Recent Advances in Crystal Engineering from Nanoscience Views: A Brief Review (original) (raw)
Related papers
Recent Developments in Crystal Engineering
Crystal Growth & Design, 2011
Crystal Growth & Design PERSPECTIVE increase via weak noncovalent interactions such as hydrogen bonds, and (c) 1D f 3D and 2D f 3D dimensional increase via interpenetration or catenation. 5 Recently, the first China-India-Singapore Symposium on Crystal Engineering held at the National University of Singapore provided an excellent forum and opportunities for the researchers from these three countries to showcase their research and exchange ideas. The focus of this perspective is to review the invited talks which were presented at this symposium by the top researchers from these countries working in the field of crystal engineering, crystal growth, and supramolecular chemistry. A wide range of topics was discussed that includes new directions in organic crystal engineering, fundamental theoretical aspects of supramolecular interactions, crystallization of biomaterials, polymorphism, co-crystals, design of organic crystals, covalent organic frameworks, porous organic frameworks, oxo clusters, rotaxanes, coordination polymers, supramolecular gels, solid-state dynamics and structural transformations, mechanical properties of pharmaceutics, sorption, optical and magnetic properties to applications in graphene and plastic solar cells.
A new method to position and functionalize metal-organic framework crystals
Nature Communications, 2011
With controlled nanometre-sized pores and surface areas of thousands of square metres per gram, metal-organic frameworks (MOFs) may have an integral role in future catalysis, filtration and sensing applications. In general, for MOF-based device fabrication, well-organized or patterned MOF growth is required, and thus conventional synthetic routes are not suitable. Moreover, to expand their applicability, the introduction of additional functionality into MOFs is desirable. Here, we explore the use of nanostructured poly-hydrate zinc phosphate (α-hopeite) microparticles as nucleation seeds for MOFs that simultaneously address all these issues. Affording spatial control of nucleation and significantly accelerating MOF growth, these α-hopeite microparticles are found to act as nucleation agents both in solution and on solid surfaces. In addition, the introduction of functional nanoparticles (metallic, semiconducting, polymeric) into these nucleating seeds translates directly to the fabrication of functional MOFs suitable for molecular size-selective applications.
From Molecules to Materials: Current Trends and Future Directions
Advanced Materials, 1998
The development, characterization, and exploitation of novel materials based on the assembly of molecular components is an exceptionally active and rapidly expanding field. For this reason, the topic of molecule-based materials (MBMs) was chosen as the subject of a workshop sponsored by the Chemical Sciences Division of the United States Department of Energy. The purpose of the workshop was to review and discuss the diverse research trajectories in the field from a chemical perspective, and to focus on the critical elements that are likely to be essential for rapid progress. The MBMs discussed encompass a diverse set of compositions and structures, including clusters, supramolecular assemblies, and assemblies incorporating biomolecule-based components. A full range of potentially interesting materials properties, including electronic, magnetic, optical, structural, mechanical, and chemical characteristics were considered. Key themes of the workshop included synthesis of novel components, structural control, characterization of structure and properties, and the development of underlying principles and models. MBMs, defined as ªuseful substances prepared from molecules or molecular ions that maintain aspects of the parent molecular frameworkº are of special significance because of the capacity for diversity in composition, structure, and properties, both chemical and physical. Key attributes are the ability in MBMs to access the additional dimension of multiple length scales and available structural complexity via organic chemistry synthetic methodologies and the innovative assembly of such diverse components. The interaction among the assembled components can thus lead to unique behavior. A consequence of the complexity is the need for a multiplicity of both existing and new tools for materials synthesis, assembly, characterization, and
Synthesis and perspectives of complex crystalline nano‐structures
2006
Research on inorganic colloidal nanocrystals has moved from the synthesis of simple structures, such as spherical nanoparticles, to more elaborate particles with shapes such as rods, stars, discs, and branched nanocrystals, and recently to nanoparticles that are composed out of sections of different materials. Nanocrystal heterostructures represent a convenient approach to the development of nanoscale building blocks, as they merge sections with different functionality in the same particle, without the need of inorganic cross-linkers. The present article gives an overview of synthesis strategies to complex nanocrystals and will highlight their structural properties, as well as discuss some envisaged applications.
Journal of the American Chemical Society, 2008
Metal-organic polyhedra and frameworks (MOPs and MOFs) were prepared by linking square units M 2(CO2)4 (M ) Cu and Zn) with a variety of organic linkers designed to control the dimensionality (periodicity) and topology of the resulting structures. We describe the preparation, characterization, and crystal structures of 5 new MOPs and 11 new MOFs (termed MOP-) and show how their structures are related to the shape and functionality of the building blocks. The gas uptake behaviors of MOP-23 and MOF-601 to -603 are also presented as evidence that these structures have permanent porosity and rigid architectures. Sun, D.; Ambrogio, M.; Fillinger, J. A.; Parkin, S.; Zhou, H.-C. J. Am. Chem. Soc. 2007, 129, 1858-1859. (3) Eddaoudi, M.; Kim, J.; Vodak, D.; Sudik, A.; Wachter, J.; O'Keeffe, M.; Yaghi, O. M. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 4900-4904. (4) (a) Chae, H. K.; Kim, J.; Delgado-Friedrichs, O.; O'Keeffe, M.; Yaghi, O. M. Angew. Chem., Int. Ed. 2003, 42, 3907-3909. (b) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O'Keeffe, M.; Yaghi, O. M. Science 2002, 295, 469-472. (c) Surblé, S.; Serre, C.; Mellot-Draznieks, C.; Millange, F. G.; Férey, G. Chem. Commun. 2006, 284-286. (5) (a) Chae, H. K.; Siberio-Pérez, D. Y.; Kim, J.; Go, Y.-B.; Eddaoudi, M.; Matzger, A. J.; O'Keeffe, M.; Yaghi, O. M. Nature 2004, 427, 523-527. (b) Devic, T.; David, O.; Valls, M.; Marrot, J.; Couty, F.; Férey, G.
2000
Metal organic framework (MOF) has emerged as a new class of porous, thermally stable material which has attracted great attention due to their wide applications in gas storage, separation, catalysis etc. Self-assembly is the operative mechanism of MOFs syntheses; however, the control of MOF self-assembly is still a challenge in the construction of predetermined, structurally well-defined MOFs. The goal of the research is to arrive at multidimensional, highly porous and functional MOFs via hierarchical assembly of smaller molecular building blocks and, at the same time, to examine the possibilities for different interesting molecular textures. This goal is to be accomplished by the knowledge of ligand coordination mode, and geometry as well as logical choices of ligands and metals from which the MOFs are to be constructed from. Preparations of novel frameworks as well as other interesting molecular architectures are highlighted with their structures characterized.
Crystal Engineering: A Brief for the Beginners
Acta Scientific Pharmaceutical Sciences, 2021
Crystals are formed by aggregation of molecules in solution. This phenomenon encourages several questions. Among them few are, how do these aggregations happen to form crystals? Why do same molecules adopt more than one crystal structure? Why does solvent occupy some crystal structures? How does crystal structure can be designed with a specified coordination of molecules and/ or ions with a specified property? What are the relationships between crystal structures and properties, for molecular crystals? At present several queries are being resolved by the crystal engineering community; a larger community constructed by organic, inorganic and physical chemists, crystallographers and solid-state scientists. This article provides brief idea to provide a basic introduction to crystal engineering and this fascinating and important subject that has moved from the fringes into the mainstream of chemistry.
Fabricating Nanostructures via Organic Molecular Templates
In the rapid growth of nanoscience and technology, organic compounds occupy a prominent position and play comprehensive roles as stabilizers , protective masks [6], templates [7-9], surface modifiers [10], position indicators [11], functional units and building blocks [12-17], and molecular "ink" [18-21], etc. Further more, organic compounds are key components in the design and fabrication of nanomachines and nanodevices. Utilization of organic molecules has allowed prototypes of nanomachines and nanodevices, such as molecular motors [22-26], conductors [27-30], logic gates [31], memories [32], rectifiers [33-36], negative differential resistance devices [37], single electron tunneling devices [38], and gears [39-41], to be developed [42].
Angewandte Chemie International Edition, 2011
During the past decade porous metal-organic material (MOM) networks constructed from metal-based nodes (metal ions or metal clusters) and bridging organic ligand (linkers) have attracted ever increasing scientific interest. [1] Their modular nature imparts structural and compositional diversity, tunable functionality, and multiple properties within a single material. In particular, that MOMs can exhibit extralarge surface area means that they represent a uniquely promising class of materials to solve technological challenges related to gas storage and separation, environmental remediation, catalysis, sensing, and drug delivery. Crystal engineering played a major role in the early development of MOMs as exemplified by the high symmetry nets that can be generated by linking polygonal or polyhedral nodes such as tetrahedra (dia), octahedra (pcu), [3c] squares (nbo), [3c, 4] and trigonal prisms (acs). The aforementioned nets might be described as platforms because they are fine-tunable in terms of both scale and properties as there are many nodes and linkers that can sustain these structures. Pyridyl linkers such as 4,4'-bipyridine were initially exploited in such a capacity [6] but the majority of extra-large surface area MOMs are based upon carboxylate linkers such as benzene-1,3-dicarboxylic acid (1,3-BDC), [7] benzene-1,4-dicarboxylic acid (1,4-BDC), [8] and benzene-1,3,5-tricarboxylic acid (BTC). Such linkers complement synthetically accessible and highly symmetrical metal carboxylate nodes such as [Cu 2 (CO 2 ) 4 ], [Zn 4 (m 4 -O)-(CO 2 ) 6 ] and [{M 3 (m 3 -O)(CO 2 )} 6 ] (M = Cr, Fe). The exploitation of [Cu 2 (CO 2 ) 4 ], the "square paddlewheel", has proven to be particularly fruitful since ligand design or the use of mixed ligands facilitates a plethora of highly porous polyhedral nets. [{M 3 (m 3 -O)(CO 2 )} 6 ], the "trigonal prism", has also afforded highly porous materials, as exemplified by MIL-100 and MIL-101. However, even though this node is remarkably robust, [14] its structures tend to form only microcrystalline materials and require harsh synthetic conditions. We describe herein a crystal engineering strategy that exploits preformed molecular building blocks (MBBs) based upon water-stable trigonal prisms that are decorated with pyridyl moieties. A two-step modular approach that opens up a broad new class of bimetallic MOMs is thereby facilitated. Two-step processes to form heterobimetallic frameworks are known and are based on the synthesis of a metal complex that is subsequently connected to a different metal ion. To the best of our knowledge, high-connectivity metal complexes that afford high symmetry nets with extra-large channels have not yet been studied in this context. Our twostep process involves isolation of a trigonal prism decorated by pyridyl moieties and then coordinating this highly soluble trigonal-prismatic Primary Molecular Building Block (tp-PMBB-1) to different metals through its six exodentate pyridyl moieties (Scheme 1). We coin the term PMMB to draw analogies to the primary building unit (PBU) in zeolite chemistry. In this context the different connections of PMBBs to various Secondary Molecular Building Blocks (SMBBs) lead to the structural diversity. This approach enables us to exploit both metal-carboxylate and metal-pyridyl bonds and ensures that the nets thereby generated will be positively charged. The first three examples of such nets, tp-PMBB-1snx-1, -snw-1, and -stp-1 (nomenclature describes both the primary building block and the topology of the resulting net) are described herein.