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DOE OSTI · 3016013

Helical Complex Ladder Polymer with Amplification of Asymmetry

Wang, Yuzhe [Cornell Univ., Ithaca, NY (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)] (ORCID:0009000481866435)·Xie, Yuchen [Cornell Univ., Ithaca, NY (United States)]·Chen, Yifu [Cornell Univ., Ithaca, NY (United States)]·Oh, Changhwan [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)] (ORCID:0000000321206676)·Fang, Qiyi [Cornell Univ., Ithaca, NY (United States)]·Chivukula, Kaushik [Cornell Univ., Ithaca, NY (United States)]·Zhang, Honghu [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)] (ORCID:0000000317847825)·Zhao, Cheng [Cornell Univ., Ithaca, NY (United States)] (ORCID:0009000028746638)·Zhang, Sarah [Cornell Univ., Ithaca, NY (United States)]·Ananth, Nandini [Cornell Univ., Ithaca, NY (United States)] (ORCID:0000000158451961)·Kulik, Heather J. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)] (ORCID:0000000193420191)·Zhong, Yu [Cornell Univ., Ithaca, NY (United States)] (ORCID:0000000186312213)
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Abstract

Here, we report a Cu–salen helical complex ladder polymer (HLP-Cu) built from covalently fused Cu(Salen) units. Point chirality from enantiopure diamines directs the formation of a rigid, π-conjugated helix. Compared with a planar analogue (LLP-Cu) and the Cu(Salen) monomer, HLP-Cu exhibits up to 5-fold stronger circular dichroism and a maximum dissymmetry factor of 7.4 × 10 –3 . Titration experiments suggest a cooperative amplification of asymmetry arising from extended conjugation and helical geometry during helix formation. Time-dependent density functional theory calculations are employed to support this hypothesis, showing that increasing conjugation length and helical order enhance the rotational strength of contributing excited states via elevated magnetic transition moments and improved alignment of electric and magnetic transition moments. Our findings provide a new polymer platform for designing functional chiral materials with tunable chiroptical and spin-dependent properties.

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36 MATERIALS SCIENCEchiroptical propertieshelical ladder polymermetal–salen complex

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Wang, Yuzhe [Cornell Univ., Ithaca, NY (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)] (ORCID:0009000481866435), Xie, Yuchen [Cornell Univ., Ithaca, NY (United States)], Chen, Yifu [Cornell Univ., Ithaca, NY (United States)], Oh, Changhwan [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)] (ORCID:0000000321206676), Fang, Qiyi [Cornell Univ., Ithaca, NY (United States)], Chivukula, Kaushik [Cornell Univ., Ithaca, NY (United States)], Zhang, Honghu [Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)] (ORCID:0000000317847825), Zhao, Cheng [Cornell Univ., Ithaca, NY (United States)] (ORCID:0009000028746638), Zhang, Sarah [Cornell Univ., Ithaca, NY (United States)], Ananth, Nandini [Cornell Univ., Ithaca, NY (United States)] (ORCID:0000000158451961), Kulik, Heather J. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)] (ORCID:0000000193420191), Zhong, Yu [Cornell Univ., Ithaca, NY (United States)] (ORCID:0000000186312213). 2026-01-13. Helical Complex Ladder Polymer with Amplification of Asymmetry. https://doi.org/10.1021/jacs.5c17973

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