Highly planar cross-conjugated alternating polymers with multiple conformational locks: synthesis, characterization and their field-effect properties

Abstract

Two highly planar cross-conjugated polymers with multiple conformational locks were designed and synthesized, and their charge transport properties were investigated.

Topological Transformation of π‐Conjugated Molecules Reduces Resistance to Crystallization

“…[1] Rigid and planar shapes have ag reater tendency to form crystalline domains. [2] Within this context, several strategies have been elaborated, such as fused ladder-type polymer backbones, [3] and intramolecular hydrogen-bonding, [4] to favor planarity along the p-conjugated backbone.C onversely,a wkward structures-in which conjugated substructures are prevented, or restricted, from achiev-ing ac oplanar conformation-constitute ag eneral strategy for achieving soft glassy semiconductors. [5] Ty pical frameworks to elaborate such materials include biphenyl, [6] triphenylamine, [7] and spirobifluorene.…”

Synthesis and Performance of (E)-3-Phenyl-2-(thiophen-2-yl)acrylonitrile-Based Small-Molecule Semiconductors

“…19 The intermediate compound 3 was prepared by using lithium diisopropylamide (LDA) and pinacol borate according to the literature. [12][13][14][15][16][17][18] Finally, the key intermediates 2a-2c were respectively coupled with compound 3 using the Suzuki coupling method with the catalyst Pd(PPh 3 ) 4 to prepare the three target conjugated compounds DPP-BVCNT, DPP-2FBVCNT, and DPP-3FBVCNT. The synthetic routes of the target conjugated compounds and intermediates are shown in Scheme 1.…”

“…Intermediate compounds 2a-2c and 3 were prepared according to the reported methods. [12][13][14][15][16][17][18][19] General Preparation Method of the Key BVCNT-Based Intermediates (2a-2c)…”

Dithienylmethanone‐Based Cross‐Conjugated Polymer Semiconductors: Synthesis, Characterization, and Application in Field‐Effect Transistors

“…The kind of conjugated type is considered to be in favor of forming long effective conjugated length, which induces improved intramolecular and intermolecular interactions, highly ordered molecular packing and close π − π stacking, thus enhanced charge transport characteristics often exhibit in polymer‐based semiconducting layers. Nevertheless, the exploration of cross‐conjugated polymers for PFETs is seldom up to date except several literatures . It is worthwhile to note that the single bonds in cross‐conjugated systems are still part of a conjugated path, meaning that intrachain transport might be partially hampered in cross‐conjugated systems .…”

“…Nowadays, there are successful approaches adopted in developing high‐performance linear conjugated polymer for PFETs such as designing planar building blocks including electron‐donating and electron‐withdrawing building blocks, tuning polymeric conjugated backbone conformation through incorporating intramolecular interactions (conformational locks), increasing the order of molecular aggregation and solution‐processability by introducing functional side chains, and optimizing the frontier orbital energy levels by loading suitable heteroatom‐substituted groups on polymeric conjugated backbones . Depended on these approaches, we had developed two dione‐bridged cross‐conjugated alternating polymers, in which the dione‐bridging moiety is firstly adopted as π ‐extended building block in constructing organic semiconductors for PFETs . The presence of noncovalent S···O and C − H···O interactions endow both polymers with planar conjugated backbone and highly ordered lamellar molecular packing in solid state.…”