Crystal Growth & Design最新文献_第4页

Electrostatic Complementarity as a Design Principle for Lamellar Packing in Nitro-Containing CHON Energetic Materials 静电互补性作为含氮CHON含能材料片层包装的设计原则

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-06 DOI: 10.1021/acs.cgd.6c00723

Rupeng Bu, Xinlei Jia, Yaoyao Linghu

{"title":"Electrostatic Complementarity as a Design Principle for Lamellar Packing in Nitro-Containing CHON Energetic Materials","authors":"Rupeng Bu, Xinlei Jia, Yaoyao Linghu","doi":"10.1021/acs.cgd.6c00723","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00723","url":null,"abstract":"The long-standing trade-off between energy density and mechanical safety has severely restricted the development of advanced energetic materials. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB), the prototypical insensitive high-energy material (IHEM), owes its low sensitivity to a graphite-like lamellar structure, yet no quantitative model currently relates its intermolecular interactions to this lamellar assembly. Herein, we systematically decipher the hierarchical intermolecular interaction network of TATB through a multi-scale theoretical approach. We first identify a bimodal non-uniform interlamellar spacing (3.125 Å and 3.154 Å) in TATB and fully quantify the three-dimensional anisotropy of its intermolecular interactions in type, strength, and directionality. By combining electrostatic potential (ESP) and van der Waals analyses, we first elucidate the electronic origin of this anisotropy. Building on a gradient amino-substituted homologous series and nitro-containing CHON molecules, we further demonstrate that ESP complementarity decisively governs two-dimensional molecular expansion. Finally, we translate these findings into three actionable molecular screening criteria: backbone planarity, alternating donor−acceptor topology, and multidirectional in-plane ESP complementarity. This work provides a quantitative theoretical framework and practical guidance for the rational design of next-generation high-performance insensitive high-energy materials.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8173–8187"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Towards Phase-Pure Cubic GaN on GaP: Suppression of Hexagonal Inclusions by Low-Temperature Buffer Engineering 在GaP上走向相纯立方氮化镓：用低温缓冲工程抑制六方夹杂物

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-12 DOI: 10.1021/acs.cgd.6c00839

José Santis Espinosa, Yoanlys Hernández Barrios, Ángel Sacramento Orduño, Carlos Marín García, Svetlana Mansurova, José Sánchez López, Salvador Garduño Vértiz

{"title":"Towards Phase-Pure Cubic GaN on GaP: Suppression of Hexagonal Inclusions by Low-Temperature Buffer Engineering","authors":"José Santis Espinosa, Yoanlys Hernández Barrios, Ángel Sacramento Orduño, Carlos Marín García, Svetlana Mansurova, José Sánchez López, Salvador Garduño Vértiz","doi":"10.1021/acs.cgd.6c00839","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00839","url":null,"abstract":"Phase-pure cubic GaN (c-GaN) was grown on GaP(001) substrates by low-pressure metal−organic chemical vapor deposition (LP-MOCVD) to evaluate the influence of substrate nitridation and low-temperature GaN buffer layers on phase stability and crystalline quality. Structural and morphological characterization by X-ray diffraction (XRD), Raman spectroscopy, and atomic force microscopy (AFM) showed that the incorporation of a low-temperature buffer layer effectively suppresses hexagonal GaN inclusions and promotes single-phase cubic growth. Raman spectra exhibited the characteristic vibra-tional modes of c-GaN, while XRD analysis revealed narrower c-GaN(200) diffraction peaks, indicating improved crystallinity, larger crystallite size, and reduced defect-related broadening. AFM measurements further demonstrated enhanced grain coalescence and surface uniformity. These findings highlight low-temperature buffer-layer engineering as an effective strategy for stabilizing cubic GaN and improving the structural quality of c-GaN/GaP heterostructures for future electronic and optoelectronic applications.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8232–8242"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ge Doping in LPCVD-Grown (010) β-Ga2O3 Homoepitaxial Films: Structural, Electrical, and Schottky Diode Characteristics lpcvd生长(010)β-Ga2O3同外延薄膜中的Ge掺杂：结构、电学和肖特基二极管特性

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-09 DOI: 10.1021/acs.cgd.6c00894

Ahmed Ibreljic, Saleh Ahmed Khan, Sourav Sarker, Stephen Margiotta, Stephen Lam, Anhar Bhuiyan

{"title":"Ge Doping in LPCVD-Grown (010) β-Ga2O3 Homoepitaxial Films: Structural, Electrical, and Schottky Diode Characteristics","authors":"Ahmed Ibreljic, Saleh Ahmed Khan, Sourav Sarker, Stephen Margiotta, Stephen Lam, Anhar Bhuiyan","doi":"10.1021/acs.cgd.6c00894","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00894","url":null,"abstract":"Ge-doped β-Ga2O3 homoepitaxial films were grown on native (010) β-Ga2O3 substrates using low-pressure chemical vapor deposition (LPCVD). Controlled n-type doping was achieved with room-temperature carrier concentrations ranging from 7.4×1017 to 2.57×1018 cm−3 and corresponding electron mobilities of 105−62 cm2/V·s. The films exhibited smooth surface morphology with RMS roughness values of 2.94−3.97 nm, while X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy confirmed phase-pure β-Ga2O3 with excellent crystalline quality and near-stoichiometric composition. Temperature-dependent Hall measurements on the film with a room-temperature carrier concentration of 7.4×1017 cm−3 and mobility of 105 cm2/V·s yielded a peak electron mobility of 234 cm2/V·s at 116 K, while charge-neutrality and transport modeling revealed a dominant shallow donor level with an activation energy of 14 meV, confirming efficient electrical activation of Ge donors. Vertical Ni/β-Ga2O3 Schottky barrier diodes fabricated using the Ge-doped drift layer exhibited good rectifying behavior with a turn-on voltage of 0.74 V, an ideality factor of 1.32, a Schottky barrier height of 1.02 eV, and a specific on-resistance of 2.49 mΩ·cm2. Capacitance−voltage measurements yielded a net donor concentration of 7.7×1017 cm−3 and a Schottky barrier height of 1.06 eV, in good agreement with Hall and current−voltage measurements. These results demonstrate that LPCVD enables controllable Ge doping while maintaining high structural and electronic quality, establishing LPCVD-grown Ge-doped β-Ga2O3 as a promising platform for future high-voltage power electronic devices.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8302–8311"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

[La3Br][GeS4]2: Cationic-Moiety-Guided Strategy Enables Record Birefringence and Broad Optical Window [La3Br][GeS4]2：阳离子基团引导的双折射记录和宽光窗

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-10 DOI: 10.1021/acs.cgd.6c01084

Cuier Deng, Yuhan Hu, Ruixi Wang, Jingyu Guo

{"title":"[La3Br][GeS4]2: Cationic-Moiety-Guided Strategy Enables Record Birefringence and Broad Optical Window","authors":"Cuier Deng, Yuhan Hu, Ruixi Wang, Jingyu Guo","doi":"10.1021/acs.cgd.6c01084","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01084","url":null,"abstract":"Birefringent crystals are essential for polarization control in optical systems, yet achieving both large birefringence (Δn) and a broad transmission window from ultraviolet to infrared remains a significant challenge. Here, we synthesize a novel birefringent crystal [La3Br][GeS4]2 (LGSB) with ultrahigh birefringence and a broadband optical transparency window, where a trigonal-planar [La3Br] cationic moiety serves as a structural “puppeteer” to modulate the ordered assembly of [GeS4] tetrahedra. More notably, theoretical calculations confirm that the non-bonding S 3p in [GeS4] and the non-bonding Br 4p in [La3Br] are both aligned and spread along a consistent direction. These unique traits endow LGSB with exceptional birefringence (Δnobv. = 0.344@546 nm), surpassing currently reported sulfur-containing chalcogenide halides, even outperforming benchmark crystals YVO4 (0.230@546 nm) and TiO2 (0.300@546 nm). Meanwhile, it delivers an ultrabroad transmission range of 0.36−23.2 μm. Thus, LGSB sets a new standard for wide-bandwidth, high-anisotropy materials and shows strong prospects for multi-band optical parametric oscillators (OPOs) and advanced photonic devices.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8497–8503"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222035","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Li+-Induced Enhancement of Excitonic Luminescence in γ-CuBr Single Crystals Grown by the Vertical Bridgman Method 垂直桥人法生长γ- cur单晶中Li+诱导的激子发光增强

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-03 DOI: 10.1021/acs.cgd.6c01110

Zhijin Zhang, Yizhe Hu, Qiuyu Yu, Jiacheng Pan, Jianguo Pan, Shangke Pan

{"title":"Li+-Induced Enhancement of Excitonic Luminescence in γ-CuBr Single Crystals Grown by the Vertical Bridgman Method","authors":"Zhijin Zhang, Yizhe Hu, Qiuyu Yu, Jiacheng Pan, Jianguo Pan, Shangke Pan","doi":"10.1021/acs.cgd.6c01110","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01110","url":null,"abstract":"The intrinsic defects in pure γ-CuBr crystal lead to obvious nonradiative recombination, thereby significantly suppressing its ultrafast free-exciton emission. In this study, we successfully grew undoped and Li+-doped CuBr:x%Li (x = 0, 1, 3, 5) single crystals using the vertical Bridgman method after purifying raw materials via recrystallization. The influence of Li+ ion incorporation on the crystal structure and photoluminescence (PL) properties was investigated. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) confirmed that Li+ is incorporated in the lattice of γ-CuBr. Moderate Li+ doping markedly enhances the near-band-edge (NBE) emission, with CuBr:3%Li composition exhibiting the highest PL intensityapproximately six times that of pure CuBr. Time-resolved PL further demonstrates an ultrafast radiative decay lifetime of 2.40 ns at 419 nm for the optimal crystal. Temperature-dependent photoluminescence (PL) measurements revealed that the thermal stability of NBE emission significantly improved after Li+ doping. The thermal activation energy of CuBr:3%Li is 382.6 meV.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8536–8542"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222006","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Flux-Grown Centimeter-Sized Sodium Niobate−Barium Titanate Solid Solution Single Crystals: Crystal Structure and Physical Properties 通量生长厘米级铌酸钠-钛酸钡固溶体单晶：晶体结构和物理性质

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-03 DOI: 10.1021/acs.cgd.6c01063

Haotian Zhou, Yongxing Wei, Changpeng Guan, Zhaotian Chen, Jialin Niu, Changqing Jin, Yike Cheng, Peijiang Li, Zhong Yang, Zengyun Jian, Zhonghua Dai, Zengzhe Xi, Li Jin

{"title":"Flux-Grown Centimeter-Sized Sodium Niobate−Barium Titanate Solid Solution Single Crystals: Crystal Structure and Physical Properties","authors":"Haotian Zhou, Yongxing Wei, Changpeng Guan, Zhaotian Chen, Jialin Niu, Changqing Jin, Yike Cheng, Peijiang Li, Zhong Yang, Zengyun Jian, Zhonghua Dai, Zengzhe Xi, Li Jin","doi":"10.1021/acs.cgd.6c01063","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01063","url":null,"abstract":"Centimeter-sized pale-yellow 0.91NaNbO3-0.09BaTiO3 (NN-9BT) single crystals were successfully grown by the flux method near the orthorhombic−tetragonal phase boundary of the NaNbO3−BaTiO3 system. The as-grown crystals display intergrowing grain features, and the maximum grain size is on the centimeter scale. Room-temperature X-ray diffraction revealed a {100}C-oriented orthorhombic structure dominated by the P21ma phase. At room temperature, the crystals exhibited a remanent polarization (Pr) of 10 μC/cm2 and a coercive field (Ec) of 32 kV/cm. The strain-electric field (S−E) response displayed an antisymmetric profile, which became increasingly pronounced with increasing temperature. The in situ piezoelectric coefficient (d33) reached a maximum value of approximately 160 pC/N at 180−190 °C before decreasing sharply near 220 °C. Temperature-dependent X-ray diffraction and Raman spectroscopy revealed a stepwise structural evolution from P21ma to Pbnm(1), Pbnm(2), and finally P4/mbm. The transition from Pbnm(1) to Pbnm(2) involved not only doubling of the b-axis but also a change in the rotational modes of the Nb/TiO6 octahedra. Impedance spectroscopy yielded an activation energy of approximately 0.986 eV, suggesting a defect-assisted thermally activated conduction mechanism.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8480–8488"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222010","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Halogen Effects and Anion Regulation in a Dual-Substituted FeIII-qsal Platform: Steering Abrupt to Two-Step SCO with Wide Hysteresis 双取代feii -qsal平台中的卤素效应和阴离子调控：转向具有宽滞后的两步SCO

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-12 DOI: 10.1021/acs.cgd.6c00923

Xin-Li Liu, Wen-Kun Yan, Yue Zhao, Yi-Fei Deng, Tianwei Wang, Yuan-Zhu Zhang, Xin-Yi Wang

{"title":"Halogen Effects and Anion Regulation in a Dual-Substituted FeIII-qsal Platform: Steering Abrupt to Two-Step SCO with Wide Hysteresis","authors":"Xin-Li Liu, Wen-Kun Yan, Yue Zhao, Yi-Fei Deng, Tianwei Wang, Yuan-Zhu Zhang, Xin-Yi Wang","doi":"10.1021/acs.cgd.6c00923","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00923","url":null,"abstract":"Achieving abrupt, hysteretic spin crossover (SCO) requires strong cooperativity, typically engineered through supramolecular interactions. In this work, we designed a dual-halogenated Hqsal ligand, 5-F-Hqsal-5-Iq, strategically incorporating both bulky iodine and electronegative fluorine moieties. This design modulates the ligand field and, more importantly, induces strong halogen-mediated supramolecular interactions. Three FeIII complexes, [Fe(5-F-qsal-5-Iq)2]A·CH3OH (A = ClO4− (1), BF4− (2), and OTf− (3)), were synthesized and characterized, all adopting a similar Chain-Layer packing motif. The steric demand of the iodine atom forces the fluorine atoms on adjacent chains into closer proximity, which enhances hydrogen bonds and fluorine-mediated interactions within the 2D layers, thereby enhancing cooperativity. Notably, complex 3 exhibits enhanced cooperativity driven by extensive and intensified supramolecular interactions involving the iodine atoms and the OTf− anion. Magnetically, 1 and 2 exhibit abrupt SCO with narrow hysteresis, while 3 exhibits a two-step transition with a remarkably wide and stable 57 K hysteresis (1 K/min) that expands to 64 K at 15 K/min. All complexes exhibit the LIESST effect, with 3 showing the most pronounced response. This study underscores how steric and electronic effects from dual-halogen substitution can be employed to modulate SCO properties, offering a rational design route to high-performance SCO materials.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8345–8355"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Vacancy-Driven Tetrahedral Distortion in Defect Diamond-Like Selenides for Exceptional Second-Order Nonlinearity 特殊二阶非线性缺陷类金刚石硒化物中空位驱动的四面体畸变

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-12 DOI: 10.1021/acs.cgd.6c01113

Shuo Wang, Xu Liu, Chenglong Zhang, Ailijiang Abudurusuli, Ming-Hsien Lee, Junben Huang

{"title":"Vacancy-Driven Tetrahedral Distortion in Defect Diamond-Like Selenides for Exceptional Second-Order Nonlinearity","authors":"Shuo Wang, Xu Liu, Chenglong Zhang, Ailijiang Abudurusuli, Ming-Hsien Lee, Junben Huang","doi":"10.1021/acs.cgd.6c01113","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01113","url":null,"abstract":"Diamond-like (DL) chalcogenides have emerged as a highly promising structural framework for infrared nonlinear optical (NLO) materials due to their inherently non-centrosymmetric structures and highly oriented tetrahedral units. Herein, a family of defect DL selenides AIIBIII2Se4 (AII = Zn, Cd; BIII = Al, Ga, In) was systematically investigated by integrating theoretical calculations and experimental characterization. These compounds crystallize in the tetragonal I<math><mover><mn>4</mn><mo>¯</mo></mover></math> space group, adopting a defect DL structure derived from infrared benchmark AgGaS2 (AGS), incorporating cation vacancies and highly distorted [BIIISe4] tetrahedral units, which significantly enhance microscopic second-order polarizability. Experimental results demonstrate that these defect DL selenides exhibit strong second-harmonic generation (SHG) intensities and tunable band gaps. Remarkably, ZnIn2Se4 demonstrates a considerable SHG response, approximately 5.5 times that of the commercial benchmark AGS with phase-matching behavior. First-principles calculations further elucidate that their effective NLO coefficients d14 range from 16.44∼34.04 pm/V (calculated by sum over-states method) and 18.49∼35.11 pm/V (DFPT method), respectively, which are attributed to the pronounced bond-angle distortions within the [BIIISe4] tetrahedra, as well as the Se 4p lone-pair-like electrons. This work confirms that vacancy-driven tetrahedral distortion engineering is a potential design strategy for high-performance infrared NLO crystals.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8543–8551"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Isomerization-Driven Photo-Coloration and Elastic Bendability: A Unique Blend of Molecular and Structural Property in Organic Single Crystals 异构化驱动的光着色和弹性弯曲性：有机单晶中分子和结构特性的独特混合

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-12 DOI: 10.1021/acs.cgd.6c00849

Shilpa Munthikkot, Velluvakandi Chaluvalappil Saheer, Srinu Tothadi, Sumy Joseph

引用次数: 0

Crystal−Amorphous−Crystal Transformation of a Photoluminescent Platinum(II) Complex: Solid-State Color Tuning via Dihedral-Angle Variations 一种光致发光铂（II）配合物的晶体-非晶态-晶体转变：通过二面角变化的固态调色

IF 3.6 2区化学

Crystal Growth & Design Pub Date : 2026-10-21 Epub Date: 2026-10-01 DOI: 10.1021/acs.cgd.6c00561

Kazuma Takahara, Ryota Nakamura, Ren Hashimoto, Ren Ueno, Keishiro Tahara, Yoshiki Ozawa, Masaaki Abe

{"title":"Crystal−Amorphous−Crystal Transformation of a Photoluminescent Platinum(II) Complex: Solid-State Color Tuning via Dihedral-Angle Variations","authors":"Kazuma Takahara, Ryota Nakamura, Ren Hashimoto, Ren Ueno, Keishiro Tahara, Yoshiki Ozawa, Masaaki Abe","doi":"10.1021/acs.cgd.6c00561","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00561","url":null,"abstract":"A new photoluminescent platinum(II) complex, cis-[PtCl2(ppt)], where ppt = 2-(2-pyridyl)-4-phenylthiazole, has been synthesized and characterized. Two polymorphs of the complex were isolated with high phase purity: an orange crystalline phase O-Cryst and a yellow crystalline phase Y-Cryst, each exhibiting distinct solid-state photoluminescence. Partially amorphous phases derived from the respective polymorphs, O-Ground and Y-Ground, were prepared by mechanical grinding. Upon exposure to acetone vapor, both amorphous phases recrystallized exclusively to the O-Cryst. The structural difference among the crystalline and amorphous phases was investigated by powder X-ray diffraction and pair distribution function (PDF) analysis, with the latter clearly revealing the local molecular packing that is inaccessible by conventional diffraction techniques. Density functional theory calculations correlated the relative energies and molecular geometry in the respective solids with the observed photoluminescence color variations. The difference in the dihedral angles between the pyridyl and phenyl rings of the ppt ligand was found to strongly govern the availability of π-delocalized orbitals, thereby accounting for the polymorphism-dependent color variation. The stimuli-induced crystal−amorphous−crystal transformation described here provides a straightforward design principle for fine-tuning of the solid-state photoluminescence while emphasizing the enormous utility of PDF analysis for elucidating local structures and the mechanisms of phase transformation in molecular crystals.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8105–8115"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221950","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0