Since the discovery of the tetrathiafulvalene (TTF)-based organic conductors, composed of TTF and tetracyanoquinodimethane in 1973, 1 investigations on the chemical, physical, and functional properties of the TTFs and its higher chalcogen analogues such as tetraselenafulvalene (TSF) and diselenadithiafulvalene (DSDTF) derivatives, have attracted much interest and been widely studied. 2 These intensified and extensive research efforts on chemistry of TTFs provide an expansion of the research scopes beyond electrically conducting materials to various fields of functional material chemistry, such as nonlinear optics, photovoltaics, molecular electronics, molecular receptors, molecular switches, logic gates, molecular machines, etc. [2][3][4][5][6][7] Among various types of TTFs and its congeners, we are particularly interested in design, synthesis, and property studies of pyrrole-containing systems. This is because these derivatives can be used as versatile building blocks to construct a wide range of functional supramolecular materials. 8 In fact, several pyrrole-annulated TTF derivatives have been synthesized, some of which were successfully applied to construct porphyrins, expand porphyrins, calix[n]pyrroles, and rotaxanes, so on. [8][9][10][11][12][13][14][15][16][17][18][19] In the particular case of TTF-calix[4]pyrrole (TTF-C4P) receptors for the colorimetric detection of nitro-aromatic explosives, it has been demonstrated that their performance such as binding affinities and colorimetric responsiveness can be dramatically enhanced through electronic modulation of the parent TTF-pyrrole building blocks used to construct the C4P frameworks. 18 This improvement was accomplished by benzene-or thiophene-annulation on TTF-pyrrole core. It is thus appreciated that appropriate electronic modulation on the fundamental building blocks is one of the key importances in determining the overall performance of the resulting supramolecular frameworks.Recently, we reported the synthesis of three aromatic heterocycles (furan, pyrazine, and 1,2,5-thiadiazole)-annulated TTF-pyrrole derivatives and systematic comparisons of these materials with three other reported aromatic-annulated ones (pyrrolo-, thiopheno-, and benzo-TTF-pyrroles) in terms of electronic, chemical, and photophysical properties. 20 It shows that degrees of electron-donating ability and magnitude of dipole moments of TTF-pyrrole can be readily tuned in a wide range by the heterocycle-annulation strategy. To the best of our knowledge, to date, there are no reports on pyrrole-containing DSDTF and very few reports are available on TSF derivatives, although the importance of the selenium containing TTF-type electron donors is well recognized in TTF chemistry. As pointed out in the literature, the replacement of sulfur atoms in the TTF core with selenium atoms is an efficient way to increase intermolecular interactions, dimensionality, and polarizability. 2 With this consideration in mind, the first novel unsymmetrical benzene-annulated DSDTF-pyrrole 5 was targeted, ...
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