Electrical conductivity in complexes of ‘crowned’-phthalocyanines with metal salts

Sielcken, O. E.; Schram, Jonas; Nolte, Roeland J. M.; Schoonman, J.; Drenth, W.

doi:10.1039/c39880000108

Cited by 26 publications

(13 citation statements)

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“…The electrical properties of 2, its K , Rb and Cs picrate complexes and those of the polysiloxane derivatives have also been studied in the solid state by AC impedance spectroscopy [17,18,20]. Seebeck measurements showed that the uncomplexed CuPcs are p-type electronic conductors, whereas the metal picrate complexes of 2 exhibit ntype electronic conductivity.…”

Section: Electronic Conductivitymentioning

confidence: 99%

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Molecular materials based on crown ether functionalized phthalocyanines

Engelkamp

Nolte

2000

J. Porphyrins Phthalocyanines

205

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This micro-review presents an overview of molecular materials derived from phthalocyanines which are substituted with crown ether rings. These flat disk-like molecules can self-assemble into ordered, well-defined structures with or without the aid of alkali metal ions. Highly ordered assemblies of crown ether phthalocyanines are capable of transporting electrons and ions, which is of interest for sensor applications.

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Section: Electronic Conductivitymentioning

confidence: 99%

“…1). The complexes of 2 with K , Rb and Cs picrates were isolated and characterized [17,18], and in all cases the complexes were stacked in columns, with the cations located in (K ) or between (Rb and Cs ) the crown ether moieties.…”

Section: Introductionmentioning

confidence: 99%

Molecular materials based on crown ether functionalized phthalocyanines

Engelkamp

Nolte

2000

J. Porphyrins Phthalocyanines

205

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“…1 [4], which are of particular interest in photoelectronic device development [9,10], 2) effective complexation to Li cations [11,12] and 3) significantly lowered isotropization temperature with respect to reference compounds with linear alkoxy chains [4]. Analogously, Pcʼs substituted with crown ethers have been studied extensively [13], specifically with regard to their complexation behavior and applicability for electronic and ionic conduction [14][15][16][17]. Each of these systems is particularly apt for the solubilization of inorganic salts, due to the complexation of cations by the ether moieties.…”

Section: Introductionmentioning

confidence: 99%

Phthalocyanines with eight oligo(ethylene oxide) alkoxy units: thermotropic phase behavior, aggregate formation and ion complexation with redox-active ions

Piet

Verheij

Zuilhof

2003

J. Porphyrins Phthalocyanines

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The thermotropic phase behavior of phthalocyanines (Pcʼs) with eight oligo(ethylene oxide) alkoxy side chains has been investigated. An increase in the number of ethylene oxide units results in a decrease in the solid-to-mesophase and isotropization temperatures. The investigated compounds display a discotic hexagonally ordered (D ho ) mesophase. The solubilization of LiI/I 2 into the polar side chains of the Pcʼs has been studied both in solution and in spin-coated films, and the effect on the aggregate formation is discussed. At higher temperatures, the Pc -LiI/I 2 complex is not stable and small crystallites are formed. The dark direct current conductivity of these films is reported as a function of LiI/I 2 concentration in the polar side groups of the Pcʼs. The observed decrease in conductivity with increasing salt concentration is related to the morphology of the material.

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“…The crown-ether-fused phthalocyanine (Pc) molecules have also been reported as a supramolecular ion ± electron cooperative system. [15] The electrical conductivity of the Pc system was tuned through the cation-binding in the crown ether moieties. However, the electronic systems of these TCNQ and Pc compounds are essentially semiconducting or insulating.…”

Section: Introductionmentioning

confidence: 99%

Ionic Channel Structures in [(M+)x([18]crown-6)][Ni(dmit)2]2 Molecular Conductors

et al. 2001

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The [(M+)x[18]crown-6)] supramolecular cations (SC+), in which M+ and [18]crown-6 are alkali metal ions (M+ = Li+, Na+, and Cs+) and 1,4,7,10,13,16-hexaoxacyclooctadecane, respectively, form ionic channel structures through the regular stacks of [18]crown-6 in [Ni(dmit)2]-based molecular conductors (dmit2+ = 2-thioxo-1,3-dithiole-4,5-dithiolate). In addition to the [Ni(dmit)2] salts that have the ionic channel structures (these salts are abbreviated as type I salts), Li+ and Na+ form dimerized [(M+)2([18]crown-6)2] units in the crystals (type II salts). The K+ and Rb+ are coordinated tightly into the [18]crown-6 cavity to form typical disk-shape SC+ units in the corresponding [Ni(dmit)2] salts (type III salts). The type I, II, and III salts have typical stoichiometries of [(M+)x([18]crown-6)][Ni(dmit)2]2, [(M+)([18]crown-6)(H2O)x(CH3CN)(1.5 - x)][Ni(dmit)2]3 (x = 1 for Li+ or 0.5 for Na+), and [M+([18]crown-6)][Ni(dmit)2]3, respectively: the salts of the same type are isostructural. In agreement with the trimer structures of [Ni(dmit)2] in the type II and III salts, they exhibit semiconducting behavior with electrical conductivities at 300 K (sigma(300 K)) of 0.01-0.1 S cm(-1). Type I salts contain a regular stack of partially oxidized [Ni(dmit)2] units, which form a quasi one-dimensional metallic band within the tight-binding approximation regime. The electrical conductivities at 300 K are 10-30 S cm(-1), and an almost temperature-independent conductivity was observed at higher temperatures. However, the one-dimensional electronic structures in these salts are strongly influenced by the static and dynamic structures of the coexisting ionic channel. The Na+ salt is a semiconductor, whose magnetic behavior is described by the disordered one-dimensional antiferromagnetic chain. On the other hand, the Cs+ salt is a exhibits metallic properties with 2 kF instability at room temperature. The Li+ salt shows a gradual transition from the high-temperature metallic phase to the low-temperature one-dimensional antiferromagnetic semiconductor phase, which was associated with the freezing of Li+ motion at lower temperatures. The preferential crystallization of type I salts was possible by controlling the equilibrium constant (Kc) of the complex formation between M+ ions and the [18]crown-6 molecule. The ionic channel structures were obtained when the KC was low in the electrocrystallization solution, while type II or III salts were formed in the high Kc region.

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Electrical conductivity in complexes of ‘crowned’-phthalocyanines with metal salts

Cited by 26 publications

References 1 publication

Molecular materials based on crown ether functionalized phthalocyanines

Molecular materials based on crown ether functionalized phthalocyanines

Phthalocyanines with eight oligo(ethylene oxide) alkoxy units: thermotropic phase behavior, aggregate formation and ion complexation with redox-active ions

Ionic Channel Structures in [(M+)x([18]crown-6)][Ni(dmit)2]2 Molecular Conductors

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