Cyclophane-Based π-Stacked Polymers



This chapter focused on the synthesis and fundamental properties of π-stacked polymers, which consist of the stacked π-electron systems created by the [m.n]cyclophane, in particular [2.2]paracyclophane, in the polymer main chain. Our recent works in this field are mainly focused on due to the limited examples, and their characteristic features are summarized. Incorporation of the [2.2]paracyclophane skeleton into a π-conjugated polymer backbone leads to a π-stacked structure. Pseudo-para-, pseudo-ortho-, and pseudo-geminal-disubstituted [2.2]paracyclophanes allow the construction of various π-stacked conformations such as straight, zigzag, and fully stacked structures. Optically active π-stacked polymers comprising the planar chiral pseudo-ortho-disubstituted [2.2]paracyclophanes open a new frontier in chiral polymer chemistry. Common π-conjugated polymers have a set of HOMO (valence band) and LUMO (conduction band) energy bandgaps, whereas in the π-stacked polymers each π-electron system has its own HOMO–LUMO energy bandgap. Various aromatic groups can be incorporated into polymers; therefore, energy and charge transfer through the polymer chain can be controlled by appropriate tuning of the bandgaps and energy levels of the stacked π-electron system. We hope that this new class of π-stacked polymers can make a fundamental contribution to the field of molecular electronics in the form of single molecular wires.


High Occupied Molecular Orbital Lower Unoccupied Molecular Orbital Fluorescence Resonance Energy Transfer Photoluminescence Spectrum Polymer Main Chain 



Our works introduced herein are mainly supported by Grant-in-Aid for Young Scientists (B) (No. 16750096) and Young Scientists (A) (No. 21685012 and No. 24685018) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.


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© Springer 2014

Authors and Affiliations

  1. 1.Department of Polymer Chemistry, Graduate School of EngineeringKyoto UniversityKyotoJapan

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