Synthesis of Conjugated Tetrathiafulvalene (TTF)-π-Acceptor Molecules − Intramolecular Charge Transfer and Nonlinear Optical Properties

Abstract

We have synthesised new conjugated donor-π-acceptor (D-π-A) chromophores 7, 9, and 12−15 in which monosubstituted tetrathiafulvalene (TTF) and trimethyl-TTF units are the donor moieties, connected by ethylenic bridges to electrondeficient benzene derivatives as the acceptor moieties. These compounds display a broad intramolecular charge transfer (ICT) band in their solution UV/Vis spectra at λ max = ca.

Tetrathiafulvalene–Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open‐Shell Characteristics on Linear and Nonlinear Optical Properties

“…Indeed, after the first example reported in 1998 by N. Martín, J. Garín and coworkers, [9] many other TTF-based pushpull derivatives with closed-shell electronic structure exhibiting large NLO responses have been described. [10][11][12][13][14][15][16][17][18] On the other hand, molecular materials with open-shell electronic structures have also aroused the interest of many researchers because of their high potentiality as NLO-phores. [19][20][21][22][23][24] Thus, a few years ago, some of us reported the second-order non-linear optical (SONLO) response of a family of polychlorotriphenylmethyl (PTM) radical derivatives showing large β hyperpolarizability values.…”

“…Regarding the building blocks, the tetrathiafulvalene (TTF) moiety has been widely used as an efficient electron‐donor unit for synthesizing TTF‐π‐A structures with appealing NLO properties. Indeed, after the first example reported in 1998 by N. Martín, J. Garín and co‐workers, many other TTF‐based push–pull derivatives with closed‐shell electronic structures exhibiting large NLO responses have been described . On the other hand, molecular materials with open‐shell electronic structures have also aroused interest because of their high potentiality as NLO‐phores .…”

5-Methyl-4-(5-Bromo-2-hydroxyphenyl)-1,3-Dithiolium Derivatives

“…The discovery of highly conductive organic charge transfer complexes tetrathiafulvalenes derivatives (TTF) with tetracyano-p-quinodimethane [1,2] has prompted interest in the synthesis of new 1,3-dithiolium salts which are well-known precursors of TTFs [3][4][5][6]. Recent reports highlighted the TTFs ability to act as donor groups in intramolecular charge-transfer complexes [7,8]. In this context, a variety of acceptor units have been investigated, nitrogen and sulfur containing cations receiving a great deal of attention [9][10][11][12][13][14][15][16][17][18][19].…”

2-Alkylimino-4-(2-Hydroxyaryl)-1,3-Dithiols Derivatives

“…For these reasons this type of compounds represent an important resource for the material chemistry with deep implications in the daily life and even in the educational process [8,9]. Recent reports highlighted the TTFs ability to act as donor groups in intramolecular chargetransfer complexes [10,11]. Thus, various acceptor units have been investigated, nitrogen and sulfur containing cations receiving a great deal of attention [12][13][14][15][16][17][18][19][20][21][22].…”