Hybrid Hairy Two-Dimensional Nanostructures with Tunable Morphologies by Inclusion Crystallization of Lead Bromide Complexes with Polystyrene- block -poly(ethylene oxide) Article Swipe

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Ya-Sen Sun , Bo Cheng Zhao , Chun-Chuen Yang , Orion Shih , Chun-Yu Chen , Chun‐Jen Su , Jhih-Min Lin , Ya-Sen Sun , Bo Cheng Zhao , Chun-Chuen Yang , Orion Shih , Chun-Yu Chen , Chun‐Jen Su , Jhih-Min Lin ·

YOU? · · 2025 · Open Access · · DOI: https://doi.org/10.1021/acs.langmuir.5c03419

We report the formation of hybrid hairy nanostructures composed of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) and lead bromide (PbBr₂) complexes in 1,3,5-trimethylbenzene (TMB). In this system, TMB acts as a selective solvent (good for the PS block and bad for the PEO block) while serving as a nonsolvent for PbBr₂. Although PbBr₂ is insoluble in neat TMB, its complexation with PS-b-PEO promotes the formation of the [PbBr₃]^- and [PbBr₄]^2- complexes. These complexes coordinate with the ether groups of the PEO block, forming host-guest interactions that drive the inclusion crystallization of two-dimensional (2D) hybrid nanostructures, including irregular nanosheets and polygonal nanoplates. The morphology of these nanostructures strongly depends on the PS-b-PEO/PbBr₂ weight ratio. Higher ratios (20/100 and 20/200) favor irregular nanosheets, while lower ratios (20/10) favor polygonal nanoplates. Structural analysis reveals that the irregular nanosheets adopt an orthorhombic Cmca lattice (a = 23.53 Å, b = 4.20 Å, c = 33.22 Å), whereas the polygonal nanoplates exhibit a hexagonal P6mm lattice (a_hex = 13.954 Å, γ = 120°). Both types of 2D structures are decorated with ultrasmall PbBr₂ nanoparticles encapsulated by PS-b-PEO chains. The PEO blocks coordinate to nanoparticle surfaces, while PS blocks swell in the TMB. This synergistic process integrates PbBr₂ complexation, host-guest coordination, inclusion crystallization, and block copolymer-mediated nanoparticle assembly. In spin-coated films, polygonal nanoplates preferentially adopt edge-on orientations, while irregular nanosheets lie flat-on. These findings offer insights into block copolymer templating of 2D organic-inorganic hybrid nanostructures.

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Crystallization Orthorhombic crystal system Materials science Nanostructure Nanoparticle Chemical engineering Bromide Copolymer Raft Solvent Supramolecular chemistry Self-assembly Template Ether Nanocrystal Nanotechnology Crystallography Polymer chemistry Morphology (biology) Macromolecule Hexagonal crystal system Block (permutation group theory) Nanocomposite Hybrid material Lead sulfide Lamellar structure Stoichiometry Chemistry

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Type: article
Language: en
Landing Page: https://doi.org/10.1021/acs.langmuir.5c03419
OA Status: hybrid
References: 68
OpenAlex ID: https://openalex.org/W7105902044

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DOI: https://doi.org/10.1021/acs.langmuir.5c03419

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Title: Hybrid Hairy Two-Dimensional Nanostructures with Tunable Morphologies by Inclusion Crystallization of Lead Bromide Complexes with Polystyrene- block -poly(ethylene oxide)

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Language: en

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Publication year: 2025

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Publication date: 2025-11-18

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Authors: Ya-Sen Sun, Bo Cheng Zhao, Chun-Chuen Yang, Orion Shih, Chun-Yu Chen, Chun‐Jen Su, Jhih-Min Lin, Ya-Sen Sun, Bo Cheng Zhao, Chun-Chuen Yang, Orion Shih, Chun-Yu Chen, Chun‐Jen Su, Jhih-Min Lin

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Landing page: https://doi.org/10.1021/acs.langmuir.5c03419

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Concepts: Crystallization, Orthorhombic crystal system, Materials science, Nanostructure, Nanoparticle, Chemical engineering, Bromide, Copolymer, Raft, Solvent, Supramolecular chemistry, Self-assembly, Template, Ether, Nanocrystal, Nanotechnology, Crystallography, Polymer chemistry, Morphology (biology), Macromolecule, Hexagonal crystal system, Block (permutation group theory), Nanocomposite, Hybrid material, Lead sulfide, Lamellar structure, Stoichiometry, Chemistry

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