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RESEARCH PAPER · Coordination Chemistry Reviews · 2024

Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) units

Bo Zhang, Mao‐Yin Ran, Xin‐Tao Wu, Hua Lin, Qi‐Long Zhu

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Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) unitsOriginalScreening Strategy Identifies an Overlooked Deep‐Ultraviolet Transparent Nonlinear Optical Crystal3Screening Strategy Identifies an Overlooked Deep‐Ultraviolet Transparent Nonlinear Optical Crystal45Achieving the Birefringence Optimization by Methyl Modulation in Organic Nonlinear Optical Crystals15Learning From Nature: The Rational Non‐Centrosymmetric Structural Design in the Honeycomb‐Like Gaudefroyite Family23A Giant Optically Anisotropic Phosphate Driven by Mixed Valence Mercury Units22From [Ba3S][GeS4] to [Ba3CO3][MS4] (M = Ge, Sn): Enhancing optical anisotropy in IR birefringent crystals via functional group implantation11Deep‐Ultraviolet Transparent Nonlinear Optical Phosphates: A New Alternative to Conventional Borates9Strategically designed anisotropic organic–inorganic metal halides (OIMHs) with superior balance between bandgap and birefringence12(C 14 H 14 N 2 )MCl 4 (M = Zn, Cd): two hybrid metal halides exhibiting strong second harmonic generation responses, large birefringence, and broadband photoluminescence12A potential UV nonlinear-optical crystal with a strong second-harmonic response: RbNa 2 Eu 2 (BO 3 ) 35Exploring new horizons in mid-to-far infrared nonlinear optical crystals: the significant potential of trigonal pyramidal [TeS 3 ] 2− functional units18Hg 2 (HTe 2 O 5 )(PO 4 ): a novel phosphate crystal with enhanced birefringence enabled by the synergistic modification of multiple functional groups12Hg 2 (SeO 3 )(TeO 3 ): a novel tellurite–selenite birefringent crystal achieved by assembling multiple functional groups11Hg[CS(NH 2 ) 2 ] 4 (SiF 6 ): a fluorosilicate crystal with large birefringence achieved via multi-functional group modification6Isovalent cation substitution drives structural transformation and infrared nonlinear optical activity in Eu-based chalcogenides11Chemical Substitution‐Driven Design of a High‐Performance Noncentrosymmetric Bismuth Molybdenum Selenite10Zwitterionic Glycine-Based Antimony Fluorides with Exceptional Ultraviolet Nonlinear Optical Properties11Pb9O4(BO3)2(NO3)4: A Lead Borate–Nitrate Containing an Anion-Centered [O8Pb18]∞ Chain with Large Optical Anisotropy2K3[HCO3]2F: a new deep-UV birefringent crystal exhibiting strong optical anisotropy17Rb 7 PbY 2 (B 5 O 10 ) 3 : A Noncentrosymmetric Rare-Earth Borate Nonlinear Optical Crystal with [B 5 O 10 ] Unit16Engineering an Excellent β ‐BaB 2 O 4 ‐Inspired UV Nonlinear Optical Material Through Secondary Building Unit Substitution21Engineering an Excellent β ‐BaB 2 O 4 ‐Inspired UV Nonlinear Optical Material Through Secondary Building Unit Substitution6Na[B3IO7(OH)] and Na2[B4IO9](IO3): Explorations of Boroiodates with Strong Second Harmonic Generation Response and Large Birefringence54Selective-crystallization strategy for the separation of rare earth elements: A minireview29Phase-Matching Second-Harmonic Generation in Zero-Dimensional Zinc Thiocyanates Ligated with Chiral Amino Acids6Hydrogen‐Bonded Assembly of Functional Units for Constructing Linear and Nonlinear Optical Crystals10Cation Equivalent Multisubstitution Realizing Structure Transformation and Balanced Nonlinear Optical Performance of Quaternary Eu-Based Chalcogenides8[C(NH2)3]Y(HCOO)4: Constructing 3D Framework for Guanidine-Based UV Nonlinear Optical Crystals with Good Performance8La3Ga5HfO14: Rare-Earth Polyhedron Coupled with Structural Protected Octahedron for Designing Nonlinear Optical Material with Wide Bandgap and Well-Balanced Properties5Fabrication and evaluation of NaSrEr(BO3)2 interlayer in Al/Si photodiode structures for photodetector applications2La(SO3NH2)2NO3·H2O: synergistic anion engineering of the first rare-earth nitrate sulfamate defying transparency-birefringence-nonlinearity trade-offs in ultraviolet nonlinear optics8Engineered Integration of Diverse Functional Units Induces Multifunctionality in Malonate‐Borate Hybrids44Incorporation of Cu2+ within the ligand cavities of porphyrin-based MOFs for enhanced nonlinear optical performance2Borosilicates as deep-ultraviolet transparent nonlinear optical crystals: Structural motifs, performance limits and future directions9Sign Reversal of Optical Nonlinearity by Pauli Blocking in Blue Light-Emitting Samarium-Doped ZnO Nanostructures2The crystal chemistry and topology of modular structures. I. Selenites of rare-earth elements5Maximizing the second-harmonic generation response via coordination-induced localization of nonbonding electrons12[C(NH 2 ) 3 ] 2 PO 3 (OH): A Deep-Ultraviolet Birefringent Crystal Enabled by Synergy of π-Conjugated Cations and Heteroleptic Tetrahedra2Charge-order-induced directional enhancement of non-diagonal second-order nonlinear optical tensor components2K 7 MgY 2 (B 5 O 10 ) 3 : a novel ultraviolet nonlinear optical crystal based on the [B 5 O 10 ] functional unit2Rb7.5Ln2.5B15O30 (Ln = Gd and Eu): All-in-One Noncentrosymmetric Pentaborates with Strong Second-Harmonic Generation and Efficient Luminescence0Tailoring linear and nonlinear optical properties of 2D Sc 2 C MXenes via surface termination modulation0Two scandium borate UV NLO crystals designed through chemical element substitution1[C(NH 2 ) 3 ]SbCl 4 : An NLO Material with Enhanced Second Harmonic Response and Birefringence3Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.27Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.21Record‐Short Phase Matchability of Silicate: Charge‐Driven Lattice Distortion Enables Deep‐UV Phase Matching and Strong Optical Nonlinearity0K 3 YGe 3 O 9 : A Rare-Earth Germanate Nonlinear Optical Crystal with a Short Ultraviolet Cutoff Edge and Moderate Second-Harmonic Generation Response1The Achievement of a Strong Second Harmonic Generation Response and a Large Birefringence in Sulfates4Anion Size‐Dependent Conformational Folding of Guanidinopropionate: Enabling Tunable Birefringence and Balanced Second‐Harmonic Generation Performance3Anion Size‐Dependent Conformational Folding of Guanidinopropionate: Enabling Tunable Birefringence and Balanced Second‐Harmonic Generation Performance0Recent Progress in Hg-Based Oxysalt Crystals for Nonlinear Optics and Birefringence Applications5High‐Performance Infrared Nonlinear Optical Crystals Discovery Guided by High‐Throughput Computation, Machine Learning, and Experimental Verification6High‐Performance Infrared Nonlinear Optical Crystals Discovery Guided by High‐Throughput Computation, Machine Learning, and Experimental Verification2Lanthanide MOFs and their composite gel glasses: Central metal ion engineering of nonlinear optical responses0Spin-Resolved Second-Harmonic Generation from Europium 4f/5d States in a Weakly Stabilized Metastable Polymorph of Eu 2 P 2 S 60Reverse Weak Polarity‐Induced Ordered Layer Control for Enhanced Second‐Harmonic Generation in Ultraviolet Nonlinear Optical Crystals2Heterovalent Coexistence‐Driven Symmetry Breaking and Dimensional Evolution: Designing Polar Heart‐Shaped Channels for Exceptional MFIR Nonlinear Optics5Assembly of Functional Units for Constructing an Ultraviolet-Transparent Nonlinear Optical Mixed Alkaline Metal Borate-Formate1K 3 Yb 2 (BO 3 ) 3 and Rb 3 Yb 2 (BO 3 ) 3 : Two Rare-Earth Borate Ultraviolet Nonlinear Optical Crystals1Tuning Second‐Order Nonlinear Optical Properties via Electronic Interaction Engineering: Distinct Roles of Nonconjugation, σ–π Conjugation, and Intramolecular Charge Transfer in Chalcogen‑Functionalized Closo ‐Carborane Hybrids0Symmetry Breaking Induced by Hydration-Number Tuning Enables Second-Order Nonlinear Optical Responses in Lanthanum Sulfate Hydrates0Non-π-conjugated tetrahedra-based optical crystals: The improvement of the linear and nonlinear optical properties by the combination of trigonal pyramidal [XO3] (X = I, Se, Te) units1Potential Deep Ultraviolet Phosphate With Y‐Based: 1 [(PO 3 ) 4 ] ∞ Chains AYP 4 O 12 (A = K, NH 4 ) and the First [P 3 O 10 ] Anionic Framework KLiYP 3 O 100Domino‐Effect Amplification via Covalent‐Chain Engineering for Giant Birefringence in NaAsQ 2 (Q = S, Se) Crystals0FBB-directed open framework evolution in alkali metal borates: Synthesis and structure property relationships of NaRb2B9O150

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