and sensitivity of voltammetric methods [ 18 , 19 , 20 ] and at the same time help to obtain important information about energy data [ 21 , 22 , 23 ].…”

Tuning the visible colour of octahedral manganese(iii) phthalocyanines via axial ligand exchange

“…There are only a few structurally characterized [PcM(H 2 O) 2 ]-containing systems, most of which are PcMn charge transfer species, or PcMg and PcDy. 13,[34][35][36] Scheme 2 Synthesis of selected 6-coordinate [PcMnL 2 ] + species and their subsequent reactions with water.…”