[Cobalt(II)L-glutamate(H2O)·H2O]∞: a new 3D chiral metal–organic interlocking network with channels
TL;DR: In this paper, a monometallic assembly of composition [Cobalt(II)L-glutamate(H2O)· H2O]∞(I) has been prepared and structurally and magnetically characterized.
Abstract: A monometallic assembly of composition [Cobalt(II)L-glutamate(H2O)·H2O]∞ (I) has been prepared and structurally and magnetically characterized. Assembly I crystallizes in the orthorhombic space group P212121 with a = 7.149(9), b = 10.468(3), c = 11.295(5)
A, V = 845.3 A3 and Z = 4. The crystal structure analysis reveals a three-dimensional network with channels parallel to the a-axis. The observed structure suggests that highly isolated Co(II) cations are present in the solid state structure – a fact verified by the temperature-dependent magnetic susceptibility (298–5 K) which is that of a classical, isolated paramagnet with μ(eff) ranging from 4.1 to 5.2 BM.
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TL;DR: The state-of-the-art on hybrid porous solids, their advantages, their new routes of synthesis, the structural concepts useful for their 'design', aiming at reaching very large pores are presented.
Abstract: This critical review will be of interest to the experts in porous solids (including catalysis), but also solid state chemists and physicists. It presents the state-of-the-art on hybrid porous solids, their advantages, their new routes of synthesis, the structural concepts useful for their ‘design’, aiming at reaching very large pores. Their dynamic properties and the possibility of predicting their structure are described. The large tunability of the pore size leads to unprecedented properties and applications. They concern adsorption of species, storage and delivery and the physical properties of the dense phases. (323 references)
5,187 citations
TL;DR: Five azido-bridged coordination polymers are prepared and characterized crystallographically and magnetically, and exhibit very different magnetic behaviors.
Abstract: Using the achiral diazine ligands bearing two bidentate pyridylimino groups as sources of conformational chirality, five azido-bridged coordination polymers are prepared and characterized crystallographically and magnetically. The chirality of the molecular units is induced by the coordination of the diazine ligands in a twisted chiral conformation. The use of L1 (1,4-bis(2-pyridyl)-1-amino-2,3-diaza-1,3-butadiene) and L2 (1,4-bis(2-pyridyl)-1,4-diamino-2,3-diaza-1,3-butadiene) induces spontaneous resolution, yielding conglomerates of chiral compounds [Mn3(L1)2(N3)6]n (1) and [Mn2(L2)2(N3)3]n(ClO4)n·nH2O (2), respectively, where triangular (1) or double helical (2) chiral units are connected into homochiral one-dimensional (1D) chains via single end-to-end (EE) azido bridges. The chains are stacked via hydrogen bonds in a homochiral fashion to yield chiral crystals. When L3 (2,5-bis(2-pyridyl)-3,4-diaza-2,4-hexadiene) is employed, a partial spontaneous resolution occurs, where binuclear chiral units are i...
504 citations
TL;DR: This feature article highlights the advances in the synthesis of Metal-Biomolecule Frameworks (MBioFs), with special emphasis on the crystal structures of these materials, their miniaturization to the submicron length scale, and their new potential storage, catalytic, and biomedical applications.
351 citations
TL;DR: A new nickel aspartate with a three-dimensional Ni-O-Ni connectivity that forms at a higher pH and is based on the same helices as in 1 which are connected by additional nickel octahedra to generate a chiral open framework with one-dimensional channels.
Abstract: In the course of our investigation aimed at the preparation of homochiral coordination polymers using readily available in optically pure form ligands and building blocks of condensed metal polyhedra, we recently reported a one-dimensional nickel aspartate compound [Ni2O(l-Asp)(H2O)2]·4H2O (1) based on helical chains with extended Ni−O−Ni bonding. Here we report a new nickel aspartate [Ni2.5(OH)(l-Asp)2]·6.55H2O (2) with a three-dimensional Ni−O−Ni connectivity that forms at a higher pH and is based on the same helices as in 1 which are connected by additional nickel octahedra to generate a chiral open framework with one-dimensional channels with minimum van der Waals dimensions of 8 × 5 A. The crystal structure of 2 was determined by synchrotron single-crystal X-ray diffraction on a 10 × 10 × 240 μm crystal.
201 citations
TL;DR: This paper looks at different perspectives offered in several ways by the outstanding properties of porous hybrid frameworks and suggested orientations concern all the aspects of the field: syntheses, structures and the dedicated potential applications related to energy, energy savings, sustainable development and health.
Abstract: From the current state-of-the-art, this paper looks at different perspectives offered in several ways by the outstanding properties of porous hybrid frameworks. These suggested orientations concern all the aspects of the field: syntheses, structures and the dedicated potential applications related to energy, energy savings, sustainable development and health.
170 citations
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TL;DR: The synthesis of a homochiral metal–organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantiOSElective manner is reported.
Abstract: Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.
3,598 citations
TL;DR: In this paper, the authors review the studies on the photofunctions of intercalation compounds, focusing mainly on the role of layered structure on the organization of photoactive species; they discuss only in connection with the microscopic structures.
Abstract: In this article, the authors review the studies on the photofunctions of intercalation compounds. (The structures and properties of host materials which have been used for immobilizing photoactive species have been summarized in the following section.) some of these studies are for the purpose of characterizing the properties of host materials and host-guest systems, and others are for the purpose of contributing to future practical applications. The well-defined layered structures as well as the ability to accommodate guest species on the surface of the layers are very useful for organizing photoactive species to evaluate and control the photofunctions. Table 1 summarizes the characteristics of typical host-guest systems studied for immobilizing photoactive species. Attention is mainly focused on the role of layered structure on the organization of photoactive species; the photofunctions of intercalation compounds are discussed only in connection with the microscopic structures. 321 refs.
962 citations
TL;DR: A disk-shaped molecule with chiral tails is shown to form long fibers of molecular diameter and micrometer length by self-assembly in chloroform, which has potential in optoelectronic applications and as components in sensor devices.
Abstract: A disk-shaped molecule with chiral tails is shown to form long fibers of molecular diameter and micrometer length by self-assembly in chloroform. The molecules are derived from crown ethers and contain a phthalocyanine ring. In the fibers, they have a clockwise, staggered orientation that leads to an overall right-handed helical structure. These structures, in turn, self-assemble to form coiled-coil aggregates with left-handed helicity. Addition of potassium ions to the fibers leaves their structure intact but blocks the transfer of the chirality from the tails to the cores, leading to loss of the helicity of the fibers. These tunable chiral materials have potential in optoelectronic applications and as components in sensor devices.
660 citations
TL;DR: In this article, the authors proposed a method for tuning the magnitude of the interaction through a given bridging network by modifying the nature of the terminal ligands, which, in some way, play the role of adjusting screws.
Abstract: When two paramagnetic transition metal ions are present in the same molecular entity, the magnetic properties can be totally different from the sum of the magnetic properties of each ion surrounded by its nearest neighbors. These new properties depend on the nature and the magnitude of the interaction between the metal ions through the bridging ligands. If both ions have an unpaired electron (e.g. Cu2+ ions), then the molecular state of lowest energy is either a spin singlet or a spin triplet. In the former case, the interaction is said to be antiferromagnetic, in the latter case ferromagnetic. The nature and the order of magnitude of the interaction can be engineered by judiciously choosing the interacting metal ions and the bridging and terminal ligands, and, thus, by the symmetry and the delocalization of the orbitals centered on the metal ions and occupied by the unpaired electrons (magnetic orbitals). The first success in this “molecular engineering” of bimetallic compounds was in the synthesis of a Cu2+VO2+ heterobimetallic complex in which the interaction is purely ferro-magnetic. The same strategy could be utilized for designing molecular ferromagnets, one of the major challenges in the area of molecular materials. Another striking result is the possibility of tuning the magnitude of the interaction through a given bridging network by modifying the nature of the terminal ligands, which, in some way, play the role of “adjusting screws”. By careful selection of the bridging and terminal ligands, a very large antiferro-magnetic interaction can be achieved, even if the metal ions are far away from each other. Some sulfur-containing bridges are especially suitable in this respect.
587 citations
TL;DR: In this paper, Pillared-layer-type coordination networks [Cu2(pzdc)2(L)n] are used to build up stable tunable channels.
Abstract: Stable tunable channels are formed by pillared-layer-type coordination networks [{Cu2(pzdc)2(L)}n] (pzdc = pyrazine-2,3-dicarboxylate; L = pyrazine, 4,4′-bipyridine, N-(4-pyridyl)isonicotinamide). Not only their channel sizes, shapes, and chemical environments are systematically built up by tuning the pillar ligands, but also the porosity is maintained in the absence of the included guest molecules. These compounds can adsorb methane, and the amount of gas adsorption is controllable by the type of pillar ligands.
530 citations