title: The role of ion pairs in the second-order NLO response of 4-X-1-methylpiridinium salts.
abstract: A series of 4-X-1-methylpyridinium cationic nonlinear optical (NLO) chromophores (X = (E)-CH=CHC(6)H(5); (E)-CH=CHC(6)H(4)-4'-C(CH(3))(3); (E)-CH=CHC(6)H(4)-4'-N(CH(3))(2); (E)-CH=CHC(6)H(4)-4'-N(C(4)H(9))(2); (E,E)-(CH=CH)(2)C(6)H(4)-4'-N(CH(3))(2)) with various organic (CF(3)SO(3)(-), p-CH(3)C(6)H(4)SO(3)(-)), inorganic (I(-), ClO(4)(-), SCN(-), [Hg(2)I(6)](2-)) and organometallic (cis-[Ir(CO)(2)I(2)](-)) counter anions are studied with the aim of investigating the role of ion pairing and of ionic dissociation or aggregation of ion pairs in controlling their second-order NLO response in anhydrous chloroform solution. The combined use of electronic absorption spectra, conductimetric measurements and pulsed field gradient spin echo (PGSE) NMR experiments show that the second-order NLO response, investigated by the electric-field-induced second harmonic generation (EFISH) technique, of the salts of the cationic NLO chromophores strongly depends upon the nature of the counter anion and concentration. The ion pairs are the major species at concentration around 10(-3) M, and their dipole moments were determined. Generally, below 5x10(-4) M, ion pairs start to dissociate into ions with parallel increase of the second-order NLO response, due to the increased concentration of purely cationic NLO chromophores with improved NLO response. At concentration higher than 10(-3) M, some multipolar aggregates, probably of H type, are formed, with parallel slight decrease of the second-order NLO response. Ion pairing is dependent upon the nature of the counter anion and on the electronic structure of the cationic NLO chromophore. It is very strong for the thiocyanate anion in particular and, albeit to a lesser extent, for the sulfonated anions. The latter show increased tendency to self-aggregate.
authors.affiliation: Dipartimento di Chimica Inorganica, Metallorganica e Analitica Lamberto Malatesta dell'Università degli Studi di Milano and Unità di Ricerca di Milano dell'INSTM, Via G. Venezian, 21-20133 Milano, Italy. francesca.tessore@unimi.it
authors.forename: Francesca
authors.initials: F
authors.lastname: Tessore
authors.forename: Elena
authors.initials: E
authors.lastname: Cariati
authors.forename: Franco
authors.initials: F
authors.lastname: Cariati
authors.forename: Dominique
authors.initials: D
authors.lastname: Roberto
authors.forename: Renato
authors.initials: R
authors.lastname: Ugo
authors.forename: Patrizia
authors.initials: P
authors.lastname: Mussini
authors.forename: Cristiano
authors.initials: C
authors.lastname: Zuccaccia
authors.forename: Alceo
authors.initials: A
authors.lastname: Macchioni