Inorganic Chemistry· 2026Q1
Cinchonidine vs Cinchonine: Stereochemical Control of Architecture and Circularly Polarized Luminescence in Chiral Cu4I4–Cluster-Based Coordination Polymers
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- 2026year
Short summary
Chiral Cu4I4–cluster-based coordination polymers synthesized using epimeric ligands cinchonidine and cinchonine exhibit distinct 1D chain vs. 3D framework architectures and circularly polarized luminescence (CPL) properties, with glum values of +6.1 × 10–3 and –2.4 × 10–3, respectively.
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Key points
- Epimeric ligands cinchonidine and cinchonine directed the synthesis of two distinct chiral Cu4I4–cluster-based coordination polymers: a 1D chain (Cu4I4(L1)) and a 3D framework (Cu4I4(L2)).
- Cu4I4(L1) features interconnected gyroscope-like and cubane-type clusters, while Cu4I4(L2) contains only cubane-type clusters.
- Cu4I4(L1) exhibits orange luminescence (λem = 614 nm, ΦPL = 21.03%) and a positive CPL signal (+6.1 × 10–3 glum).
- Cu4I4(L2) shows yellow emission (λem = 575 nm, ΦPL = 1.32%) and a negative CPL signal (–2.4 × 10–3 glum).
- DFT calculations correlate luminescence and CPL differences to variations in frontier orbital distributions and electronic transition pathways.
AI-generated from the title and abstract; the full text is not read.
Abstract
Abstract Employing the epimeric ligands, cinchonidine (L1) and cinchonine (L2), two chiral Cu(I) coordination polymers were synthesized: a 1D chain Cu4I4(L1) and a 3D framework Cu4I4(L2). Structural analyses reveal that Cu4I4(L1) incorporates interconnected distorted gyroscope-like and cubane-type Cu4I4 clusters, whereas Cu4I4(L2) comprises solely cubane-type Cu4I4 clusters. This architectural divergence could be attributed to the distinct spatial preferences of the two N-donor atoms in the epimeric ligands. Photoluminescence studies show that Cu4I4(L1) emits orange light with a single broad band (λem = 614 nm, ΦPL = 21.03%), while Cu4I4(L2) displays yellow emission consisting of multiple bands (λem = 575 nm, ΦPL = 1.32%). DFT calculations correlate these differences to the variations in frontier orbital distributions and electronic transition pathways. Notably, the two compounds exhibit distinct circularly polarized luminescence with maximum glum values of +6.1 × 10–3 for Cu4I4(L1) and –2.4 × 10–3 for Cu4I4(L2). This work illustrates how subtle stereochemical differences in epimeric ligands direct the structural self-assembly of chiral Cu(I)-cluster-based coordination polymers, thereby tuning their photophysical and chiroptical properties, and provides a valuable guideline for designing CPL-active Cu(I)-cluster-based materials.
The authors' abstract, as published at the source. Inorganic Chemistry, 2026 · DOI ↗
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Field: Inorganic Chemistry
Inorganic ChemistryChemistry