Ligand Exchange Process Research Articles

Aqueous phase transfer of near-infrared ZnCuInS2/ZnS quantum dots: Synthesis and characterization

Cadmium-free and NIR fluorescent QDs are promising candidates for bio-application. Thus, we present the synthesis of ternary ZnCuInS2/ZnS (ZCIS/ZnS) quantum dots (QDs) where the molar variation of Cu/Zn of the precursors was used to tune the optical and structural properties. QDs with Cu/Zn molar ratio of 2/1 passivated with ZnS exhibited the best optical properties. They showed dominant near-infrared photoluminescence (approx. 850 nm) and highest quantum yield (approx. 52 %, λexc = 500 nm). Therefore, they were further subject to modification to ensure their transfer to the aqueous phase and improve biocompatibility. For this, different functionalization approaches were used. The first method relied on encapsulation with polymers like PSMA (poly(styrene co-maleic anhydride)) and PMAO (poly(maleic anhydride-alt-1-octadecene) coupled with polyetheramine (JEFF; Jeffamine M-1000), and the second relied on hydrophilization with PMAO. Furthermore, we also applied a surface ligand exchange process using DHLA (dihydrolipoic acid) and polyethylene glycol (PEG)-appended DHLA. The comprehensive study indicated that ZnCuInS2/ZnS QDs functionalized with PMAO (ZnCuInS2/ZnS@PMO) exhibited the highest photoluminescence (PL QY) along with ensured high colloidal stability in aqueous media. Moreover, no noticeable deterioration of the photoluminescence profile was observed for all used functionalization approaches. However, a significant decrease in QY was observed for almost all functionalized QDs except those that were PMO-capped. The synthesized QDs were systematically characterized by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), UV–Vis absorption spectroscopy, and fluorescence spectroscopy. Biological studies indicate that the obtained hydrophilic ZCIS QDs are biocompatible and localized intracellularly inside endosomes.

Solvent‐Engineering‐Assisted Ligand Exchange Strategy for High‐Efficiency AgBiS2 Quantum Dot Solar Cells

AbstractAs the initial synthesized colloidal quantum dots (CQDs) are generally capped with insulating ligands, ligand exchange strategies are essential in the fabrication of CQD films for solar cells, which can regulate the surface chemical states of CQDs to make them more suitable for thin‐film optoelectronic devices. However, uncontrollable surface adsorption of water molecules during the ligand exchange process introduces new defect sites, thereby impairing the resultant device performance, which attracts more efforts devoted to it but remains a puzzle. Here, we develop a solvent‐engineering‐assisted ligand exchange strategy to revamp the surface adsorption, improve the exchange efficiency, and modulate the surface chemistry for the environmentally friendly lead‐free silver bismuth disulfide (AgBiS2) CQDs. The optimized AgBiS2 CQD solar cells deliver an outstanding champion power conversion efficiency (PCE) of up to 8.95 % and improved long‐term stability. Our strategy is less environment‐dependent and can produce solar cells with negligible performance variance for several batches across several months. Our work demonstrates the critical role of solvents for ligand exchange in the surface chemistry of CQDs and the realization of high‐performance photovoltaic devices in a highly reproducible manner.

Crosslinkable Ligands for High-Density Photo-Patterning of Perovskite Nanocrystals.

Perovskite nanocrystals (PNCs) are promising luminescent materials for electronic color displays due to their high luminescence efficiency, widely-tunable emission wavelengths, and narrow emission linewidth. Their application in emerging display technologiesnecessitates precise micron-scale patterningwhile maintaining good optical performance. Although photolithography is a well-established micro-patterning technique in the industry, conventional processes are incompatible with PNCs as the use of polar solvents can damage the ionic PNCs, causingsevere luminescence quenching. Here,we report the rational design and synthesis of a new bidentate photo-crosslinkable ligand for the direct photo-patterning of PNCs. Each ligand contains two photosensitive acrylate groups and two carboxylate groups, and is introduced to the PNCs via an entropy-driven ligand exchange process. In a close-packed thin film, the acrylate ligands photo-polymerize and crosslink under ultraviolet light, rendering the PNCs insoluble in developing solvents. A high-density crosslinked PNC film with an optical density of 1.1 is attained at 1.4µm thickness, surpassing industry requirements on the absorption coefficient. Micron-scale patterning is further demonstrated using direct laser writing, producing well-defined 20µm features. This study thus offers an effective and versatile approach for micro-patterning PNCs, and may also be broadly applicable to other nanomaterial systems.

Synergistic effect of oxygen vacancies and functionalized ligands selectively enhanced the photocatalytic oxidation of methane to carbon monoxide

The titanium-based metal–organic framework MIL-125(Ti) has been widely investigated in photocatalytic carbon dioxide reduction and water splitting, but rarely studied in photocatalytic methane conversion by employing only water as an oxidant under mild conditions. Simultaneously controlling products with high yield and selectivity is highly challenging in methane conversion. Herein, we develop a series of functionalized titanium metal–organic frameworks via a facile organic ligand exchange process. The abundant Ti3+ active sites induced by oxygen vacancies and functionalized ligands synergistically facilitate the adsorption and activation of methane molecules. The carbon monoxide yield over NH2-MIL-125(Ti) increased to 198.6 μmol·gcat−1·h−1 with a high selectivity of 87.1 % under simulated solar illumination. Combined with in-situ characterizations and density functional theoretical calculations, the results confirmed that Ti3+ active sites induced by oxygen vacancies and amino functional groups synergistically enhanced the photocatalytic conversion of methane and elucidate CH4-to-CO conversion mechanism. This study does not only provide insights into the rational design of metal–organic frameworks with copious oxygen vacancies and functional groups, but also provides some significant cognition for photocatalytic methane conversion.

Solvent-Engineering-Assisted Ligand Exchange Strategy for High-Efficiency AgBiS2 Quantum Dot Solar Cells.

As the initial synthesized colloidal quantum dots (CQDs) are generally capped with insulating ligands, ligand exchange strategies are essential in the fabrication of CQD films for solar cells, which can regulate the surface chemical states of CQDs to make them more suitable for thin-film optoelectronic devices. However, uncontrollable surface adsorption of water molecules during the ligand exchange process introduces new defect sites, thereby impairing the resultant device performance, which attracts more efforts devoted to it but remains a puzzle. Here, we develop a solvent-engineering-assisted ligand exchange strategy to revamp the surface adsorption, improve the exchange efficiency, and modulate the surface chemistry for the environmentally friendly lead-free silver bismuth disulfide (AgBiS2) CQDs. The optimized AgBiS2 CQD solar cells deliver an outstanding champion power conversion efficiency (PCE) of up to 8.95% and improved long-term stability. Our strategy is less environment-dependent and can produce solar cells with negligible performance variance for several batches across several months. Our work demonstrates the critical role of solvents for ligand exchange in the surface chemistry of CQDs and the realization of high-performance photovoltaic devices in a highly reproducible manner.

Synergic Surface Modifications of PbS Quantum Dots by Sodium Acetate in Solid-State Ligand Exchange toward Short-Wave Infrared Photodetectors.

PbS quantum dots (QDs) are promising for short-wave infrared (SWIR) photodetection and imaging. Solid-state ligand exchange (SSLE) is a low-fabrication-threshold QD solid fabrication method. However, QD treatment by SSLE remains challenging in seeking refined surface passivation to achieve the desired device performance. This work investigates using NaAc in the ligand exchange process to enhance the film morphology and electronic coupling configuration of QD solids. By implementing various film and photodetector device characterization studies, we confirm that adding NaAc with a prominent adding ratio of 20 wt % NaAc with tetrabutylammonium iodide (TBAI) in the SSLE leads to an improved film morphology, reduced surface roughness, and decreased trap states in the QD solid films. Moreover, compared to the devices without NaAc treatment, those fabricated with NaAc-treated QD solids exhibit an enhanced performance, including lower dark current density (<100 nA/cm2), faster response speed, higher responsivity, detectivity, and external quantum efficiency (EQE reaching 25%). The discoveries can be insightful in developing efficient, low-cost, and low-fabrication-threshold QD SWIR detection and imager applications.

Lead-Free Nanocrystal Inks for Flexible Optoelectronic Devices

The exploration of AgBiS2 quantum dots (QDs) as an environmentally friendly alternative to previously-explored infrared-absorbing QDs has continued to gain interest in the past few years. Applications in optoelectronic devices are facilitated by colloidally stable inks that can be used to deposit films with favorable material properties on diverse substrates, including flexible substrates applicable to lightweight and wearable sensors. Here, we demonstrate that a rapid biphasic ligand exchange process can be used to make a AgBiS2 QD ink. The properties of deposited films are explored in lateral photoconductive devices and in heterojunction photovoltaic devices. In addition to this, we also demonstrated the use of this environmentally benign QD ink in flexible devices: the photo response was unchanged when the device was flat or bent. These results demonstrate the versatility of solution-phase ligand exchange approaches to QD-based optoelectronic devices.

Benzyl viologen dichloride as a novel ligand for CdSe CQDs in hybrid QDs/organic photodiodes

The use of colloidal quantum dots (CQDs) in advanced optoelectronic devices requires the substitution of bulky long ligands with short organic ligands. The search for a short-ligand that can create stable quantum solids without compromising the confinement of the CQDs is of paramount importance.Within this context, we present a novel surface passivation ligand, benzyl viologene dichloride (BVD-Cl), as a replacement for the conventional trioctylphosphine oxide (TOPO) capping of CdSe CQDs. BVD-Cl enables the creation of a CdSe quantum solid while retaining quantum confinement. To demonstrate the efficacy of this ligand-exchange process, we utilised Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray spectrometry (EDX), high-resolution transmission electron microscopy (HR-TEM), and X-ray photoemission spectroscopy (XPS). We then implanted the new BVD-Cl:CdSe quantum film as the main inorganic QDs layer into a hybrid photodiode combined with poly 3-hexylthiophene (P3HT) as the organic layer. The photodiode demonstrated high sensitivity to light stimuli and rectifying behaviour, with a responsivity of 70 mA/W at 550 nm. Our observations imply that using BVD-Cl as a surface passivation ligand for CQDs has significant implications for the development of advanced optoelectronic devices.

Synthesis and Characterization of Epitaxially-Fused Quantum Dot Superlattices at the Single Grain Limit

Epitaxially-fused superlattices of colloidal quantum dots (QD epi-SLs) may exhibit electronic minibands and high-mobility charge transport, but doing so requires epi-SLs with extremely high degrees of spatial and chemical (compositional) uniformity. In this talk, I will discuss both our efforts to understand and improve the epi-SL formation process, as well as recent charge transport studies on single epi-SL grains.Epi-SLs are synthesized from a parent SL structure, typically composed of QDs with long insulating ligands. Over the past several years, we have developed insight into the physical and chemical mechanisms by which this parent SL structure is converted into an epi-SL. I will present detailed, multi-model structural characterization of the SL structures, which unveils the astonishing choreographic process by which millions of QDs rotate and translate, in concert, to form the epi-SL.This structural transformation is initiated by chemical changes to the QD ligand layer, usually through manual introduction of liquids into the SL film. Mechanistic studies into this ligand-exchange process reveal a multi-step chemical sequence that initiates with a simple acid-base reaction. We exploit this insight to fabricate epi-SLs by means of photochemical triggering (using ultraviolet illumination) rather than alternative “hands-on” techniques which suffer from poor experimental control and pronounced chemical inhomogeneity and structural damage in the films. The use of light to trigger the SL conversion process enables much finer control in both the temporal and spatial domains, opening the door to much larger-area SL films and direct photopatterning of epi-SLs.In the latter portion of the talk, I will present recent work charge transport studies in individual, highly-ordered PbSe QD epi-SL grains. One technical challenge in making these devices is the inherent mismatch in using traditional microfabrication techniques to make single-grained devices of air-sensitive materials. Here, we demonstrate the air-free fabrication of microscale field-effect transistors (μ-FETs) with channels consisting of single PbSe QD epi-SL grains (~ 1 -10 µm grain sizes) and analyze charge transport phenomena in these samples. The devices exhibit p-channel or ambipolar transport with a hole mobility as high as 3.5 cm2 V–1 s–1 at 290 K and 6.5 cm2 V–1 s–1 at 170–220 K, one order of magnitude larger than that of previous QD solids.

Chemically Tailored Metal‐Organic Frameworks for Enhanced Capture of Short‐ and Long‐Chain Per‐ and Polyfluoroalkyl Substances from Water

AbstractPer‐ and polyfluoroalkyl substances (PFAS) are emerging as bioaccumulative and toxic water pollutants, posing a large threat to human and aquatic organisms. This threat is aggravated by their extreme persistence to common degradation methods. Adsorption is regarded as the most conventional method to treat these contaminants, however, existing sorbents present considerable limitations on performance. The development of more efficient PFAS adsorbents is therefore of urgent need. The class of metal‐organic frameworks (MOFs) can hold great promise for these purposes, featuring porous materials with high tailoring potential. Herein, a series of functionalized Zr‐MOFs have been designed with boosted capacities for the adsorption of short‐ and long‐chain perfluorinated carboxylic acids of environmental interest. The approach relies on chemistry‐based concepts to introduce targeted post‐synthetic modifications that promote PFAS···MOF interactions, specifically through coordinative bonding and hydrophobic effects. In particular, the framework TFA‐MOF‐808 (TFA = trifluoroacetic acid) displays the highest capture capacities reported for MOF materials in this pollutant class. Mechanistic studies, assisted by advanced synchrotron characterization techniques and theoretical calculations, support a ligand exchange process occurring during the adsorption phenomena. The results demonstrate the potential of this design approach in developing advanced PFAS sorbents with optimal performance.

Competitive Binding Kinetics of Methylmercury-Cysteine with Dissolved Organic Matter: Critical Impacts of Thiols on Adsorption and Uptake of Methylmercury by Algae.

Complexes with low-molecular-weight thiols are crucial species of methylmercury (MeHg) excreted by anaerobic Hg-methylating microbes, notably, MeHg-cysteine (MeHg-Cys). As MeHg-Cys diffuses into surface water, it would undergo a ligand exchange process with dissolved organic matter (DOM) under nonsulfidic conditions, inevitably altering MeHg speciation and bioavailability to phytoplankton. In this study, we investigated the competitive binding kinetics between MeHg-Cys and Suwannee River natural organic matter, and their influence on the adsorption and uptake of MeHg by the cyanobacterium, Synechocystis sp. PCC6803. Liquid chromatography-inductively coupled plasma mass spectrometry was employed to monitor the kinetics processes involving competition of DOM with Cys for MeHg binding, which revealed that competitive binding kinetics were dictated by the abundance of thiol moieties in DOM. Thiol concentrations of 0.97 and 49.34 μmol of thiol (g C)-1 resulted in competitive binding rate constant (k values) of 0.30 and 3.47 h-1, respectively. Furthermore, the time-dependent competitive binding of DOM toward MeHg-Cys significantly inhibited MeHg adsorption and uptake by cyanobacteria, an effect that was amplified by an increased thiol abundance in DOM. These findings offer valuable insights into the kinetic characteristics of MeHg's fate and transport, as well as their impact on bioconcentration in aquatic organisms within natural aquatic ecosystems.

Multifaceted anchoring ligands for uniform orientation and enhanced cubic-phase stability of perovskite quantum dots

All-inorganic CsPbI3 perovskite quantum dots (PQDs) hold significant potential for next-generation photovoltaics due to their unique optoelectronic properties, and the surface-bound ligand playing a key role in the stability and functionality of CsPbI3 PQDs. Initially used long-chain ligands in PQDs synthesis stabilize the black phase but hinder charge transport when employed to solar cells, necessitating their replacement with shorter ones. However, this leads to the formation of surface defects and loss of tensile strain, resulting in the transition to the undesired orthorhombic phase (δ-phase) and compromising PQD solar cell performance. Therefore, developing a ligand exchange process that achieves the optimal balance between conductivity and stability in PQD solid films continues to be a significant challenge. To address these issues, we developed an efficient ligand-exchange process utilizing a multifaceted anchoring ligand, 2-thiophenemethylammonium iodide (ThMAI). The larger ionic size of ThMA+ compared to Cs+ facilitates the restoration of surface tensile strain in PQDs, while its thiophene and ammonium groups enable effective passivation of surface defects. Owing to these advantages, ThMAI-treated CsPbI3 PQD thin films exhibit improved carrier lifetime, uniform PQD orientation, and increased ambient stability. As a result, the ThMAI-treated CsPbI3 PQD solar cells demonstrate an improved power conversion efficiency (PCE) of 15.3 % and an enhanced device stability.

Water-Soluble Lead Sulfide Nanoparticles: Direct Synthesis and Ligand Exchange Routes.

Colloidal semiconductor nanoparticles (NPs) represent an emergent state of matter with unique properties, bridging bulk materials and molecular structures. Their distinct physical attributes, such as bandgap and photoluminescence, are intricately tied to their size and morphology. Ligand passivation plays a crucial role in shaping NPs and determining their physical properties. Ligand exchange (LE) offers a versatile approach to tailoring NP properties, often guided by Pearson's Hard-Soft Acid-Base theory. Lead sulfide (PbS), a semiconductor of considerable interest, exhibits size-dependent tunable bandgaps from the infrared to the visible range. Here, we present two methods for synthesizing water-soluble, polyvinylpyrrolidone (PVP)-coated PbS NPs. The first involves direct synthesis in an aqueous solution while utilizing PVP as the surfactant for the formation of nano-cubes with a crystal coherence length of ~30 nm, while the second involves LE from octadecylamine-coated PbS truncated nano-cubes to PVP-coated PbS NPs with a crystal coherence length of ~15 nm. Multiple characterization techniques, including X-ray diffraction, transmission electron microscopy, Fourier-transform infrared spectroscopy, and thermal gravimetric analysis, confirmed the results of the synthesis and allowed us to monitor the ligand exchange process. Our findings demonstrate efficient and environmentally friendly approaches for synthesizing PVP-coated PbS NPs.

Dyotropic Rearrangement of an Iron–Aluminium Complex

Ligand exchange processes at metal complexes underpin their reactivity and catalytic applications. While mechanisms of ligand exchange at single site complexes are well established, occurring through textbook associative, dissociative and interchange mechanisms, those involving heterometallic complexes are less well developed. Here we report the reactions of a well‐defined Fe–Al hydride complex with exogeneous ligands (CO and CNR, R = Me, tBu, Xyl = 2,6‐Me2C6H3). Based on DFT calculations we suggest that these reactions occur through a dyotropic rearrangement, this involves initial coordination of the exogenous ligand at Al followed by migration to Fe, with simultaneous migration of a hydride ligand from Fe to Al. Such processes are rare for heterometallic complexes. We study the bonding and mechanism of the dyotropic rearrangement through in‐depth computational analysis (NBO, IBOs, CLMO analysis, QTAIM, NCIplot, IMGH), shedding new light on how the electronic structure of the heterometallic core responds to the migration of ligands between metal sites. The dyotropic rearrangement fundamentally changes the nature of the hydride ligands, exposing new nucleophilic reactivity as evidenced by insertion reactions with CO2, isocyanates, as well as isocyanides.

Dyotropic Rearrangement of an Iron-Aluminium Complex.

Ligand exchange processes at metal complexes underpin their reactivity and catalytic applications. While mechanisms of ligand exchange at single site complexes are well established, occurring through textbook associative, dissociative and interchange mechanisms, those involving heterometallic complexes are less well developed. Here we report the reactions of a well-defined Fe-Al dihydride complex with exogenous ligands (CO and CNR, R=Me, tBu, Xyl=2,6-Me2C6H3). Based on DFT calculations we suggest that these reactions occur through a dyotropic rearrangement, this involves initial coordination of the exogenous ligand at Al followed by migration to Fe, with simultaneous migration of a hydride ligand from Fe to Al. Such processes are rare for heterometallic complexes. We study the bonding and mechanism of the dyotropic rearrangement through in-depth computational analysis (NBO, IBOs, CLMO analysis, QTAIM, NCIplot, IGMH), shedding new light on how the electronic structure of the heterometallic core responds to the migration of ligands between metal sites. The dyotropic rearrangement fundamentally changes the nature of the hydride ligands, exposing new nucleophilic reactivity as evidenced by insertion reactions with CO2, isocyanates, as well as isocyanides.

Sensitization of Europium Oxide Nanoparticles Enhances Signal-to-Noise over Autofluorescence with Time-Gated Luminescence Detection.

Clinical translation of nanoparticle-based therapeutics has been limited, and a lack of preclinical delivery characterization is partly to blame, limiting our understanding of the mechanisms of failure. The improvement of the preclinical delivery assessment requires nanoparticles with higher detectability. This work focused on the exploration of several aromatic carboxylic ligands (terephthalic acid, quinaldic acid, and kynurenic acid) for the sensitization of europium oxide nanoparticles with a long emission lifetime to overcome cellular autofluorescence, a key confounder of detection in luminescence-based bioimaging. A facile one-pot synthesis and ligand exchange process generated and sensitized ultrasmall Eu2O3 cores. As reflected in the emission spectra and lifetimes, ligand binding yielded unique coordination environments around Eu3+. Then, the efficacy of sensitization was tested against the autofluorescence provided by tissue lysate. Normal (simultaneous excite-read) measurements showed integrated signal improvements over autofluorescence of 2.2-, 3.9-, and 14.0-fold for EuTA, EuQA, and EuKA, respectively. In time-gated mode, the improvements over autofluorescence were more dramatic with fold differences of 75-, 89-, and 108-fold for EuTA, EuQA, and EuKA, respectively. The investigation of novel sensitizers expands the breadth of the field of sensitized lanthanide oxide nanoparticles, and the signal enhancement observed with sensitization and time-gating supports the utility of the generated samples for future bioimaging applications.

Facile Synthesis and Characterization of Uniform Au Nanospheres Capped by Citrate for Biomedical Applications.

We report a simple and versatile method for effectively replacing the toxic ligands, such as cetyltrimethylammonium bromide (CTAB) and cetyltrimethylammonium chloride (CTAC), on the surface of Au nanospheres with different sizes by citrate. The method involves the deposition of an ultrathin shell of fresh Au in the presence of sodium citrate at an adequate concentration. After the ligand exchange process, multiple techniques are used to confirm that the surface of the resultant Au nanospheres is covered by citrate while there is no sign of aggregation. We also demonstrate the mitigation of cell toxicity after exchanging the surface-bound CTAB/CTAC with citrate, opening the door to a range of biomedical applications.

Tail-group tailoring for narrower green electroluminescence: The role of methoxysilane derivatives in QLEDs

Metal halide perovskite nanocrystals (PeNCs) are garnering significant interest as the future of light-emitting materials, primarily due to their exceptional emission characteristics, which include strong excitonic absorption and narrow-band, high-intensity emission. These properties are intricately linked to the surface chemistry of the nanocrystals, which can be effectively manipulated through the choice of ligands and specific reaction conditions during synthesis or subsequent ligand exchanges. In the first, we explore the ligand exchange processing in hexane with thiol-functionalized methoxysilanes, notable for their short chain and bifurcated structure. In the case of surface-modified PeNCs using methoxysilane, strain engineering is dominated by the tail group, which plays an even more important role than size dispersion in their effects on color purity and gamut. In addition, the methoxysilane ligand-induced lattice strain may also significantly alter charge transporting hehavior, as is demonstrated on zinc oxide (ZnO) using 3-aminopropyltrimethoxysilane (APTMS). These interesting observations arise from nanostrained optoelectronic materials, and are attractive for the development of high-purity electroluminescence devices.

PbS Colloidal Quantum Dots: Ligand Exchange in Solution

PbS colloidal quantum dots (CQDs) have the advantages of adjustable band gap, large exciton Bohr radius, controllable size, easy synthesis, and potential multi-exciton effect, making them attractive for photodetectors and solar cells. However, the long ligand chain wrapped on PbS CQDs limits carrier transport, and defect states of as-synthesized CQDs increase non-radiative recombination, negatively affecting photovoltaic performance. Surface properties determine the characteristics of CQDs, so ligand exchange processes are crucial. Because solution phase ligand exchange reduces labor and time requirements, it is more advantageous than solid phase ligand exchange. This review discusses the solution phase ligand exchange process of PbS CQDs, emphasizing the impact of surface ligands on conformation and conductivity.

Structure-Assisted Boronic Acid Implanted Mesoporous Metal-Organic Frameworks for Specific Extraction of cis-Diol Molecules.

cis-Diol-containing molecules, an essential type of compounds in living organisms, have attracted intensive research interest from various fields. The analysis of cis-diol-containing molecules is still suffering from some drawbacks, including low abundance and abundant interference. Metal-organic frameworks (MOFs) have proven to be an ideal sorbent for sample preparation. However, most of the reported MOFs are mainly restricted to a microporous regime (pore size <2 nm), which greatly limits the application. Herein, a facile strategy is established to construction of boronate affinity MOFs via the postsynthetic ligand-exchange process. Owing to the fact that the ligand-exchange process was assisted by the structural integrity of the primitive metal-organic framework and the great compatibility of click chemistry, the obtained EPBA-PCN-333(Fe) is able to realize the maximum maintaining the porosity and crystallinity of the parent material. Several intriguing features of EPBA-PCN-333(Fe) (e.g., excellent selectivity, efficient diffusion, good accessibility, and size exclusion effect) are experimentally demonstrated via a series of cis-diol-containing molecules with different molecular sizes (small molecules, glycopeptides, and glycoproteins). The binding performance of EPBA-PCN-333(Fe) is evaluated by employing catechol as the test molecule (binding capacity: 0.25 mmol/g, LOD: 200 ng/mL). Finally, the real-world applications of EPBA-PCN-333(Fe) were demonstrated by the detection of nucleosides of human urine samples.