Recent Advances in Design and Synthesis of Diselenafulvenes, Tetraselenafulvalenes, and Their Tellurium Analogs and Application for Materials Sciences

Abstract

The first organic metals were obtained based on tetrathiafulvalene. The most significant advance in the field of organic metals was the discovery of superconductivity. The first organic superconductors were obtained based on tetramethyltetraselenafulvalene. These facts demonstrate great importance of tetraselenafulvalenes and their precursors, diselenafulvenes, for materials sciences. Derivatives of 1,4-diselenafulvene and 1,4,5,8-tetraselenafulvalene are useful building blocks for organic synthesis and donor units for the preparation of charge-transfer complexes and radical ion salts, the construction of organic metals, superconductors, organic Dirac materials, semiconductors, ferromagnets, and other conductive materials. This review covers the literature on the design, synthesis, and application of 1,4,5,8-tetraselenafulvalenes and 1,4-diselenafulvenes and their tellurium analogs over the past 15–20 years. These two classes of compounds are interconnected, since the main part of methods for the synthesis of tetraselenafulvalenes is based on the diselenafulvene derivatives as starting compounds. Special attention is paid to the development of novel efficient synthetic approaches to these classes of compounds. Conducting properties and distinguishing features of materials based on tetraselenafulvalenes and their tellurium analogs as well as examples of materials with high conductivity are discussed.

New charge-transfer complexes of 1,2,5-chalcogenadiazoles with tetrathiafulvalenes

“…To this end, a priori quantum chemical modeling is the most important technique. A particular attention can be paid to heavier chalcogen-associated dispersion interactions 111,112 as the driving force, and to Se and Te congeners of TTFs 113 and 1,2,5-selena/telluradiazoles as D and A structural blocks.…”

Supramolecular architectures featuring Se⋯N secondary-bonding interactions in crystals of selenium-rich molecules: a comparison with their congeners

“…There is clearly on-going interest in material applications for the heavier chalcogens, e.g. as synthetic precursors for nanoparticle generation, 172 magnetic 173 and conductive materials, 174,175 in the biosynthesis of small molecules 176 and in the medicinal chemistry/biological context. 177 The aforementioned applications are complemented by the exciting recent report of the experimental imaging of the anisotropic distribution of electron density for a σ-hole for halogen atoms.…”

Polyunsaturated sulfur/selenium-containing products based on regio- and stereoselective nucleophilic addition and substitution reactions of 1,2-bis[(Z)-2-(vinylsulfanyl)ethenyl] diselane

“…A series of selenium-containing molecules have special magnetic, conductive, and optical properties and found a large number of technological applications as conductors, semiconductors, magnets, and NLO materials. 3,4,47–49 The best known of these are derivatives based on 1,4-diselenafulvene and 1,4,5,8-tetraselenafulvalene, which are currently widely used for the synthesis of various materials with conductivity. 49…”

“…3,4,47–49 The best known of these are derivatives based on 1,4-diselenafulvene and 1,4,5,8-tetraselenafulvalene, which are currently widely used for the synthesis of various materials with conductivity. 49…”

“…43,44 A series of selenium-containing molecules have special magnetic, conductive, and optical properties and found a large number of technological applications as conductors, semiconductors, magnets, and NLO materials. 3,4,[47][48][49] The best known of these are derivatives based on 1,4-diselenafulvene and 1,4,5,8-tetraselenafulvalene, which are currently widely used for the synthesis of various materials with conductivity. 49 Bis(ethylenedithio)diselenadithiafulvalene is a unique object for obtaining conducting material and the Dirac electron systems (DES) at atmospheric pressure and studies of their electrical, magnetic, and optical properties.…”