Markovnikov or anti-Markovnikov selective thiol-ene click (TEC) reactions and the synthesis of β-hydroxysulfides via aerial dioxygen activation are prevalent C-S bond forming reactions of styrenes and thiophenols. Herein, by choosing appropriate environments using solvents with additives or neat conditions, any one of these three reactions was achieved exclusively in excellent yields.
Herein we demonstrate that an anti-Markovnikov selective thiol-yne-click (TYC) reaction could be achieved between phenyl acetylenes and thiophenols by exploiting a newly identified SÀ H···π non-covalent interaction without using any catalysts, additives and solvents. Natural bond orbital (NBO) analyses also supported that SÀ H···π and cooperative π-π stacking interactions helped to promote this regioselective reaction. The hydrothiolated products were isolated in near quantitative yields. Also, the concept of selfsorting was demonstrated when styrene, phenyl acetylene and thiophenols were reacted in one pot. Owing to the stronger SÀ H···π preference of ethynyl � H over the vinyl = H hydrogen bond, selectively, TYC product formation was found to be dominating over the thiol-ene-click (TEC) product.
Applications of organic
cocrystal systems to obtain semiconductor
materials with low band gap, balanced electron and hole carrier mobility,
low cost, solution processability, air stability, and easy preparative
route have been widely sought after in recent years. Herein, we describe
two organic donor–acceptor cocrystals (T2TC1)·toluene and T1P1TC2 comprising pyrene (P), triphenylene
(T) as the π-donors, and tetracyanoquinodimethane
(TCNQ) (TC) as the π-acceptor exhibiting significant
ambipolar semiconductor nature with charge carrier mobility values
in the range 0.01–0.03 cm2 V–1 s–1. Both the cocrystals possess mixed D–A
stack comprising triphenylene and TCNQ molecules, whereas the other
triphenylene or pyrene molecule is inserted between adjacent mixed
DA stacks. The cocrystals are characterized with appropriate band
gap (1.5–2.5 eV) and lower lying lowest unoccupied molecular
orbital level (−4.1 to −4.3 eV) for ambipolar charge
transport, low preparation cost, solution processability which make
them ideal organic semiconductor materials for practical application.
Theoretical studies show that high ambipolar semiconductor nature
is a result of synergism between two principal charge carrier transfer
pathways in cocrystal system viz. superexchange and direct paths owing
to the unique supramolecular features of cocrystals (T2TC1)·toluene and T1P1TC2.
Charge transfer cocrystals of 2,7-di-tert-butylpyrene donor and tetracyanoquinodimethane, tetracyanobenzene and 1,3-dinitrobenzene acceptor exhibited switchable semi-conductivity.
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