Crystal engineering of organic and metal-organic solids

2010 ◽  
Author(s):  
Dejan-Kresimir Bucar
Keyword(s):  
Crystal Engineering ◽  
Organic Solids ◽  
Metal Organic

Magnetic Ordering via Itinerant Ferromagnetism in a Metal-Organic Framework

2020 ◽  
Author(s):  
Jesse Park ◽  
Brianna Collins ◽  
Lucy Darago ◽  
Tomce Runcevski ◽  
Michael Aubrey ◽  
...  
Keyword(s):  
Charge Transport ◽  
Magnetic Order ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Magnetic Ordering ◽  
Double Exchange ◽  
Itinerant Ferromagnetism ◽  
Organic Solids ◽  
Metal Organic ◽  
Organic Framework

<b>Materials that combine magnetic order with other desirable physical attributes offer to revolutionize our energy landscape. Indeed, such materials could find transformative applications in spintronics, quantum sensing, low-density magnets, and gas separations. As a result, efforts to design multifunctional magnetic materials have recently moved beyond traditional solid-state materials to metal–organic solids. Among these, metal–organic frameworks in particular bear structures that offer intrinsic porosity, vast chemical and structural programmability, and tunability of electronic properties. Nevertheless, magnetic order within metal–organic frameworks has generally been limited to low temperatures, owing largely to challenges in creating strong magnetic exchange in extended metal–organic solids. Here, we employ the phenomenon of itinerant ferromagnetism to realize magnetic ordering at <i>T</i><sub>C</sub> = 225 K in a mixed-valence chromium(II/III) triazolate compound, representing the highest ferromagnetic ordering temperature yet observed in a metal–organic framework. The itinerant ferromagnetism is shown to proceed via a double-exchange mechanism, the first such observation in any metal–organic material. Critically, this mechanism results in variable-temperature conductivity with barrierless charge transport below <i>T</i><sub>C</sub> and a large negative magnetoresistance of 23% at 5 K. These observations suggest applications for double-exchange-based coordination solids in the emergent fields of magnetoelectrics and spintronics. Taken together, the insights gleaned from these results are expected to provide a blueprint for the design and synthesis of porous materials with synergistic high-temperature magnetic and charge transport properties. </b>

Classification and role of modulators on crystal engineering of metal organic frameworks (MOFs)

2021 ◽  
Vol 444 ◽  
pp. 214064
Author(s):  
Danni Jiang ◽  
Chao Huang ◽  
Jian Zhu ◽  
Ping Wang ◽  
Zhiming Liu ◽  
...  
Keyword(s):  
Crystal Engineering ◽  
Metal Organic Frameworks ◽  
Metal Organic

Crystal engineering of nonporous organic solids for methane sorption

2005 ◽  
pp. 4420 ◽  
Author(s):  
Praveen K. Thallapally ◽  
Trevor B. Wirsig ◽  
Leonard J. Barbour ◽  
Jerry L. Atwood
Keyword(s):  
Crystal Engineering ◽  
Organic Solids ◽  
Methane Sorption

scholarly journals Hydrogen-bonding 2D metal–organic solids as highly robust and efficient heterogeneous green catalysts for Biginelli reaction

2011 ◽  
Vol 52 (47) ◽  
pp. 6220-6222 ◽  
Author(s):  
Peng Li ◽  
Sridhar Regati ◽  
Raymond J. Butcher ◽  
Hadi D. Arman ◽  
Zhenxia Chen ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Biginelli Reaction ◽  
Organic Solids ◽  
Metal Organic

Crystal Engineering for Catalysis

2018 ◽  
Vol 9 (1) ◽  
pp. 283-309 ◽  
Author(s):  
Jeffrey D. Rimer ◽  
Aseem Chawla ◽  
Thuy T. Le
Keyword(s):  
Crystal Engineering ◽  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Computational Design ◽  
Crystal Nucleation ◽  
Synthesis Methods ◽  
Crystalline Materials ◽  
Simultaneous Control ◽  
Metal Organic ◽  
Controlled Environments

Crystal engineering relies upon the ability to predictively control intermolecular interactions during the assembly of crystalline materials in a manner that leads to a desired (and predetermined) set of properties. Economics, scalability, and ease of design must be leveraged with techniques that manipulate the thermodynamics and kinetics of crystal nucleation and growth. It is often challenging to exact simultaneous control over multiple physicochemical properties, such as crystal size, habit, chirality, polymorph, and composition. Engineered materials often rely upon postsynthesis (top-down) processes to introduce properties that would otherwise be challenging to attain through direct (bottom-up) approaches. We discuss the application of crystal engineering to heterogeneous catalysts with a focus on four general themes: ( a) tailored nanocrystal size, ( b) controlled environments surrounding active sites, ( c) tuned morphology with well-defined facets, and ( d) hierarchical materials with disparate pore size and active site distributions. We focus on nonporous materials, including metals and metal oxides, and two classes of porous materials: zeolites and metal organic frameworks. We review novel synthesis methods involving synergistic experimental and computational design approaches, the challenges facing catalyst development, and opportunities for future advancement in crystal engineering.

scholarly journals Direct evidence for 2-fold to 3-fold change of interpenetration in a MOF

2014 ◽  
Vol 70 (a1) ◽  
pp. C636-C636
Author(s):  
Himanshu Aggarwal ◽  
Prashant Bhatt ◽  
Charl Benzuidenhout ◽  
Leonard Barbour
Keyword(s):  
Single Crystal ◽  
Crystal Engineering ◽  
Molecular Level ◽  
Metal Organic Framework ◽  
Structural Rearrangement ◽  
Structure Property ◽  
Ambient Conditions ◽  
Physical Conditions ◽  
Structure Property Relationships ◽  
Metal Organic

Single-crystal to single-crystal transformations has recently received much attention in the field of crystal engineering. Such transformations not only provide insight into the changes taking place within the crystal at the molecular level, but they also aid our understanding of the structure-property relationships. Discrete crystals have been shown to tolerate considerable dynamic behavior at the molecular level while maintaining their single-crystal character. Examples that are common in the literature include bond formation/cleavage,[1] guest uptake,[2] release or exchange as well as polymorphic phase transformations. However, there are rare examples of the structural transformations on the host framework initiated by removal of guest or change in physical conditions such as temperature or pressure. We have investigated a known doubly-interpenetrated metal organic framework with the formula [Zn2(ndc)2(bpy)] which possesses minimal porosity when activated. We have shown not only that the material converts to its triply-interpenetrated analogue upon desolvation, but that the transformation occurs in a single-crystal to single-crystal manner under ambient conditions.[3] This contribution probes the limits to which a single-crystal material can undergo structural rearrangement while still maintaining the macroscopic integrity of the crystal as a discrete entity.

Synthesis, structure and photocatalytic degradation of organic dyes of a copper(II) metal–organic framework (Cu–MOF) with a 4-coordinated three-dimensional CdSO4 topology

2019 ◽  
Vol 75 (8) ◽  
pp. 1053-1059 ◽  
Author(s):  
Lin-Lu Qian ◽  
Zhi-Xiang Wang ◽  
Hai-Xin Tian ◽  
Min Li ◽  
Bao-Long Li ◽  
...  
Keyword(s):  
Photocatalytic Degradation ◽  
Crystal Engineering ◽  
Photoelectron Spectroscopy ◽  
Organic Dyes ◽  
Metal Organic Framework ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Organic ◽  
And Storage

Metal–organic frameworks (MOFs) have attracted much interest in the fields of gas separation and storage, catalysis synthesis, nonlinear optics, sensors, luminescence, magnetism, photocatalysis gradation and crystal engineering because of their diverse properties and intriguing topologies. A Cu–MOF, namely poly[[(μ2-succinato-κ2 O:O′){μ2-tris[4-(1,2,4-triazol-1-yl)phenyl]amine-κ2 N:N′}copper(II)] dihydrate], {[Cu(C4H4O4)(C24H18N10)]·2H2O} n or {[Cu(suc)(ttpa)]·2H2O} n , (I), was synthesized by the hydrothermal method using tris[4-(1,2,4-triazol-1-yl)phenyl]amine (ttpa) and succinate (suc2−), and characterized by IR, powder X-ray diffraction (PXRD), luminescence, optical band gap and valence band X-ray photoelectron spectroscopy (VB XPS). Cu–MOF (I) shows a twofold interpenetrating 4-coordinated three-dimensional CdSO4 topology with point symbol {65·8}. It presents good photocatalytic degradation of methylene blue (MB) and rhodamine B (RhB) under visible-light irradiation. A photocatalytic mechanism was proposed and confirmed.

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