emission maximum is shifted to the red region.12

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Small-molecule cyclotri-or cyclotetraphosphazenes and their linear high polymeric analogues bearing amino, phosphino, or organohalogeno side groups have been quaternized by treatment with methyl iodide or triphenylphosphine. Quaternization occurred at the side-group sites except with the piperidino derivatives, where the reactive sites were the skeletal nitrogen atoms. The quaternized species reacted with lithium 7,7,8,8-tetracyanoquinodimethane (LiTCNQ) to generate TCNQ "simple salts", and these (or their onium precursors) reacted with neutral TCNQ to generate the "complex salts". The electrical conductivities of the cyclic trimeric phosphazene complex salts ( 10-3-10-2 R-I cm-l) were higher than those of their high polymeric counterparts.This work forms part of a general investigation of the way in which different side-group structures affect the chemical and physical properties of ring systems and high polymers based on a phosphazene skeleton.'-3 In earlier studies we have explored the influence of simple alkoxy, aryloxy, or amino side gr0ups,4,~ biologically active side groups, such as steroidal: amino acid ester,' procaine,* or heparin units,9 metalloporphyrin structures,I0 and, most recently, transition-metal organometallic units."J2 In this paper we describe an extension of these general principles to the quaternization of a variety of cyclic and high polymeric phosphazenes and to the use of the resultant onium derivatives for salt formation with 7,7,8,8-tetracyanoquinodimethane (TCNQ).'3-23 NC TCNQTCNQ forms two series of crystal-stacked, salt-like, electroactive complexes. In the first, TCNQ accepts an electron from a metal or organic donor to yield so-called "simple" salts of formula M"+(TCNQ-),.24 The TCNQ radical anions form electrically conducting stacks in the crystal structure. Such simple salts generally have low to intermediate level electrical conductivities (10-'2-104 f2-' cm-I). The second class consists of the so-called "complex" salts formed by the addition of neutral TCNQ to t h e simple-salt structures, t o give species of formula M+"-(TCNQ-),(TCNQ). Many complex salts have high electrical conductivities ( 10-3-102 f2-l c~-I ) . *~ (1) Allcock, H. R. Allcock, H. R.; Fuller, T. J.; Mack, D. P.; Matsumura, K.; Smeltz, K. M. Macromolecules 1977, 10, 824. (8) Allcock, H. R.; Austin, P. E.; Neenan, T. X . Macromolecules 1982, 15, 689. (9) Neenan, T. X.; Allcock, H. R. Biomaterials 1982, 3, 2, 78. (10) Allcock, H. R.; Greigger, P. P.; Gardner, J. E.; Schmutz, J. L. J . Am. Chem. SOC. 1979, 101, 606. (1 1) Allcock, H. R.; Lavin, K. D.; Tollefson, N. M.; Evans, T. L. Organometallics 1983, 2, 267. (12) Allcock, H. R.; Lavin, K. D.; Riding, G. H.; Suszko, P. R.; Whittle, R. R. J . Am. Chem. SOC. 1984, 106, 2337. (13) Goodings, E. P. Chem. SOC. Rev. 1976, 95. (14) Herman, A. M.; Yen, S. P. S.; Rembaum, A.; Landel, R. F. J . Polym. Sci., Polym. Lett. Ed. 1971, 9, 627. Scheme I R I Phorphozono Phosphoron.' I-. I C NQ Phosphazono' TCNQ--Phonphorono'UCNQ); Scheme I1 CF3CH20;p,CI C5~ION;p~NC5HI0 N0 ' N N'...