Synthesis and Properties Study of Novel Unsymmetrical Pyrrolo‐annulated Benzo‐diselenadithiafulvalene

Abstract

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, ...

Design, synthesis and photophysical properties of novel star-shaped truxene-based heterocycles utilizing ring-closing metathesis, Clauson–Kaas, Van Leusen and Ullmann-type reactions as key tools

“…Inspired from the available potential applications, and also bearing in mind the applicability of truxene-based materials from future perspective in addition to as a part of our major program on the synthesis of PAHs in general and functionalized truxenes in particular, our voyage for the synthesis of truxene-based heterocyclic systems commence with the construction of tripyrrolotruxene derivative 6 (Scheme 2). Basically, our interest to generate pyrrole-based C 3 -symmetric truxene derivatives was because of a range of applications of the pyrrole moiety in diverse fields, for instance, a wide variety of medicinally active as well as smart functional materials possessing the pyrrole as a fundamental subunit [28][29][30]. Additionally, 3,4disubstituted pyrrole derivatives are versatile building blocks for the production of diverse bioactive molecules like co-enzyme, alkaloids, porphyrins and other related macrocycles [31,32].…”

Applications of Oxone® in Organic Synthesis: An Emerging Green Reagent of Modern Era

“…The organochalcogens exhibits a wide range of pharmacological activities such as antidepressant, antiviral,anticholinesterasic, antifungal, anxiolytic, anti‐inflammatory, and antioxidant in addition to their importance in toxicologymaterials science, electrochemistry, bio‐chemistry and chiral catalysis. On the other hand, naphthalene and its derivatives are well‐known for their innumerable biological properties like anticancer, antifungal, and antiviral activities besides a wide spectrum of potential applications in materials and polymer chemistry [316–323] . Therefore, keeping in mind the importance of organoselenium compounds, Perin et al .…”

“…On the other hand, naphthalene and its derivatives are well-known for their innumerable biological properties like anticancer, antifungal, and antiviral activities besides a wide spectrum of potential applications in materials and polymer chemistry. [316][317][318][319][320][321][322][323] Therefore, keeping in mind the importance of organoselenium compounds, Perin et al reported a green procedure for the synthesis of 2-organoselanyl-naphthalenes 410 a-e from alkynols 409& diaryl diselenides 408 using an aqueous solution of oxone under ultrasonic irradiation (Scheme 131). [324] By employing this methodology, the authors have assembled a variety of 2-organoselanyl-naphthalenes in decent yields and the proposed mechanistic pathway for this reaction is described in the Scheme 132.…”

Recent developments in calix[4]pyrrole (C4P)-based supramolecular functional systems

“…Considering the involvement of numerous natural receptors in regulating the intricate phenomena in nature through noncovalent interactions, the science of supramolecular chemistry took birth, imitating the basic design and functions of natural receptors for the construction of artificial functional receptors realizing particular goals. [1][2][3][4][5][6][7][8] Among the numerous supramolecular receptors, 9,10 the non-aromatic tetrapyrrolic synthetic macrocyclic receptor (C4P) has emerged as significant receptor and ligand for diverse purposes owing to its structural variety, easy one-pot synthesis, and recognition ability towards anions, ion-pairs, neutral molecules, and metal ions of fundamental importance. [11][12][13][14][15][16][17][18][19][20][21][22][23] Adolf von Baeyer (1835-1917, a German Chemist, Noble Prize in Chemistry, 1905) is credited for the discovery of the parent C4P in 1886 through the acid-mediated condensation of pyrrole with acetone in a single step (Fig.…”