Metal-Coordination-Induced Fusion Creates Hollow Crystalline Molecular Superstructures

Gregorio, Maria Chiara di; Ranjan, Priyadarshi; Houben, Lothar; Shimon, Linda J. W.; Rechav, Katya; Lahav, Michal; Boom, Milko E. van der

doi:10.1021/jacs.8b03055

Cited by 25 publications

(21 citation statements)

References 49 publications

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“…The positive charges of the metal centers are balanced by chloride (Cl − ), as indicated by an average ratio of Cl/Ni = 2.2. These anions (from chloroform) 29 , 30 , 34 , 37 – 39 are not resolved as part of the crystallographic structures. The reaction with NiCl 2 and TPVA under solvothermal conditions resulted in uniform, sub-micron-sized crystals having a different morphology than observed in this study with NiBr 2 39 .…”

Section: Resultsmentioning

confidence: 99%

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Molecular cannibalism: Sacrificial materials as precursors for hollow and multidomain single crystals

et al. 2021

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The coexistence of single-crystallinity with a multidomain morphology is a paradoxical phenomenon occurring in biomineralization. Translating such feature to synthetic materials is a highly challenging process in crystal engineering. We demonstrate the formation of metallo-organic single-crystals with a unique appearance: six-connected half-rods forming a hexagonal-like tube. These uniform objects are formed from unstable, monodomain crystals. The monodomain crystals dissolve from the inner regions, while material is anisotropically added to their shell, resulting in hollow, single-crystals. Regardless of the different morphologies and growth mechanism, the crystallographic structures of the mono- and multidomain crystals are nearly identical. The chiral crystals are formed from achiral components, and belong to a rare space group (P622). Sonication of the solvents generating radical species is essential for forming the multidomain single-crystals. This process reduces the concentration of the active metal salt. Our approach offers opportunities to generate a new class of crystals.

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Section: Resultsmentioning

confidence: 99%

“…23 ). An excess of metal salt is known to stabilize and direct the formation of organic crystals with ligands that are structurally similar to TPVA 29 . Inactivating pyridine coordinating sites by excess of metal salts can be the cause of the here observed differences in growth kinetics (Fig.…”

Section: Resultsmentioning

confidence: 99%

Molecular cannibalism: Sacrificial materials as precursors for hollow and multidomain single crystals

et al. 2021

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“…41 A recent report on molecular superstructures also showed the importance of metal-coordination-induced fusion kinetics on the formation of superstructures. 42…”

Section: Superstructure Evolution Mechanismmentioning

confidence: 99%

Temperature-Controlled Evolution of Nanoporous MOF Crystallites into Hierarchically Porous Superstructures

Feng

Day

et al. 2019

Chem

105

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Hierarchically porous superstructures have been successfully assembled from nanoporous MOF crystallites. Benefiting from the dynamic coordination bond formation, hierarchical helical or multichannel tubular superstructures can be accessed through oriented assembly of MOF crystallites. This temperaturecontrolled structural evolution also enables the formation of crystalline hollow MOF tubes via self-templating and self-healing processes. Further incorporation of multiple components into these frameworks provides a fresh route for preparing stable, multivariate, and hierarchical frameworks with accessible catalytically active sites for heterogeneous catalysis.

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“…We have also demonstrated the metal-mediated formation of fused and hollow organic crystals. 67 Furthermore, these pyridine-based ligands have been used for the formation of three-dimensional halogen-bond-based organic frameworks (XBOFs). 68 …”

Section: Introductionmentioning

confidence: 99%

Chiral and SHG-Active Metal–Organic Frameworks Formed in Solution and on Surfaces: Uniformity, Morphology Control, Oriented Growth, and Postassembly Functionalization

et al. 2020

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We demonstrate the formation of uniform and oriented metal–organic frameworks using a combination of anion effects and surface chemistry. Subtle but significant morphological changes result from the nature of the coordinative counteranion of the following metal salts: NiX 2 with X = Br – , Cl – , NO 3 – , and OAc – . Crystals could be obtained in solution or by template surface growth. The latter results in truncated crystals that resemble a half structure of the solution-grown ones. The oriented surface-bound metal–organic frameworks (sMOFs) are obtained via a one-step solvothermal approach rather than in a layer-by-layer approach. The MOFs are grown on Si/SiOx substrates modified with an organic monolayer or on glass substrates covered with a transparent conductive oxide (TCO). Regardless of the different morphologies, the crystallographic packing is nearly identical and is not affected by the type of anion or by solution versus the surface chemistry. A propeller-type arrangement of the nonchiral ligands around the metal center affords a chiral structure with two geometrically different helical channels in a 2:1 ratio with the same handedness. To demonstrate the accessibility and porosity of the macroscopically oriented channels, a chromophore (resorufin sodium salt) was successfully embedded into the channels of the crystals by diffusion from solution, resulting in fluorescent crystals. These “ colored ” crystals displayed polarized emission (red) with a high polarization ratio because of the alignment of these dyes imposed by the crystallographic structure. A second-harmonic generation (SHG) study revealed Kleinman symmetry-forbidden nonlinear optical properties. These surface-bound and oriented SHG-active MOFs have the potential for use as single nonlinear optical (NLO) devices.

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Metal-Coordination-Induced Fusion Creates Hollow Crystalline Molecular Superstructures

Cited by 25 publications

References 49 publications

Molecular cannibalism: Sacrificial materials as precursors for hollow and multidomain single crystals

Molecular cannibalism: Sacrificial materials as precursors for hollow and multidomain single crystals

Temperature-Controlled Evolution of Nanoporous MOF Crystallites into Hierarchically Porous Superstructures

Chiral and SHG-Active Metal–Organic Frameworks Formed in Solution and on Surfaces: Uniformity, Morphology Control, Oriented Growth, and Postassembly Functionalization

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