Nucleobase-Functionalized 1,6-Dithiapyrene-Type Electron-Donors: Supramolecular Assemblies by Complementary Hydrogen-Bonds and π‑Stacks

Synthesis, crystal structures and redox properties of 1,6-dithiapyrene (DTPY)-type electron-donors functionalized with nucleobases (uracil, cytosine and adenine) were investigated. The electrochemical measurements showed that the uracil-substituted derivatives were slightly stronger electron-donors than DTPY, and the cytosine- and adenine-substitution caused a slight weakening of the electron-donating ability. In the crystal structures, DTPY-nucleobases constructed multidimensional assemblies by complementary hydrogen-bonds on the nucleobase moieties and π-stacks and S···S interactions on the DTPY skeleton. The uracil derivative formed two kinds of hydrogen-bonded pairs with different H-bonding modes (Watson–Crick and reverse Watson–Crick types), both of which were further linked through π-stacks on the DTPY skeleton to construct one-dimensional alternating columns. In the CH₂Cl₂ solvated crystal, the uracil derivative built up a two-dimensional π-layer by the complementary hydrogen-bonds and π-stacks. In the cytosine derivative, the complementary hydrogen-bonded pair assembled by the π-stacks and S···S interactions of the DTPY skeleton constructed a two-dimensional network. The adenine derivative formed a channel structure by the one-dimensional π-stack of complementary hydrogen-bonded pairs, where crystalline water molecules with a ladder-like hydrogen-bonded chain were included. Charge-transfer complexes of DTPY-nucleobases with tetracyanoquinodimethane possessed a neutral ground state and exhibited semiconductive behaviors with room temperature conductivities of 10^–6 to 10^–7 S cm^–1

Nucleobase-Functionalized 1,6-Dithiapyrene-Type Electron-Donors: Supramolecular Assemblies by Complementary Hydrogen-Bonds and π‑Stacks

Synthesis, crystal structures and redox properties of 1,6-dithiapyrene (DTPY)-type electron-donors functionalized with nucleobases (uracil, cytosine and adenine) were investigated. The electrochemical measurements showed that the uracil-substituted derivatives were slightly stronger electron-donors than DTPY, and the cytosine- and adenine-substitution caused a slight weakening of the electron-donating ability. In the crystal structures, DTPY-nucleobases constructed multidimensional assemblies by complementary hydrogen-bonds on the nucleobase moieties and π-stacks and S···S interactions on the DTPY skeleton. The uracil derivative formed two kinds of hydrogen-bonded pairs with different H-bonding modes (Watson–Crick and reverse Watson–Crick types), both of which were further linked through π-stacks on the DTPY skeleton to construct one-dimensional alternating columns. In the CH₂Cl₂ solvated crystal, the uracil derivative built up a two-dimensional π-layer by the complementary hydrogen-bonds and π-stacks. In the cytosine derivative, the complementary hydrogen-bonded pair assembled by the π-stacks and S···S interactions of the DTPY skeleton constructed a two-dimensional network. The adenine derivative formed a channel structure by the one-dimensional π-stack of complementary hydrogen-bonded pairs, where crystalline water molecules with a ladder-like hydrogen-bonded chain were included. Charge-transfer complexes of DTPY-nucleobases with tetracyanoquinodimethane possessed a neutral ground state and exhibited semiconductive behaviors with room temperature conductivities of 10^–6 to 10^–7 S cm^–1

Nucleobase-Functionalized 1,6-Dithiapyrene-Type Electron-Donors: Supramolecular Assemblies by Complementary Hydrogen-Bonds and π‑Stacks

Synthesis, crystal structures and redox properties of 1,6-dithiapyrene (DTPY)-type electron-donors functionalized with nucleobases (uracil, cytosine and adenine) were investigated. The electrochemical measurements showed that the uracil-substituted derivatives were slightly stronger electron-donors than DTPY, and the cytosine- and adenine-substitution caused a slight weakening of the electron-donating ability. In the crystal structures, DTPY-nucleobases constructed multidimensional assemblies by complementary hydrogen-bonds on the nucleobase moieties and π-stacks and S···S interactions on the DTPY skeleton. The uracil derivative formed two kinds of hydrogen-bonded pairs with different H-bonding modes (Watson–Crick and reverse Watson–Crick types), both of which were further linked through π-stacks on the DTPY skeleton to construct one-dimensional alternating columns. In the CH₂Cl₂ solvated crystal, the uracil derivative built up a two-dimensional π-layer by the complementary hydrogen-bonds and π-stacks. In the cytosine derivative, the complementary hydrogen-bonded pair assembled by the π-stacks and S···S interactions of the DTPY skeleton constructed a two-dimensional network. The adenine derivative formed a channel structure by the one-dimensional π-stack of complementary hydrogen-bonded pairs, where crystalline water molecules with a ladder-like hydrogen-bonded chain were included. Charge-transfer complexes of DTPY-nucleobases with tetracyanoquinodimethane possessed a neutral ground state and exhibited semiconductive behaviors with room temperature conductivities of 10^–6 to 10^–7 S cm^–1

Nucleobase-Functionalized 1,6-Dithiapyrene-Type Electron-Donors: Supramolecular Assemblies by Complementary Hydrogen-Bonds and π‑Stacks

Synthesis, crystal structures and redox properties of 1,6-dithiapyrene (DTPY)-type electron-donors functionalized with nucleobases (uracil, cytosine and adenine) were investigated. The electrochemical measurements showed that the uracil-substituted derivatives were slightly stronger electron-donors than DTPY, and the cytosine- and adenine-substitution caused a slight weakening of the electron-donating ability. In the crystal structures, DTPY-nucleobases constructed multidimensional assemblies by complementary hydrogen-bonds on the nucleobase moieties and π-stacks and S···S interactions on the DTPY skeleton. The uracil derivative formed two kinds of hydrogen-bonded pairs with different H-bonding modes (Watson–Crick and reverse Watson–Crick types), both of which were further linked through π-stacks on the DTPY skeleton to construct one-dimensional alternating columns. In the CH₂Cl₂ solvated crystal, the uracil derivative built up a two-dimensional π-layer by the complementary hydrogen-bonds and π-stacks. In the cytosine derivative, the complementary hydrogen-bonded pair assembled by the π-stacks and S···S interactions of the DTPY skeleton constructed a two-dimensional network. The adenine derivative formed a channel structure by the one-dimensional π-stack of complementary hydrogen-bonded pairs, where crystalline water molecules with a ladder-like hydrogen-bonded chain were included. Charge-transfer complexes of DTPY-nucleobases with tetracyanoquinodimethane possessed a neutral ground state and exhibited semiconductive behaviors with room temperature conductivities of 10^–6 to 10^–7 S cm^–1

Nucleobase-Functionalized 1,6-Dithiapyrene-Type Electron-Donors: Supramolecular Assemblies by Complementary Hydrogen-Bonds and π‑Stacks

Synthesis, crystal structures and redox properties of 1,6-dithiapyrene (DTPY)-type electron-donors functionalized with nucleobases (uracil, cytosine and adenine) were investigated. The electrochemical measurements showed that the uracil-substituted derivatives were slightly stronger electron-donors than DTPY, and the cytosine- and adenine-substitution caused a slight weakening of the electron-donating ability. In the crystal structures, DTPY-nucleobases constructed multidimensional assemblies by complementary hydrogen-bonds on the nucleobase moieties and π-stacks and S···S interactions on the DTPY skeleton. The uracil derivative formed two kinds of hydrogen-bonded pairs with different H-bonding modes (Watson–Crick and reverse Watson–Crick types), both of which were further linked through π-stacks on the DTPY skeleton to construct one-dimensional alternating columns. In the CH₂Cl₂ solvated crystal, the uracil derivative built up a two-dimensional π-layer by the complementary hydrogen-bonds and π-stacks. In the cytosine derivative, the complementary hydrogen-bonded pair assembled by the π-stacks and S···S interactions of the DTPY skeleton constructed a two-dimensional network. The adenine derivative formed a channel structure by the one-dimensional π-stack of complementary hydrogen-bonded pairs, where crystalline water molecules with a ladder-like hydrogen-bonded chain were included. Charge-transfer complexes of DTPY-nucleobases with tetracyanoquinodimethane possessed a neutral ground state and exhibited semiconductive behaviors with room temperature conductivities of 10^–6 to 10^–7 S cm^–1

Intermolecular Hydrogen-Bond Networks and Physical Properties of BF₄^– and TCNQ^{<b>•</b>–} Salts of Three-Fold Symmetric Tris(alkylamino)phenalenyliums

Synthesis, redox properties, and crystal structures of tris­(alkylamino)­phenalenyliums (TAP) having alkyl groups (<i>n</i>-Pr, <i>i</i>-Pr, <i>t</i>-Bu) and their charge-transfer salts with tetracyanoquinodimethane radical anion (TCNQ^{<b>•</b>–}) were investigated. The electrochemical measurements revealed that TAP exhibits two irreversible reduction processes to neutral radical and anion species. The introduction of an alkylamino group caused a large negative shift of the first reduction potential and a significant decrease of the on-site Coulomb repulsion because of the electron-donating nature of amino groups and the extension of the π-electronic system. In the crystal structures of the BF₄^– salts, the TAP skeleton possesses a nearly 3-fold symmetric molecular plane indicating the delocalization of positive charge. The face-to-face stack of TAP formed π-dimer or columnar structures, which were connected through intermolecular N–H···F hydrogen bonds with BF₄^– to construct multidimensional network structures. The TCNQ^{<b>•</b>–} salts prepared by the metathesis method were characterized as fully ionic salts with a 1:1 component ratio. In the crystal structures, both TAP and TCNQ^{<b>•</b>–} molecules formed π-dimers, and the intermolecular hydrogen bonds between TAP and TCNQ^{<b>•</b>–} constructed a two-dimensional sheet

Intermolecular Hydrogen-Bond Networks and Physical Properties of BF₄^– and TCNQ^{<b>•</b>–} Salts of Three-Fold Symmetric Tris(alkylamino)phenalenyliums

Synthesis, redox properties, and crystal structures of tris­(alkylamino)­phenalenyliums (TAP) having alkyl groups (<i>n</i>-Pr, <i>i</i>-Pr, <i>t</i>-Bu) and their charge-transfer salts with tetracyanoquinodimethane radical anion (TCNQ^{<b>•</b>–}) were investigated. The electrochemical measurements revealed that TAP exhibits two irreversible reduction processes to neutral radical and anion species. The introduction of an alkylamino group caused a large negative shift of the first reduction potential and a significant decrease of the on-site Coulomb repulsion because of the electron-donating nature of amino groups and the extension of the π-electronic system. In the crystal structures of the BF₄^– salts, the TAP skeleton possesses a nearly 3-fold symmetric molecular plane indicating the delocalization of positive charge. The face-to-face stack of TAP formed π-dimer or columnar structures, which were connected through intermolecular N–H···F hydrogen bonds with BF₄^– to construct multidimensional network structures. The TCNQ^{<b>•</b>–} salts prepared by the metathesis method were characterized as fully ionic salts with a 1:1 component ratio. In the crystal structures, both TAP and TCNQ^{<b>•</b>–} molecules formed π-dimers, and the intermolecular hydrogen bonds between TAP and TCNQ^{<b>•</b>–} constructed a two-dimensional sheet

Isomerically Pure Anthra[2,3‑<i>b</i>:6,7‑<i>b</i>′]-difuran (<i>anti</i>-ADF), -dithiophene (<i>anti</i>-ADT), and -diselenophene (<i>anti</i>-ADS): Selective Synthesis, Electronic Structures, and Application to Organic Field-Effect Transistors

A new straightforward synthesis of isomerically pure anthra­[2,3-<i>b</i>:6,7-<i>b</i>′] -difuran (<i>anti</i>-ADF), -dithiophene (<i>anti</i>-ADT), and -diselenophene (<i>anti</i>-ADS) from readily available 2,6-dimethoxyanthracene is described. The present successful synthesis makes it possible to overview the linear-shaped <i>anti</i>-acenedichalcogenophene compounds, that is, benzo­[1,2-<i>b</i>:4,5-<i>b</i>′]-, naphtho­[2,3-<i>b</i>:6,7-<i>b</i>′]-, and anthra­[2,3-<i>b</i>:6,7-<i>b</i>′]- difuran, -dithiophene, and -diselenophene. By comparing their electrochemical and photochemical properties, the electronic structures of acenedichalcogenophenes can be expressed as the outcome of balance between the central acene core and the outermost chalcogenophene rings. Among isomerically pure parent <i>anti</i>-anthradichalcogenophenes, <i>anti</i>-ADT and <i>anti</i>-ADS can afford crystalline thin films by vapor deposition, which acted as active layer in organic field-effect transistors with mobility as high as 0.3 cm² V^–1 s^–1 for ADT and 0.7 cm² V^–1 s^–1 for ADS. The mobility of isomerically pure <i>anti</i>-ADT is higher by several times than those reported for isomercally mixed ADT, implying that the isomeric purity could be beneficial for realizing the better FET mobility. We also tested the diphenyl derivatives of <i>anti</i>-ADF, -ADT, and -ADS as the active material for OFET devices, which showed high mobility of up to 1.3 cm² V^–1 s^–1

Isomerically Pure Anthra[2,3‑<i>b</i>:6,7‑<i>b</i>′]-difuran (<i>anti</i>-ADF), -dithiophene (<i>anti</i>-ADT), and -diselenophene (<i>anti</i>-ADS): Selective Synthesis, Electronic Structures, and Application to Organic Field-Effect Transistors

A new straightforward synthesis of isomerically pure anthra­[2,3-<i>b</i>:6,7-<i>b</i>′] -difuran (<i>anti</i>-ADF), -dithiophene (<i>anti</i>-ADT), and -diselenophene (<i>anti</i>-ADS) from readily available 2,6-dimethoxyanthracene is described. The present successful synthesis makes it possible to overview the linear-shaped <i>anti</i>-acenedichalcogenophene compounds, that is, benzo­[1,2-<i>b</i>:4,5-<i>b</i>′]-, naphtho­[2,3-<i>b</i>:6,7-<i>b</i>′]-, and anthra­[2,3-<i>b</i>:6,7-<i>b</i>′]- difuran, -dithiophene, and -diselenophene. By comparing their electrochemical and photochemical properties, the electronic structures of acenedichalcogenophenes can be expressed as the outcome of balance between the central acene core and the outermost chalcogenophene rings. Among isomerically pure parent <i>anti</i>-anthradichalcogenophenes, <i>anti</i>-ADT and <i>anti</i>-ADS can afford crystalline thin films by vapor deposition, which acted as active layer in organic field-effect transistors with mobility as high as 0.3 cm² V^–1 s^–1 for ADT and 0.7 cm² V^–1 s^–1 for ADS. The mobility of isomerically pure <i>anti</i>-ADT is higher by several times than those reported for isomercally mixed ADT, implying that the isomeric purity could be beneficial for realizing the better FET mobility. We also tested the diphenyl derivatives of <i>anti</i>-ADF, -ADT, and -ADS as the active material for OFET devices, which showed high mobility of up to 1.3 cm² V^–1 s^–1

Borylation on Benzo[1,2‑<i>b</i>:4,5‑<i>b</i>′]- and Naphtho[1,2‑<i>b</i>:5,6‑<i>b</i>′]dichalcogenophenes: Different Chalcogene Atom Effects on Borylation Reaction Depending on Fused Ring Structure

The direct borylation reactions of two types of α-silyl-protected acenedichalcogenophenes, i.e., benzo[1,2-<i>b</i>:4,5-<i>b</i>′]- and naphtho[1,2-<i>b</i>:5,6-<i>b</i>′]dichalcogenophenes, were examined, and it was observed that the reaction efficiency largely depends on the fused ring structure and chalcogenophene ring