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RESEARCH PAPER · Journal of the American Chemical Society · 2024

Lone Pair Induced 1D Character and Weak Cation–Anion Interactions: Two Ingredients for Low Thermal Conductivity in Mixed-Anion Metal Chalcohalide CuBiSCl2

Xingchen Shen, Koushik Pal, Paribesh Acharyya, Bernard Raveau, Philippe Boullay, Oleg I. Lebedev, Carmelo Prestipino, Susumu Fujii, Chun‐Chuen Yang, I‐Yu Tsao, Adèle Renaud, Pierric Lemoine, Christophe Candolfi, Emmanuel Guilmeau

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Lone Pair Induced 1D Character and Weak Cation–Anion Interactions: Two Ingredients for Low Thermal Conductivity in Mixed-Anion Metal Chalcohalide CuBiSCl2OriginalAtomic hopping induced dynamic disorder phonon scattering and suppressed thermal transport in Cu4TiSe42Copper delocalization leads to ultralow thermal conductivity in chalcohalide CuBiSeCl 211Exploring Combined Stereochemically Active Lone-Pair and Rattling Effects in Thermoelectrics with Machine Learning Potentials8Tuning the Reaction Chemistry for the Sulfo-Bromination of Bismuth, Leading to Dual-Tapered Bi-Sulfobromide Platelet Nanocrystals and Their Heterostructures7Copper(I)-Based Coordination Polymers for Photocatalytic Benzylic C(sp 3 )–H-Oxidation via Energy Transfer5Layered Ordered Multianion Semiconductor Bi18O21.6Se1.8Cl7.2 with Low c-Axial Thermal Conductivity0Mechanisms and design principles for optimizing lattice thermal conductivity in chalcogenides: A comprehensive review7High n -type thermoelectric performance due to anisotropic charge-phonon transport in CuBiSCl 26Antimony Sulfobromide Nanowire Bundles Exhibiting Ambipolar Photoelectrochemical Photocurrent Switching0Local Thermal Conductivity Patterning in Rotating Lattice Crystals of Anisotropic Sb 2 S 33Assessing the Impact of Static Instability on Intrinsic Defects in Photovoltaic Material CuBiSCl 2 by First-Principles Molecular Dynamics Simulation1Tailoring optical and ferroelectric properties in Sb 1− x Bi x SI van der Waals chalcohalides towards solar absorber applications4Forced bond ionization–driven design of ultralow lattice thermal conductivity materials for flexible thermoelectrics4The Predictive Power of Chemical Bonding Analysis in Materials: A Perspective on Optoelectronic Properties4Rational Analyses of Heat Capacity for Thermoelectric Materials2Cu-substitution-driven orbital and phonon engineering breaks the thermoelectric trade-off in n-type Fe 2 VAl-based alloys0First-principles investigation of CuBiSeCl 2 : a quaternary halide chalcogenide material for advanced optoelectronic and thermoelectric energy harvesting and conversion technologies2Layered mixed-anion chalcohalides Pb 4 Sb 4 Q 9 Cl 2 (Q = S, Se): puckered 2D frameworks, indirect band gaps, and low thermal conductivity0Structural chemistry and applications of heteroanionic rare-earth metal chalcogenide halides1Synergistic effects of K-atom rattling, anisotropy, and antibonding states on high thermoelectric performance in KAuSe 20Te–Se replacement induced structural transition and enhanced band gaps in Cd 5 Se 4 O 12 Cl 2 and Cd 5 Se 4 O 12 Br 21Wide Bandgap Oxychalcogenide With Low Effective Mass, Strong Excitonic Effects, and High Figure of Merit: BaTa 4 Te 3 O 171Unveiling the impact of bonding asymmetry on the lattice thermal conductivity of MnXS2Cl (X=Sb, Bi) for promising thermoelectric applications1Four-phonon anharmonicity and inverted thermal conductivity in M Bi SCl 2 ( M = Ag , Cu ) induced by s - d orbital coupling0Cu 7.62 Bi 6 Se 12 Cl 6 I: Discovery of a Low Band Gap, Low Thermal Conductivity Mixed-Anion Material0Intrinsically ultralow thermal conductivity in all-inorganic superatomic bulk crystals0Interplay between Cu Delocalization and Bonding Anisotropy on the Thermoelectric Performance of Double-Cation Chalcohalides CuBiSeX 2 (X = Cl, Br)1Ambipolar thermoelectric performance enabled by low lattice thermal conductivity and high-mobility carriers in Ag 3 SX ( X = Cl , Br, I) antiperovskites2Unveiling the Electronic Landscape in Lead-Free Silver (Copper)–Bismuth–Sulfide (Halide) Semiconductors: Insights into Charge Carrier Transport and Trapping Characteristics1Exceptional n-Type Thermoelectric Performance in Anisotropic K 2 Te 3 via Lone-Pair Electron and Dual-Rattling Mode Engineering0Multicentered p–s–p* Antibonding Interaction Induces Strong Anharmonicity and High Thermoelectric Performance in Complex Metal Chalcohalide Tl 5 Te 2 I0Selective photocatalytic conversion of formaldehyde over polarized chalcohalides: Control of hydrogen and hydrocarbon formation0O/N Mixed-Anion Defect Engineering Mediates Structural Evolution and Li-ion Transport in La24Li23Ti5O53N30Suppressing Second-Order Jahn–Teller Distortion of Bi3+ by Smaller Y3+-Substitution in Bi3O4Cl0Mixed-Anion Mischief: Lone Pairs Meet Ionic Bonds to Suppress Thermal Transport in Quasi-1D Bi3Se4Br0Synergistic Suppression of Ionic Conduction and Lattice Thermal Conductivity Through Trigonally Coordinated [CuI 3 ] 2− Units and Zero‐Dimensionality in Cs 3 Cu 2 I 50

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  9. Antimony Sulfobromide Nanowire Bundles Exhibiting Ambipolar Photoelectrochemical Photocurrent Switching

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  14. The Predictive Power of Chemical Bonding Analysis in Materials: A Perspective on Optoelectronic Properties

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  15. Rational Analyses of Heat Capacity for Thermoelectric Materials

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  17. First-principles investigation of CuBiSeCl 2 : a quaternary halide chalcogenide material for advanced optoelectronic and thermoelectric energy harvesting and conversion technologies

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  18. Layered mixed-anion chalcohalides Pb 4 Sb 4 Q 9 Cl 2 (Q = S, Se): puckered 2D frameworks, indirect band gaps, and low thermal conductivity

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  21. Te–Se replacement induced structural transition and enhanced band gaps in Cd 5 Se 4 O 12 Cl 2 and Cd 5 Se 4 O 12 Br 2

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  24. Four-phonon anharmonicity and inverted thermal conductivity in M Bi SCl 2 ( M = Ag , Cu ) induced by s - d orbital coupling

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  31. Multicentered p–s–p* Antibonding Interaction Induces Strong Anharmonicity and High Thermoelectric Performance in Complex Metal Chalcohalide Tl 5 Te 2 I

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