Incorporating an Alternating Donor–Acceptor Structure into a Ladder Polymer Backbone

Abstract

Incorporation of the donor-acceptor structure of an alternating conjugated copolymer into a rigid ladder polymer backbone is reported. The resulting ladder polymers show optical features typical of rigid ladder polymers, but present an increased Stokes shift if compared to their non-polar counterparts. This behavior reflects the occurrence of charge transfer processes during excitation and leads to a positive solvatochromism.

Synthesis of Ladder Polymers: Developments, Challenges, and Opportunities

“…[45] Nearly quantitative ladder-formation can be achieved by carefully designing relativelyb ulky substituents of the benzyl alcohol (or ether)t hat lacks a-H to eliminate intermolecularc rosslinkinga nd b-elimination. [46] This chemistry has been widely used to produce ladderp olymers containing fluorene units, whicha re particularly attractive light-emitting materials. [46,47] Swagera nd co-workersd esigned poly(o,o-diethynyl-p-phenylene), the acetylenic functionalities of which undergo annulation with neighboring backbone phenylg roups under strongly acidic conditions to form angular poly(acene) (Scheme 5a).…”

“…[46] This chemistry has been widely used to produce ladderp olymers containing fluorene units, whicha re particularly attractive light-emitting materials. [46,47] Swagera nd co-workersd esigned poly(o,o-diethynyl-p-phenylene), the acetylenic functionalities of which undergo annulation with neighboring backbone phenylg roups under strongly acidic conditions to form angular poly(acene) (Scheme 5a). [48] Chalifoux and co-workersr e-cently extended this approach to synthesize ladder-type poly-(rylene).…”

Organometallic‐Mediated Alternating Radical Copolymerization of tert‐Butyl‐2‐Trifluoromethacrylate with Vinyl Acetate and Synthesis of Block Copolymers Thereof

“…For other monomer pairs, highly ordered monomer sequence control is still challenging . Regarding fluorinated polymers, recently, Studer and coworkers and the Scherf's team attempted the synthesis of predominantly alternating copolymers composed of hexafluoroisopropyl acrylate with 7‐octenyl vinyl ether and N ‐dialkylated benzothiadiazolodithienopyrrole with a dibrominated terephthalophenone derivative, respectively. Recently, Jordan's group reported (phosphinoarenesulfonate)Pd fluoride complex catalyst reactivation following β‐F elimination in ethylene/vinyl fluoride copolymerization …”

Ladder‐type Heteroarenes: Up to 15 Rings with Five Imide Groups

“…In addition, intermolecular packing and film morphology on larger scale also play critical roles . Ladder‐type molecules with highly planar backbones and well‐delocalized π‐conjugation have attracted intensive attention as small‐molecule semiconductors and building blocks for polymers, molecular wires, and ladder polymers . Among them, pentacenes show substantial hole mobility, and benzothienobenzothiophene and dinaphthothienothiophene exhibit remarkable mobility with excellent OTFT stability .…”