Electronic conduction and polarization in polyphthalocyanines

Abstract

The polymeric hydrogen form of phthalocyanine is found to be more conductive than the metallic derivatives, in contrast to the behavior of the monomers. In addition, the polymers were found to be much more conductive than the corresponding monomers with the resistivity of the polymers ranging from 7 ohm‐cm to about 3 × 106 ohm‐cm. The polymers were found to have moderately high dielectric constants ranging from 16 to 1300 at room temperature, depending upon the applied pressure. Based on the dependences of the conductivity and permittivity upon the electric field strength, the average molecular length of the conductive paths within the polymer molecule has been estimated to be 100–1000 Å. In view of these estimated lengths, together with the exponential dependence of the permittivity and conductivity upon the pressure and temperature, the dispersion of the dielectric constants in the range of 10–100 KHz, and the chemical architecture of these ribbonlike polymers, the electronic behavior of these polymers is concluded to be consonant with the model of essentially one‐dimensional conduction within and along the chains by freed charges. Much as in a number of previously studied highly conjugated polymers, the present polyphthalocyanines are semiconducting and exhibit nomadic polarization, with dielectric constants ranging from 70 to 1300.

Phthalocyanines in Macromolecular Phases - Methods of Synthesis and Properties of the Materials

“…We studied in detail the photoelectrochemical reduction of oxygen to water. [156 -158, 180] This reduction consists of two-step two-electron or one-step four-electron transfer, as shown in Equation (19) and (20). [181] On the other hand, phthalocyanines with electron-withdrawing substituents, such as octacyano derivative 9 are characterized as n-type materials.…”

Novel Network Polymeric Phthalocyanines: Synthesis and Characterization

“…[3] Compared to low molecular weight phthalocyanines, relatively few reports describe the synthesis and properties of polymeric phthalocyanines. For the polycyclotetramerization, bifunctional monomers based on tetracarbonitriles for polymers, [4][5][6][7][8][9] various oxy-, arylenedioxy-and alkylenedioxy-bridged diphthalonitriles for polymers [10][11][12][13][14] and other nitriles [15][16][17] or tetracarboxylic acid derivates [18][19][20][21] have been employed, mainly in the presence of metal salts or metals. The polymers exhibit not only very large and accessible surface areas [22] but also good thermal stabilities under inert gas up to $500 8C and under oxidative conditions up to $350 8C.…”

“…The intensity ratio of l ¼ 236-298 nm and l max (706-883 nm) of the Q-bands in the polymeric phthalocyanines (3)(4)(5)(6)(7)(8)(9) can be seen in Table 2. In all cases, the intensities in the UV (soret band transition) and Vis (Q-band transition) were I UV /I Vis 1.…”

Tetrathia Macrocycle-bridged Dimeric with Hexakis (alkylthio) Substituents and Network Polymer Phthalocyanines

“…catalytic, electrocatalytic, electrochemical and photochemical activities [1][2][3]. Synthesis and structure of the polymer were studied in detail for the reaction of 1,2,4,5-benzenetetracarbonitrile with various metal salts or metals [4][5][6][7][8][9].…”