Tetrathiafulvalene/tetracyanoquinodimethane polymers

Tetracyanoquinodimethane (TCNQ) and many of its derivatives are easily reduced to anions of the type TCNQ-, which form salts with various cations. With many cations, e.g., tetrathiafulvalene cations (TTF+), and N-methyl phenazinium cations (NMP+), the TCNQ- anions form electronically conducting salts (- molecular metals, -> charge-transfer complexes) that can be used as electrodes, especially because of their electrocatalytic properties (- biosensors, -> electrocatalysis, -> molecular metals) [i,ii]. TCNQ undergoes insertion electrochemical reactions (-> insertion electrochemistry) leading to TCNQ salts [iii, iv]. Polymers... 

Polymers from tetracyanotetrathiafulvalen and metal salts exhibit 029 of 10 to 10 ohm cm . Doping with tetracyanoquinodimethane has no influence on a. This is surprising because doping of tetrathiafulvalene leads to the well known metallic conductivity. 

Our approach to reduce the effects of swelling in negative resists was to use a high Tg polymer. Other approaches have been reported (38). Tetrathiafulvalene (TTF) is a strong electron donor and forms its radical cation by forming a complex with an electron acceptor such as tetracyanoquinodimethane and halogen. 

Hertler WR (1976) Charge-transfer polymers containing 7,7,8,8-tetracyanoquinodimethan and tetrathiafulvalene. J Org Chem 41 1412-1416... 

Prior to development of synthetic i-stacked polymers, characteristic features of jc-stacked molecules had been studied for small molecule systems. A representative example is the tetrathiafulvalene (TTF)-tetracyanoquinodimethane (TCNQ) complex in crystal prepared by the Johns Hopkins group [Cowan et al., Journal of the American Chemical Society, vol. 95, p. 948 (1973)]. In the TTC-TCNQ complex, charges generated by the donor-acceptor interaction between TTF and TCNQ are transported/delocalized through independent columns of TTF and TCNQ stacks in crystal, leading to a molecular conductor. In order to find parallels of the TTF-TCNQ crystal, various combinations of donor and acceptor molecules were studied. 

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