Post-synthetic modification and chemical modulation of the ZIF-8 MOF using 3-mercaptopropionic acid (MPA): a multi-technique study on thermodynamic and kinetic aspects

Segovia, Gustavo M.; Allegretto, Juan A.; Bindini, Elisa; Pizarro, Lucía Belén; Lüdtke, Tanja; Moya, Sergio; Silvio, Desirè Di; Tuninetti, Jimena Soledad; Picco, Agustín Silvio; Ceolı́n, Marcelo; Azzaroni, Omar; Rafti, Matías

doi:10.1039/d1me00080b

Cited by 5 publications

(3 citation statements)

References 64 publications

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“…Moreover, when a small amount of HPBI was added (Figure 5b,c), the single primary peak of pure ZIF-8 split into two peaks. As we have excluded the effect of solvent on the variation of sedimentation coefficient, the smaller peak should stand for the ZIF-8 particles whose surfaces were "coordinatively etched" 34 by HPBI molecules at the site of Zn 2+ . The larger peak can be attributed to the agglomeration of ZIF-8 particles, either pure or surface-etched ones.…”

Section: Resultsmentioning

confidence: 99%

Unraveling the Strong Fluorescence Enhancement of HPBI Molecules by ZIF-8 Colloidal Suspensions via Adsorption Analysis

Zhang

Yuan

et al. 2023

Langmuir

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Enhancing the fluorescence of organic dye by colloidal particles is one of the most promising routes to optimize fluorescence detection. However, in addition to metallic particles, which serve as the most frequently used particles and have been found to employ the plasmonic resonance to provide strong fluorescence enhancement, neither new types of colloidal particles nor new fluorescence mechanisms have been intensively explored in recent years. In this work, strongly enhanced fluorescence was observed when 2-(2-hydroxyphenyl)-1H-benzimidazole (HPBI) molecules were simply mixed with zeolitic imidazolate framework-8 (ZIF-8) colloidal suspensions. Moreover, the enhancement factor ΔI = I HPBI+ZIF‑8/IHPBI does not increase accordingly with the increasing amount of HPBI. To find out how the strong fluorescence was triggered and affected by the amount of HPBI, multiple techniques were applied to analyze the adsorption behavior. By combining analytical ultracentrifugation with first-principles calculations, we proposed that HPBI molecules were adsorbed onto the surface of ZIF-8 particles coordinatively and electrostatically, depending on the concentration of HPBI molecules. The coordinative adsorption would result in a new kind of fluorescence emitter. The new fluorescence emitters tend to distribute on the outer surface of ZIF-8 particles periodically. The distance between each fluorescence emitter is fixed and much smaller than the wavelength of the excitation light. Thus, it can be concluded that collective spontaneous emission might be triggered.

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Section: Resultsmentioning

confidence: 99%

Unraveling the Strong Fluorescence Enhancement of HPBI Molecules by ZIF-8 Colloidal Suspensions via Adsorption Analysis

Zhang

Yuan

et al. 2023

Langmuir

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“…For coordination complexes, reaction parameters, such as reaction stoichiometry, temperature, pH, concentration, and additives, have been proven to be effective strategies to tune their structures and properties. − However, the kinetic and thermodynamic factors should also be considered to achieve their controllable syntheses. Thermodynamics and kinetics both can determine the arrangement of atoms in crystal materials, where thermodynamics defines the most stable arrangement with the lowest total free energy, while kinetics controls the path and time scale in reaching the thermodynamic state. − However, the arrangement of atoms can be arrested at local minima to generate metastable or kinetically controlled products, which could be observed in the one-pot self-assembly process of coordination complexes, and led to the formation of not only thermodynamic but also kinetic products. − Kinetic products have been studied to convert them into the more stable thermodynamic form by applying appropriate stimuli such as reaction time, temperature, pressure, light, guest molecule removal, or exchange. − For the oligomeric luminescent cuprous complexes, − the kinetic and thermodynamic factors can singly or together play important roles to precisely regulate the cuprous complexes’ structures and luminescence. − …”

Section: Introductionmentioning

confidence: 99%

Controllable Preparation and Direct Observation of an Interconversion between Kinetically and Thermodynamically Stable Luminescent Multicuprous Coordination Complexes

Cao,

Li,

Tan

et al. 2024

Crystal Growth & Design

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We report the controlled preparation of kinetically and thermodynamically luminescent multinuclear cuprous coordination complexes. On reaction of the bidentate P/N-ligand (2-(diphenylphosphino)pyridine, abbreviated as dppy) and copper(I) with a similar stoichiometry but in different concentration conditions at ambient temperature, hexagonal crystals of [Cu 2 (μ-dppy) 3 Cl]PF 6 •CH 2 Cl 2 (1) or polyhedron crystals of [Cu 4 (μ-dppy) 6 Cl](PF 6 ) 3 (2) were formed as kinetic or thermodynamic products, respectively. Investigation of the structures, morphologies, theoretical calculation, and photophysical properties of the multinuclear cuprous coordination complexes demonstrates the formation of and differences between kinetically and thermodynamically stable conformations. Single-crystal X-ray structural analyses indicated that 1 features the head-to-head orientation dppy bridged dinuclear trefoil-like Cu 2 -core with one terminal Cl − , and tetranuclear 2 can be regarded as a Cl − bridged dimer of 1 with two-third flipping head-to-tail dppy ligands. The density functional theory (DFT) calculations demonstrated that 2 had a lower frontier molecular orbital energy than 1, with an energy difference of 320.76 kJ/mol. Intriguingly, the controllable reversible transformation between 1 and 2 can be achieved under suitable conditions. By soaking the crystal in the mother liquor or alcohol, the kinetically stable 1 can slowly transform to the thermodynamically stable 2, or conversely, 2 can also quickly reconstruct to 1 when it is soaked in a chloride solution. Steadily changing morphologies, photoluminescence, as well as powder X-ray diffraction patterns were observed during the gradual transformation process. Based on structural analyses, a feasible transforming mechanism was proposed. The energetic and structural analyses of and the interconversion process between kinetically and thermodynamically stable multicuprous complexes here provide insights into the relations among the structures, morphologies, and properties of the metal−organic coordination materials at the molecular level.

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“…Recent advances in the study of MOF interactions with substrates, particularly using isothermal titration calorimetry (ITC), allow for detailed investigations into the nature and magnitude of adsorption energies, even when noncovalent interactions are involved. − Determining where and how a dye or substrate attaches to a MOF may be critical to improving a photocatalytic array, as the spacing and density of dyes will dramatically affect the photochemical properties of the assembly.…”

Section: Introductionmentioning

confidence: 99%

Noncovalent Surface Modification of Metal–Organic Frameworks: Unscrambling Adsorption Properties via Isothermal Titration Calorimetry

et al. 2022

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Despite the importance of noncovalent interactions in the utilization of metal−organic frameworks (MOFs), using these interactions to functionalize MOFs has rarely been explored. The ease of functionalization and potential for surface-selective functionalization makes modification via noncovalent interactions promising for the creation of porous photocatalytic assemblies. Using isothermal titration calorimetry, photoluminescence measurements, and desorption experiments, we have explored the nature and magnitude of the interactions of [Ru(bpy) 2 (bpy-R)] 2+ -functionalized dyes with the surface of MIL-96, where R = C 3 , C 8 , C 12 , and C 18 alkyl chains of either straight-chain or cyclic conformations. The orientation of the dyes appears to be flat against the surface with respect to the long alkyl chains, and the surface concentration approaches a monolayer at high initial concentrations of dye. Strangely, the dodecyl-functionalized dye, despite having a smaller interaction energy and larger footprint than either octylfunctionalized dye, achieves the highest maximum surface concentration. Based on photoluminescence spectra, desorption experiments, and ITC data, we believe this is due to the core of the dye being lifted from the surface as the chain length increases. Our understanding of these interactions is important for further utilization of this method for the functionalization of the internal and external surface areas of MOFs.

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Post-synthetic modification and chemical modulation of the ZIF-8 MOF using 3-mercaptopropionic acid (MPA): a multi-technique study on thermodynamic and kinetic aspects

Abstract: We hereby report on thermodynamic and kinetic aspects of ZIF-8 MOF synthesis from methanolic solutions of precursors and 3-mercaptopropionic acid (MPA) acting as chemical modifying agent. MPA bears great interest...

Cited by 5 publications

References 64 publications

Unraveling the Strong Fluorescence Enhancement of HPBI Molecules by ZIF-8 Colloidal Suspensions via Adsorption Analysis

Unraveling the Strong Fluorescence Enhancement of HPBI Molecules by ZIF-8 Colloidal Suspensions via Adsorption Analysis

Controllable Preparation and Direct Observation of an Interconversion between Kinetically and Thermodynamically Stable Luminescent Multicuprous Coordination Complexes

Noncovalent Surface Modification of Metal–Organic Frameworks: Unscrambling Adsorption Properties via Isothermal Titration Calorimetry

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