Naphthalene Bis(4,8-diamino-1,5-dicarboxyl)amide Building Block for Semiconducting Polymers

Abstract

We report a new naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide (NBA) building block for polymeric semiconductors. Computational modeling suggests that regio-connectivity at the 2,6- or 3,7-NBA positions strongly modulates polymer backbone torsion and, therefore, intramolecular π-conjugation and aggregation. Optical, electrochemical, and X-ray diffraction characterization of 3,7- and 2,6-dithienyl-substituted NBA molecules and corresponding isomeric NBA-bithiophene copolymers P1 and P2, respectively, reveals the key role of regio-connectivity. Charge transport measurements demonstrate that while the twisted 3,7-NDA-based P1 is a poor semiconductor, the planar 2,6-functionalized NBA polymers (P2-P4) exhibit ambipolarity, with μ and μ of up to 0.39 and 0.32 cm/(V·s), respectively.

Processable High Electron Mobility π‐Copolymers via Mesoscale Backbone Conformational Ordering

“…Side chains longer than 2OD are required to effectively solubilize NBA‐TVT copolymers. [ 22 ] Considering extended conjugation of DTBT and DTBTff, long, branched alkyl groups (2DH) were thought necessary to solubilize P2, P3, and P4. Scheme presents the synthetic route used to NBA2DH and the corresponding dibrominated monomer, 2NBA2DH‐Br 2 .…”

“…The naphthalene bis(4,8‐diamino‐1,5‐dicorboxyl)amide (NBA, Figure 1B) building block, pioneered by this Laboratory to address the conformational pitfall of NDI‐arene backbone twisting induced by the imide group steric bulk, is an ideal structural platform for harmonizing both strategies i) and ii) above. [ 22 ] In our initial communication, crystal structures of the isomeric di(thein‐2‐yl) NBA small molecules, 3,7‐NBA‐T 2 and 2,6‐NBA‐T 2 , revealed NBA‐thiophene dihedral angles (θs) of ≈50° versus ≈ 10°, respectively, demonstrating that NBA regioconnectivity can either drive or frustrate backbone planarity. Subsequently, corresponding regioisomeric NBA copolymers with 2,2'‐bithiophene (T2), 3,7‐P(NBA2OD‐T2) and P(NBA2OD‐T2) (Figure 1B), were synthesized, and computational modeling, optical absorption, and X‐ray diffraction indeed reveal that P(NBA2OD‐T2) has significantly greater backbone planarity than 3,7‐P(NBA2OD‐T2) and the NDI‐based P(NDI2OD‐T2).…”

“…A) Selected examples of high‐performance semiconducting co‐polymers based on NDI, BT, DTBT, and DTBTff building blocks; [ 17,19c,21a ] B) Structure of the NBA building block with structures and μ e of the copolymers investigated previously. [ 22 ] C) Structures of the NBA polymers in this study; and structures of 2OD, 2DH, and 2TH sidechains used to solubilize NBA polymers.…”

An A‐D‐A′‐D‐A Conjugated Molecule Entailing Diazapentalene Unit for an n‐Type Organic Semiconductor

“…The past decades have witnessed the significant progresses of organic and polymeric semiconductors. [1][2][3][4][5] Various conjugated frameworks, such as diketopyrrolopyrrole (DPP), [6][7][8][9][10][11][12][13][14][15] naphthodithiophenediimide (NDTI), [16][17][18][19][20][21][22][23] benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV) [24] and isoindigo, [25][26][27][28] have been explored to construct the conjugated molecules and polymers for semiconductors of high charge mobilities. For instance, the electron deficiency,p lanar conjugated structure and easyf unctionalizatione nableD PP as av ersatile building block for organic and polymerics emiconductors.…”

New Aryl‐Substituted 2,2′‐Bithiophenes: Synthesis, Optoelectronic Properties and DFT Studies

“…Oligo‐ and polythiophenes can be synthesized by various transition metal (TM)‐catalyzed cross‐coupling reactions. Using such C−C bond forming reactions, molecular building blocks containing pre‐constructed thiophene units can be readily linked to suitable cross‐coupling partners (e. g. alkenes, alkynes, and arenes), yielding π‐conjugated thiophene oligomers and polymers . Many oligo‐/polythiophenes which have been reported in the literature, are linear polythiophenes with alkyl chains and/or with polar functional groups as substituents .…”