Metal–organic frameworks in pursuit of size: the development of macroscopic single crystals

Abstract

Metal-organic frameworks are versatile structures with many different applications, from the industry to the clinic. Despite multiple synthesis approaches are possible to coordinate metals and organic ligands, some common strategies...

Isotope Effect-Enabled Crystal Enlargement in Metal–Organic Frameworks

“…Synthesizing a large single crystal is intriguing not only in its critical role to correlate the intrinsic property with the material structure 13,14 but also for the utilities (e.g., optical 15 and electrical 16 devices) where crystal size matters. 17 Some reports also revealed that large MOF crystals show superior 18 or even inverted 19 performance compared to the smaller counterparts. However, the fast nucleation kinetics in most MOFs usually results in small crystals because the precursors are rapidly consumed to generate new nuclei while a few are left for growth, 20 posing a great difficulty in synthesizing large MOF single crystals.…”

“…Metal–organic frameworks (MOFs), piled up by simple molecular bricks following the idea of reticular chemistry, − are cutting-edge porous crystalline materials with almost infinite possibilities in terms of both architecture and functionality. − Typically, most MOFs are obtained in powder form or as nanocrystals, which, however, limits some applications where only large bulk single crystals are qualified. Synthesizing a large single crystal is intriguing not only in its critical role to correlate the intrinsic property with the material structure , but also for the utilities (e.g., optical and electrical devices) where crystal size matters . Some reports also revealed that large MOF crystals show superior or even inverted performance compared to the smaller counterparts.…”

Phase‐Coherent Optical Frequency Up‐Conversion with Millimeter‐Size Zn(3‐ptz)2 Metal‐Organic Framework Single Crystals

“…Growing MOF single crystals to millimeter dimensions is a significant challenge. [27][28][29][30] Unlike more commonly used nonlinear optical materials such as potassium dihydrogen phosphate KH 2 PO 4 (KDP), of which the growth mechanism and kinetics are well known, [31] the general factors that control the self-assembly and crystallization mechanisms of MOF structures are largely unknown. [32][33][34] Recent progress in this direction was reported in Ref.…”

Terbium(iii)-based coordination polymer with millimeter-size single crystals and high selectivity and sensitivity for folic acid

“…Among them, complexes with large-size crystals are not only conducive to the accurate determination and analysis of structures but also provide a potential possibility for use in single crystal devices in practical applications. 25,26 Therefore, large single crystals are considered to be a convenient platform to study the intrinsic properties of a complex and to assess the "structure-property" interconnection. Despite the increasing interest in large-size complex single crystals, the strategies for obtaining such materials have not been fully studied, resulting in a relatively slow development in this field, because the influence of the external environment and internal factors on the crystal formation process is extremely complex (such as the reaction temperature, time, pH, cooling rate, reactant concentration, ratio, etc.).…”