1,720,979 research outputs found
Selective adsorption of chlorinated volatile organic compound vapours by microcrystalline 1D coordination polymers
No full textMicrocrystalline 1D coordination polymers 1-3Pwd are able to adsorb vapours of chlorinated volatile organic compounds (Cl-VOCs), displaying interesting selectivity patterns, as demonstrated by 1H-NMR and X-ray diffraction analyses. Due to their dynamic breathing-like behavior, chemical and thermal stabilities and adsorption selectivity, these isostructural coordination polymers are promising to be used as filters for toxic Cl-VOCs
Paracetamol Inclusion in Mechanically Interlocked Nanocages
Full text linkThe solid-state synthesis and fast crystallization under kinetic control of poly-[n]-catenanes self-assembled of mechanically interlocked metal organic cages (MOCs) is virtually unexplored. This is in part, due to the lack of suitable crystals for single crystal X-ray diffraction (SC-XRD) analysis which limits their progress as advanced functional materials. Here we report the unprecedented inclusion of paracetamol in the cavities of amorphous materials constituted of M12L8, interlocked MOCs synthesized by mechanochemistry under kinetic control. Full structure determination of a low-crystallinity and low-resolution powders of the M12L8 poly-[n]-catenane including paracetamol has been carried out combining XRD data and Density Functional Theory (DFT) calculations using a multi-step approach. Each M12L8 cage contains six paracetamol guests which is confirmed by thermal analysis and NMR spectroscopy. The paracetamol loading has been also carried out by the instant synthesis method using a saturated paracetamol solution in which TPB and ZnI2 self-assemble immediately (i. e., 1–5 seconds) encapsulating ~7 paracetamol molecules in the M12L8 nanocages under kinetic control also giving a good selectivity. Benzaldehyde has been included in the M12L8 cages using amorphous M12L8 polycatenanes showing that the icosahedral cages can serve as potential nanoreactors for instance to study Henry reactions in the solid-state
Kinetic trapping of 2,4,6-tris(4-pyridyl)benzene and ZnI2 into M12L8 poly-[n]-catenanes using solution and solid-state processes
Full text link: Here, we show that in a supramolecular system with more than 20 building blocks forming large icosahedral M12L8 metal-organic cages (MOCs), using the instant synthesis method, it is possible to kinetically trap and control the formation of interlocking M12L8 nanocages, giving rare M12L8 TPB-ZnI2 poly-[n]-catenane. The catenanes are obtained in a one-pot reaction, selectively as amorphous (a1) or crystalline states, as demonstrated by powder X-ray diffraction (powder XRD), thermogravimetric (TG) analysis and 1H NMR. The 300 K M12L8 poly-[n]-catenane single crystal X-ray diffraction (SC-XRD) structure including nitrobenzene (1) indicates strong guest binding with the large M12L8 cage (i.e., internal volume ca. 2600 Å3), allowing its structural resolution. Conversely, slow self-assembly (5 days) leads to a mixture of the M12L8 poly-[n]-catenane and a new TPB-ZnI2 (2) coordination polymer (i.e., thermodynamic product), as revealed by SC-XRD. The neat grinding solid-state synthesis also yields amorphous M12L8 poly-[n]-catenane (a1'), but not coordination polymers, selectively in 15 min. The dynamic behavior of the M12L8 poly-[n]-catenanes demonstrated by the amorphous-to-crystalline transformation upon the uptake of ortho-, meta- and para-xylenes shows the potential of M12L8 poly-[n]-catenanes as functional materials in molecular separation. Finally, combining SC-XRD of 1 and DFT calculations specific for the solid-state, the role of the guests in the stability of the 1D chains of M12L8 nanocages is reported. Energy interactions such as interaction energies (E), lattice energies (E*), host-guest energies (Ehost-guest) and guest-guest energies (Eguest-guest) were analysed considering the X-ray structure with and without the nitrobenzene guest. Not only the synthetic control achieved in the synthesis of the M12L8 MOCs but also their dynamic behavior either in the crystalline or amorphous phase are sufficient to raise scientific interest in areas ranging from fundamental to applied sides of chemistry and material sciences
Experimental X-ray and DFT Structural Analyses of M12L8 Poly-[n]-catenanes Using exo-Tridentate Ligands
Full text linkABSTRACT: Despite their potential applications in host-guest chemistry, there are only five reported structures of poly-[n]-catenanes self-assembled by elusive M12L8 icosahedral nanocages. This small number of structures of M12L8 poly-[n]-catenanes is because selfassembly of large metal-organic cages (MOCs) with large windows allowing catenation by means of mechanical bonds is very challenging. Structural reports of M12L8 poly-[n]-catenanes are needed to increase our knowledge about the self-assembly and genesis of such materials. Poly-[n ]-catenane (1 center dot p-CT) self-assembly of interlocked M12L8 icosahedral cages (M = Zn(II) and L = 2,4,6-tris-(4-pyridyl)benzene (TPB)) including a new aromatic guest (p-chlorotoluene (p-CT)) is reported by single-crystal XRD. Despite the huge internal M12L8 voids (> 2500 angstrom 3), p-CT is ordered, allowing a clear visualization of the relative host-guest positions. DFT calculations have been used to compute the electrostatic potential of the TPB ligand, and various aromatic guests (i.e., o-dichlorobenzene (o-DCB), p-chloroanisole (p-CA), and nitrobenzene (NBz)) included (ordered) within the M12L8 cages were determined by single-crystal XRD. The computed maps of electrostatic potential (MEPs) allow for the rationalization of the guest's inclusion seen in the 3D X-ray structures. Although more crystallographic X-ray structures and DFT analysis are needed to gain insights of guest inclusion in the large voids of M12L8 poly-[n]-catenanes, the reported combined experimental/DFT structural analyses approach can be exploited to use isostructural M12L8 poly-[n]-catenanes as hosts for molecular separation and could find applications in the crystalline sponge method developed by Fujita and co-workers. We also demonstrate, exploiting the instant synthesis method, in solution (i.e., o-DCB), and in the solid-state by neat grinding (i.e., without solvent), that the isostructural M12L8 poly-[n]-catenane self-assembled with 2,4,6-tris-(4-pyridyl)pyridine (TPP) ligand and ZnX2 (where X = Cl, Br, and I) can be kinetically synthesized as crystalline (yields Pe. 60%) and amorphous phases (yields Pe. 70%) in short time and large quantities. Despite the change in the aromatic nature at the center of the rigid exo-tridentate pyridine-based ligand (TPP vs TPB), the kinetic control gives the poly-[n]-catenanes selectively. The dynamic behavior of the TPP amorphous phases upon the uptake of aromatic guest molecules can be used in molecular separation applications like benzene derivatives
Dynamic single crystal to polycrystal transformation of a 1D-coordination polymer and its second harmonic generation
No full textUpon guest CHCl3 release, the one-dimensional (1D) coordination polymer 1·CHCl3 gives rise to a non-porous structure, 1, following a unit cell volume reduction of ca. 22%. Due to the considerable structural transformation, the single crystal does not maintain its integrity, and therefore the structure determination has been carried out by combining single crystal X-ray diffraction and ab initio X-ray powder diffraction analyses. The result shows a symmetry breaking transformation leading to an acentric crystalline material (1), which shows nonlinear optical properties such as second harmonic generatio
Kinetically Controlled Fast Crystallization of M12L8 Poly-[n]-catenanes Using the 2,4,6-Tris(4-pyridyl)benzene Ligand and ZnCl2 in an Aromatic Environment
Full text linkKinetic control in the presence of six aromatic solvents has been successfully applied in the synthesis of a poly-[n]-catenane composed of interlocked M
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icosahedral nanometric cages (i.e., internal voids of 2500 Å3). When the exotridentate tris-pyridyl benzene ligand and ZnCl2 with appropriate templating molecules because of good ligand aromatic interactions are used, the metal-organic cages can be synthesized very fast, homogeneously, and in large quantities as microcrystalline materials. Synchrotron single-crystal X-ray data (100 K) allowed the resolution of nitrobenzene guest molecules at the internal walls of the M
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nanocages, whereas in the central part of the cages the solvent is highly disordered. The guest release occurs in two steps with the disordered nitrobenzene guests released in the first step (lower temperatures) because of the absence of strong cage-guest interactions. Density functional theory calculations provided a rationalization of these outcomes and, in particular, solid-state approaches, showed theoretical evidence of the kinetic nature in the formation of the poly-[n]-catenane by the analysis of the packing energy in terms of monomeric and dimeric cages
Multiple single-crystal-to-single-crystal guest exchange in a dynamic 1D coordination polymer
Full text linkInsights into the formation of chiral second sphere coordination complexes with aromatic tris amines: combined single crystal X-ray crystallography and molecular modeling analyses
Full text linkInsights into the formation of chiral second sphere coordination complexes with aromatic tris amines: combined single crystal X-ray crystallography and molecular modeling analyses
Antonino Famulari, Massimo Cametti and Stefano Valdo Meille (Politecnico di Milano), and Javier Martí-Rujas (Center for Nano Science and Technology@Polimi, Istituto Italiano di Tecnologia)
Control over the formation of non-centrosymmetric chiral materials is highly desirable due to their potential applications in areas such as ferroelectricity, piezo- and pyroelectricity, and second harmonic generation.[1] The development of a reliable approach to induce the formation of a chiral material from achiral molecules remains a great challenge in the field of molecular chemistry.[2] Furthermore, the understanding of the driving forces behind those aggregations is a prerequisite for the design and construction of chiral molecular arrays. C3-symmetrical tripodal molecules have emerged as attractive organic frameworks for the construction of chiral coordination compounds.[3] In the present contribution we report about a family of isostructural, chiral supramolecular networks obtained in the solid state by exploiting second sphere coordination interactions in the self-assembly of 2 achiral tris amines with tetrahalometallate and halide ions. Quantum-Mechanical calculations (including the usage of approaches specific for crystalline solid phases) provided important insights into the intramolecular and packing interactions which determine chirality, pointing to a direct effect of the methyl groups of the central benzene ring of the tris amines. [4]
[1] (a) P. A. Maggard, C. L. Stern and K. R. Poeppelmeier, J. Am. Chem. Soc., 2001, 123, 7742–7743; (b) M. Liu, L. Zhang and T. Wang, Chem. Rev., 2015, DOI: 10.1021/ Q5 cr500671p. [2] P. S. Halasyamani and K. R. Poeppelmeyer, Chem. Mater., 1998, 10, 2753–2769. [3] Z. Dai and J. W. Canary, New J. Chem., 2007, 31, 1708–1718. [4] H. Yu, L. Li, J. Gao, J. Tong, W. Zheng, M. Cametti, A. Famulari, S.V. Meille, F. Guo and J. Martí-Rujas Journal Article Dalton Trans., 2016,44, 15960-15965. DOI: 10.1039/C5DT02387D
Thiophenes and Their Benzo Derivatives: Structure
No full textThis article details recent advances in the structural and spectroscopic investigation of thiophene molecules and their benzo-derivatives. These species are gaining a large interest for multiple applications as organic semiconductors. Key concepts accompanying the whole discussion are those related to the double aromatic/biradicaloid and quinoidal characters that characterize these molecular materials, which have important consequences on their optoelectronic properties and thus need to be known and possibly predicted. Relevance is also given to the description of cases featuring different aggregation phenomena at the solid state, which is also central for charge transport and light emission properties
Highly Dynamic and Tunable Behavior of 1D Coordination Polymers Based on the Bispidine Ligand
No full textLigands L1 and L2 have been designed, synthesized, and used to build for the first time bispidine-based coordination polymers (CPs) in combination with Mn II . The novel CPs have been structurally characterized by single-crystal (SC) and powder X-ray diffraction (P-XRD) techniques, showing that they are composed of 1D ribbon-like chains that adopt various arrangements depending on the trapped solvent species. These materials show highly dynamic behavior as they undergo heterogeneous solid/liquid and solid/vapor multiple solvent exchange processes, comprising crystalline–amorphous–crystalline, selective adsorption and SC-to-SC transformations, where major structural reorganization of the 1D ribbons are observed. By tuning inter-ribbon interactions through expansion of the ligand's accessible surface, the dynamic behavior can be effectively modulated
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