Precisely Tuning Band Gaps of Hexabenzocoronene-Based MOFs Toward Enhanced Photocatalysis.

Precise adjusting the band gaps in metal-organic frameworks (MOFs) is crucial for improving their visible-light absorption capacity during photocatalysis, presenting both a formidable challenge and a charming opportunity. This present study employed a symmetry-reduction strategy to pre-design six novel 4-connected ligands with systematic substituents (-NO2, -H, -tBu, -OCH3, -OH and -NH2) and synthesized the corresponding pillared-layer Zr-MOFs (NKM-668) retaining the hexaphenylbenzene fragment. Subsequently, the NKM-668 MOFs were transformed into large-π-conjugated hexabenzocoronene-based MOFs (pNKM-668) via the Scholl reaction. These twelve MOFs exhibited broad and tunable band gaps over 1.41 eV (ranging from 3.25 eV to 1.84 eV), and the photocatalytic CO2 conversion rate raised by 33.2-fold. This study not only enriches the type of hexaphenylbenzene-based MOFs, but also paves the way for nanographene-containing MOFs in the further application of photocatalysis.

Engineering Hygroscopic MOF-Based Silk Via Bioinspired Interfacial Assembly for Fast Moisture Manipulation.

Metal-organic frameworks (MOFs) have emerged as exceptional moisture sorbents in low humidity conditions. However, their typical powdered form often results in agglomeration, impeding water diffusion kinetics and practical handling. To enhance the accessibility and diversify the integration of MOFs, a universal and scalable bionic interfacial assembly method is introduced for fabricating MOF-based silk. The resulting silk, enriched with a high content of MOF-303, demonstrates a significant water adsorption capacity of 315.1 mg g-1 at 25% relative humidity, exhibiting a three fold faster water absorption compared with that of stacked MOFs powder on a gram-scale. Furthermore, it achieves efficient water release, with a rate of 8.1 mg g-1 min-1 under sunlight after surface photothermal modification. Through one-step drawing assembly, electrothermal wires can be incorporated into MOF-based silk and demonstrate fast and reversible moisture adsorption/desorption for indoor humidity control. It is envisioned that this assembling method and integrated functional silk will yield valuable insights into the rational engineering of MOFs toward practical applications in moisture management, molecule absorption, etc.

Macroscopic Twisting of Chiral Metal Halide Single Crystals Driven by Thermo-Induced Topochemical Dehydration.

Dynamic twisting crystals, combining the features of dynamic crystals and twisting crystals, promise advanced applications in targeted drug delivery, biosensors, microrobots, and spiral optoelectronics. However, the determination of dynamic twisting crystals with specific directions remains a formidable challenge in practical applications. Herein, based on organic-inorganic hybrid metal halide (OIHMH) single crystals, we have realized the chirality-induced macroscopic twisting of single crystals driven by a thermo-induced topochemical dehydration reaction. These crystals exhibit molecular-chirality-induced twisting upon heating, along with reversals in their linear chiroptical circular dichroism and nonlinear chiroptical second harmonic generation circular dichroism. Such an induced twisting has been attributed to the alteration of the helical arrangement of chiral cation post-topochemical dehydration. The feasibility of tuning the macroscopic twisting of OIHMH single crystals and the switching in their linear and nonlinear chiroptical properties might open up new avenues for developing dynamic crystals for microactuating and optoelectronic applications.

Chirality-Mediated 1D-to-2D Phase Transition in Hybrid Lead Halide Perovskites.

Dimensionality engineering plays a pivotal role in optimizing the performance, ensuring long-term stability, and expanding the versatile applications of lead halide perovskites (LHPs). Currently, the manipulation of LHP dimensions primarily occurs during the synthesis stage, a procedure hampered by constraints, including synthetic complexity and irreversibility. This investigation successfully achieved a transition from one-dimensional (1D) to two-dimensional (2D) structures in chiral LHPs by applying hydrostatic pressure. Remarkably, this pressure-induced transition in dimensionality is absent in the racemic analogue due to the staggered arrangement of inorganic chains and the elevated steric hindrance posed by the organic cations. Notably, the hydrogen bonding between organic cations and the inorganic framework adopts a symmetrical arrangement in the racemic system but a helical configuration along the 1D chain direction in the chiral counterparts. This distinct helical arrangement induces a consequential distortion in the inorganic moiety, resulting in the emergence of a spin-polarized Rashba-Dresselhaus texture that explains the chirality's electronic spin origin. Furthermore, both experimental and density functional theory calculation results demonstrate that the 1D-to-2D phase transition in chiral halide perovskites can induce significant modifications in the electronic structures and associated optical emissions. In summary, the findings unveil novel avenues for manipulating optoelectronic properties in chiral perovskites through dimensionality engineering.

Liquid-Phase Exfoliation of 3D Metal-Organic Frameworks into Nanosheets.

Traditionally, the acquisition of 2D materials involved the exfoliation of layered crystals. However, the anisotropic bonding arrangements within 3D crystals indicate they are mechanically reminiscent of 2D counterparts and could also be exfoliated into nanosheets. This report delineates the preparation of 2D nanosheets from six representative 3D metal-organic frameworks (MOFs) through liquid-phase exfoliation. Notably, the cleavage planes of exfoliated nanosheets align perpendicular to the direction of the minimum elastic modulus (Emin) within the pristine 3D frameworks. The findings suggest that the in-plane and out-of-plane bonding forces of the exfoliated nanosheets can be correlated with the maximum elastic modulus (Emax) and Emin of the 3D frameworks, respectively. Emax influences the ease of cleaving adjacent layers, while Emin governs the ability to resist cracking of layers. Hence, a combination of large Emax and small Emin indicates an efficient exfoliation process, and vice versa. The ratio of Emax/Emin, denoted as Amax/min, is adopted as a universal index to quantify the ease of mechanical exfoliation for 3D MOFs. This ratio, readily accessible through mechanical experiments and computation, serves as a valuable metric for selecting appropriate exfoliation methods to produce surfactant-free 2D nanosheets from various 3D materials.

Rational Tuning the Proton Conductivity and Stability of Hydrogen-Bonded Organic Frameworks.

In the development of proton conductors, it is crucial to regulate proton conduction pathways and enhance structural stability. In this study, we designed and constructed three hydrogen-bonded organic frameworks (HOFs), namely, NKM-HOF-9, NKM-HOF-10, and NKM-HOF-11, with different dimensional hydrogen-bonding pathways using 4,4'-sulfonyldibenzoic acid and various bases. They are cost-effective and easy to synthesize, allowing for their large-scale production at room temperature. By purposefully altering the ammonium ions, we achieved enhancements in the conductivity and stability of these HOFs. Proton conductivity studies at different humidities and temperatures revealed that at 85 °C and 98% relative humidity, the proton conductivity of NKM-HOF-10 reached 1.7 × 10-3 S cm-1, surpassing that of NKM-HOF-9 by 1 order of magnitude. This improvement was accomplished by increasing the number of proton donors from the base, which resulted in a transition of the hydrogen bond network from discontinuous to continuous, thereby enhancing the proton conduction performance. Moreover, stability tests showed that raising the base's pKa could improve the stability of these frameworks. NKM-HOF-11, which features the highest pKa, demonstrated superior stability by maintaining its structural integrity even at 450 °C.

Flexible Metal-Organic Frameworks: From Local Structural Design to Functional Realization.

ConspectusFlexible metal-organic frameworks (MOFs), also known as soft porous crystals, exhibit dynamic behaviors in response to external physical and chemical stimuli such as light, heat, electric or magnetic field, or the presence of particular matters, on the premise of maintaining their crystalline state. The reversible structural transformation of flexible MOFs, a unique characteristic seldomly found in other types of known solid-state materials, affords them distinct properties in the realms of molecule separation, optoelectronic devices, chemical sensing, information storage, biomedicine applications, and so on. The mechanisms underlying their dynamic behaviors can be comprehensively investigated at the molecular level by means of in situ single-crystal or powder X-ray diffraction as well as other in situ spectroscopic techniques due to the high regularity of these crystalline materials during stimuli-responsive phase transitions. Through the introduction of specific stimuli-responsive groups/moieties into the well-defined and ordered molecular arrays, targeted applications can be achieved, and the performance of flexible MOFs can also be further improved via rational structural design.In this Account, we summarize our progress on the design, synthesis, and applications of flexible MOFs over the past few years. First, we highlight the construction principle of flexible MOFs, emphasizing the pivotal role of local structural design. Using an F-modified ligand, a flexible MOF with remarkable structural transformations can be obtained; the regulation of the metal coordination environment and interpenetrating frameworks is also crucial for achieving flexible MOFs. We also propose a strong correlation strategy based on the supramolecular interactions between the guest molecules and the framework, which realizes the temperature-responsive dynamic spatial "open-closed" regulation. Mechanisms of the dynamic behaviors investigated by the in situ techniques were also presented for the obtained materials. Second, some representative specific applications of the newly developed dynamic coordination systems were reviewed. The gas molecule responsive flexible MOFs show efficient short-chain alkane separation properties with discriminatory sorption behavior toward similar gaseous substrates. Smart sensing of temperature, pressure, and volatile organic compounds was achieved by several novel flexible fluorescent MOFs, with optimization potential through state-of-the-art chemical design. Furthermore, multiferroic materials with multiple bistable states and high working temperatures were also obtained based on flexible MOFs.Finally, we provide a discussion of the challenges of flexible MOFs in future research, including precise and efficient synthesis, in-depth structure-property relationship investigation, performance optimization, and industrialization. We hope that this Account will stimulate further research interest in developing next-generation smart materials based on flexible MOFs for applications in challenging chemical separation, extreme environmental sensing, massive information storage, and beyond.

Porous Organic Cage as an Efficient Platform for Industrial Radioactive Iodine Capture.

Herein, we firstly develop porous organic cage (POC) as an efficient platform for highly effective radioactive iodine capture under industrial operating conditions (typically ≥150 °C), ≤150 ppmv of I2). Due to the highly dispersed and readily accessible binding sites as well as sufficient accommodating space, the constructed NKPOC-DT-(I-) (NKPOC=Nankai porous organic cage) demonstrates a record-high I2 uptake capacity of 48.35 wt % and extraordinary adsorption capacity of unit ionic site (~1.62) at 150 °C and 150 ppmv of I2. The I2 capacity is 3.5, 1.6, and 1.3 times higher than industrial silver-based adsorbents Ag@MOR and benchmark materials of TGDM and 4F-iCOF-TpBpy-I- under the same conditions. Furthermore, NKPOC-DT-(I-)Me exhibits remarkable adsorption kinetics (k1=0.013 min-1), which is 1.2 and 1.6 times higher than TGDM and 4F-iCOF-TpBpy-I- under the identical conditions. NKPOC-DT-(I-)Me thus sets a new benchmark for industrial radioactive I2 adsorbents. This work not only provides a new insight for effectively enhancing the adsorption capacity of unit functional sites, but also advances POC as an efficient platform for radioiodine capture in industry.

Near-Full-Spectrum Emission Realized in a Single Lead Halide Perovskite across the Visible-Light Region.

The engineering of tunable photoluminescence (PL) in single materials with a full-spectrum emission represents a highly coveted objective but poses a formidable challenge. In this context, the realization of near-full-spectrum PL emission, spanning the visible light range from 424 to 620 nm, in a single-component two-dimensional (2D) hybrid lead halide perovskite, (ETA)2PbBr4 (ETA+=(HO)(CH2)2NH3 +), is reported, achieved through high-pressure treatment. A pressure-induced phase transition occurs upon compression, transforming the crystal structure from an orthorhombic phase under ambient conditions to a monoclinic structure at high pressure. This phase transition driven by the adaptive and dynamic configuration changes of organic amine cations enables an effective and continuous narrowing of the band gap in this halide crystal. The hydrogen bonding interactions between inorganic layers and organic amine cations (N-H⋅⋅⋅Br and O-H⋅⋅⋅Br hydrogen bonds) efficiently modulate the organic amine cations penetration and the octahedral distortion. Consequently, this phenomenon induces a phase transition and results in red-shifted PL emissions, leading to the near-full-spectrum emission. This work opens a possibility for achieving wide PL emissions with coverage across the visible light spectrum by employing high pressure in single halide perovskites.

Stimulus-Induced Dynamic Behavior Regulation of Flexible Crystals through the Tuning of Module Rigidity.

Introducing dynamic behavior into periodic frameworks has borne fruit in the form of flexible porous crystals. The detailed molecular design of frameworks in order to control their collective dynamics is of particular interest, for example, to achieve stimulus-induced behavior. Herein, by varying the degree of rigidity of ditopic pillar linkers, two isostructural flexible metal-organic frameworks (MOFs) with common rigid supermolecular building bilayers were constructed. The subtle substitution of single (in bibenzyl-4,4'-dicarboxylic acid; H2BBDC) with double (in 4,4'-stilbenedicarboxylic acid; H2SDC) C-C bonds in pillared linkers led to markedly different flexible behavior of these two MOFs. Upon the removal of guest molecules, both frameworks clearly show reversible single-crystal-to-single-crystal transformations involving the cis-trans conformation change and a resulting swing of the corresponding pillar linkers, which gives rise to Flex-Cd-MOF-1a and Flex-Cd-MOF-2a, respectively. Strikingly, a more favorable gas-induced dynamic behavior in Flex-Cd-MOF-2a was verified in detail by stepwise C3H6/C3H8 sorption isotherms and the corresponding in situ powder X-ray diffraction experiments. These insights are strongly supported by molecular modeling studies on the sorption mechanism that explores the sorption landscape. Furthermore, a consistency between the macroscopic elasticity and microscopic flexibility of Flex-Cd-MOF-2 was observed. This work fuels a growing interest in developing MOFs with desired chemomechanical functions and presents detailed insights into the origins of flexible MOFs.

Surface-Grafted Single-Atomic Pt-Nx Complex with a Precisely Regulating Coordination Sphere for Efficient Electron Acceptor-Inducing Interfacial Electron Transfer.

Based on the electron-withdrawing effect of the Pt(bpy)Cl2 molecule, a simple post-modification amide reaction was firstly used to graft it onto the surface of NH2-MIL-125, which performed as a highly efficient electron acceptor that induced the conversion of the photoinduced charge migration pathway from internal BDC→TiOx migration to external BDC→PtNx migration, significantly improving the efficiency of photoinduced electron transfer and separation. Furthermore, precisely regulating over the first coordination sphere of Pt single atoms was achieved using further post-modification with additional bipyridine to investigate the effect of Pt-Nx coordination numbers on reaction activity. The as-synthesized NML-PtN2 exhibited superior photocatalytic hydrogen evolution activity of 7.608 mmol g-1 h-1, a remarkable improvement of 225 and 2.26 times compared to pristine NH2-MIL-125 and NML-PtN4, respectively. In addition, the superior apparent quantum yield of 4.01 % (390 nm) and turnover frequency of 190.3 h-1 (0.78 wt % Pt SA; 129 times compared to Pt nanoparticles/NML) revealed the high solar utilization efficiency and hydrogen evolution activity of the material. And macroscopic color changes caused by the transition of carrier migration paths was first observed. It holds profound significance for the design of MOF-Molecule catalysts with efficient charge carrier separation and precise regulation of single-atom coordination sphere.

Planar Chlorination Engineering: A Strategy of Completely Breaking the Geometric Symmetry of Fe-N4 Site for Boosting Oxygen Electroreduction.

Introducing asymmetric elements and breaking the geometric symmetry of traditional metal-N4 site for boosting oxygen reduction reaction (ORR) are meaningful and challenging. Herein, the planar chlorination engineering of Fe-N4 site is first proposed for remarkably improving the ORR activity. The Fe-N4/CNCl catalyst with broken symmetry exhibits a half-wave potential (E1/2) of 0.917 V versus RHE, 49 and 72 mV higher than those of traditional Fe-N4/CN and commercial 20 wt% Pt/C catalysts. The Fe-N4/CNCl catalyst also has excellent stability for 25 000 cycles and good methanol tolerance ability. For Zn-air battery test, the Fe-N4/CNCl catalyst has the maximum power density of 228 mW cm-2 and outstanding stability during 150 h charge-discharge test, as the promising substitute of Pt-based catalysts in energy storage and conversion devices. The density functional theory calculation demonstrates that the adjacent C─Cl bond effectively breaks the symmetry of Fe-N4 site, downward shifts the d-band center of Fe, facilitates the reduction and release of OH*, and remarkably lowers the energy barrier of rate-determining step. This work reveals the enormous potential of planar chlorination engineering for boosting the ORR activity of traditional metal-N4 site by thoroughly breaking their geometric symmetry.

Supramolecular Assembly Frameworks (SAFs): Shaping the Future of Functional Materials.

Supramolecular assembly frameworks (SAFs) represent a new category of porous materials, utilizing non-covalent interactions, setting them apart from metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). This category includes but is not restricted to hydrogen-bonded organic frameworks and supramolecular organic frameworks. SAFs stand out for their outstanding porosity, crystallinity, and stability, alongside unique dissolution-recrystallization dynamics that enable significant structural and functional modifications. Crucially, their non-covalent assembly strategies allow for a balanced manipulation of porosity, symmetry, crystallinity, and dimensions, facilitating the creation of advanced crystalline porous materials unattainable through conventional covalent or coordination bond synthesis. Despite their considerable promise in overcoming several limitations inherent to MOFs and COFs, particularly in terms of solution-processability, SAFs have received relatively little attention in recent literature. This Minireview aims to shed light on standout SAFs, exploring their design principles, synthesis strategies, and characterization methods. It emphasizes their distinctive features and the broad spectrum of potential applications across various domains, aiming to catalyze further development and practical application within the scientific community.

A Highly Stable Microporous Calcium-Based MOF for C2H2/CO2 Separation with Low Regenerative Energy.

Most of the porous materials used for acetylene/carbon dioxide separation have the problems of poor stability and high energy requirements for regeneration, which significantly hinder their practical application in industries. Here, we report a novel calcium-based metal-organic framework (NKM-123) with excellent chemical stability against water, acids, and bases. Additionally, it has exceptional thermal stability, retaining its structural integrity at temperatures up to 300 °C. This material exhibits promising potential for separating C2H2 and CO2 gases. Furthermore, it demonstrates an adsorption heat of 29.3 kJ mol-1 for C2H2, which is lower than that observed in the majority of MOFs used for C2H2/CO2 separations. The preferential adsorption of C2H2 over that of CO2 is confirmed by dispersion-corrected density functional theory (DFT-D) calculations. In addition, the potential of industrial feasibility of NKM-123 for C2H2/CO2 separation is confirmed by transient breakthrough tests. The robust cycle performance and structural stability of NKM-123 during multiple breakthrough tests show great potential in the industrial separation of light hydrocarbons.

Metalation of metal-organic frameworks: fundamentals and applications.

Metalation of metal-organic frameworks (MOFs) has been developed as a prominent strategy for materials functionalization for pore chemistry modulation and property optimization. By introducing exotic metal ions/complexes/nanoparticles onto/into the parent framework, many metallized MOFs have exhibited significantly improved performance in a wide range of applications. In this review, we focus on the research progress in the metalation of metal-organic frameworks during the last five years, spanning the design principles, synthetic strategies, and potential applications. Based on the crystal engineering principles, a minor change in the MOF composition through metalation would lead to leveraged variation of properties. This review starts from the general strategies established for the incorporation of metal species within MOFs, followed by the design principles to graft the desired functionality while maintaining the porosity of frameworks. Facile metalation has contributed a great number of bespoke materials with excellent performance, and we summarize their applications in gas adsorption and separation, heterogeneous catalysis, detection and sensing, and energy storage and conversion. The underlying mechanisms are also investigated by state-of-the-art techniques and analyzed for gaining insight into the structure-property relationships, which would in turn facilitate the further development of design principles. Finally, the current challenges and opportunities in MOF metalation have been discussed, and the promising future directions for customizing the next-generation advanced materials have been outlined as well.

Broadband Emission Induced by Band-Edge Carrier Reconfiguration in 2D Hybrid Lead Halide Perovskites.

Broadband emission in hybrid lead halide perovskites (LHPs) has gained significant attention due to its potential applications in optoelectronic devices. The origin of this broadband emission is primarily attributed to the interactions between electrons and phonons. Most investigations have focused on the impact of structural characteristics of LHPs on broadband emission, while neglecting the role of electronic mobility. In this work, the study investigates the electronic origins of broadband emission in a family of 2D LHPs. Through spectroscopic experiments and density functional theory calculations, the study unveils that the electronic states of the organic ligands with conjugate effect in LHPs can extend to the band edges. These band-edge carriers are no longer localized only within the inorganic layers, leading to electronic coupling with molecular states in the barrier and giving rise to additional interactions with phonon modes, thereby resulting in broadband emission. The high-pressure photoluminescence measurements and theoretical calculations reveal that hydrostatic pressure can induce the reconfiguration of band-edge states of charge carriers, leading to different types of band alignment and achieving macroscopic control of carrier dynamics. The findings can provide valuable guidance for targeted synthesis of LHPs with broadband emission and corresponding design of state-of-the-art optoelectronic devices.

Reticular Modulation of Piezofluorochromic Behaviors in Organic Molecular Cages by Replacing Non-Luminous Components.

Organic piezochromic materials that manifest pressure-stimuli-responses are important in various fields such as data storage and anticounterfeiting. The manipulation of piezofluorochromic behaviors for these materials is promising but remains a great challenge. Herein, a non-luminous components regulated strategy is developed and organic molecular cages (OMCs), a burgeoning class of crystalline organic materials with structural dynamics, are first explored for the design of piezofluorochromic materials with tunable luminescence. A series of OMCs based on aggregation-induced emission (AIE) chromophores, termed Cage 1-3, are synthesized and their piezofluorochromic behaviors are investigated by diamond anvil cell technique. Due to the sufficient voids between its flexible chromophores offered by the OMC structure, Cage 1 exhibits thermofluorochromic and piezofluorochromic properties. Moreover, the piezofluorochromic performance of this OMC could be further promoted by replacing its non-luminous components with improved flexibilities, and a remarkable luminescence peak shift by 150 nm together with a response sensitivity of 13.8 nm GPa-1 was achieved upon hydrostatic compression. The cage structure plays a vital role in facilitating efficient and reversible piezofluorochromic behaviors. This study has shed light on the rational design and exploitation of OMCs as an exceptional platform to accomplish customizable piezofluorochromic behaviors and enlarge their potential applications in pressure-based luminescence.

Mechanoresponsive Flexible Crystals.

Flexible crystals have gained significant attention owing to their remarkable pliability, plasticity, and adaptability, making them highly popular in various research and application fields. The main challenges in developing flexible crystals lie in the rational design, preparation, and performance optimization of such crystals. Therefore, a comprehensive understanding of the fundamental origins of crystal flexibility is crucial for establishing evaluation criteria and design principles. This Perspective offers a retrospective analysis of the development of flexible crystals over the past two decades. It summarizes the elastic standards and possible plastic bending mechanisms tailored to diverse flexible crystals and analyzes the assessment of their theoretical basis and applicability. Meanwhile, the compatibility between crystal elasticity and plasticity has been discussed, unveiling the immense prospects of elastic/plastic crystals for applications in biomedicine, flexible electronic devices, and flexible optics. Furthermore, this Perspective presents state-of-the-art experimental avenues and analysis methods for investigating molecular interactions in molecular crystals, which is vital for the future exploration of the mechanisms of crystal flexibility.

Reticular synthesis of 8-connected carboxyl hydrogen-bonded organic frameworks for white-light-emission.

The rational design and construction of hydrogen-bonded organic frameworks (HOFs) are crucial for enabling their practical applications, but controlling their structure and preparation as intended remains challenging. Inspired by reticular chemistry, two novel blue-emitting NKM-HOF-1 and NKM-HOF-2 were successfully constructed based on two judiciously designed peripherally extended pentiptycene carboxylic acids, namely H8PEP-OBu and H8PEP-OMe, respectively. The large pores within these two HOFs can adsorb fluorescent molecules such as diketopyrrolopyrrole (DPP) and 9-anthraldehyde (AnC) to form HOFs ⊃ DPP/AnC composites, subsequently used in the fabrication of white-light-emitting devices (WLEDs). Specifically, two WLEDs were assembled by coating NKM-HOF-1 ⊃ DPP-0.13/AnC-3.5 and NKM-HOF-2 ⊃ DPP-0.12/AnC-3 on a 330 nm ultraviolet LED bulb, respectively. The corresponding CIE coordinates were (0.29, 0.33) and (0.32, 0.34), along with corresponding color temperatures of 7815 K and 6073 K. This work effectively demonstrates the feasibility of employing reticular chemistry strategies to predict and design HOFs with specific topologies for targeted applications.

Multi-stimuli-responsive luminescence enabled by crown ether anchored chiral antimony halide phosphors.

Stimuli-responsive optical materials have provided a powerful impetus for the development of intelligent optoelectronic devices. The family of organic-inorganic hybrid metal halides, distinguished by their structural diversity, presents a prospective platform for the advancement of stimuli-responsive optical materials. Here, we have employed a crown ether to anchor the A-site cation of a chiral antimony halide, enabling convenient control and modulation of its photophysical properties. The chirality-dependent asymmetric lattice distortion of inorganic skeletons assisted by a crown ether promotes the formation of self-trapped excitons (STEs), leading to a high photoluminescence quantum yield of over 85%, concomitant with the effective circularly polarized luminescence. The antimony halide enantiomers showcase highly sensitive stimuli-responsive luminescent behaviours towards excitation wavelength and temperature simultaneously, exhibiting a versatile reversible colour switching capability from blue to white and further to orange. In situ temperature-dependent luminescence spectra, time-resolved luminescence spectra and theoretical calculations reveal that the multi-stimuli-responsive luminescent behaviours stem from distinct STEs within zero-dimensional lattices. By virtue of the inherent flexibility and adaptability, these chiral antimony chlorides have promising prospects for future applications in cutting-edge fields such as multifunctional illumination technologies and intelligent sensing devices.