Self-assembly Through Non-coordinating Intermolecular Forces, Part 2 [1]. Synthesis, Crystal Structure and Packing of [Cu2(μ-phthalazine)3(phthalazine)2][CF3SO3]2

2008 ◽  
Vol 63 (10) ◽  
pp. 1169-1174
Author(s):  
Laurent Plasseraud ◽  
Hélène Cattey ◽  
Philippe Richard
Keyword(s):  
Self Assembly ◽  
Electrostatic Interactions ◽  
Building Blocks ◽  
Intermolecular Forces ◽  
Acetonitrile Solution ◽  
The Novel ◽  
X Ray Diffraction ◽  
Monoclinic System ◽  
Dimensional Network ◽  
Copper Centre

Abstract Treatment of the copper(I) trifluoromethanesulphonate toluene complex {[Cu(CF3SO3)]2 · C6H5Me} (1) with phthalazine (phtz, C8H6N2) in dichloromethane-acetonitrile solution yielded, via the bis(acetonitrile)tris(μ-phthalazine)dicopper(I) trifluoromethanesulphonate intermediate (2), the novel bis(phthalazine)tris(μ-phthalazine)dicopper(I) trifluoromethanesulphonate salt (3). Compound 3 was completely characterised and the molecular structure determined by single-crystal X-ray diffraction. Complex 3 crystallises in the monoclinic system, space group C2/c, with a = 26.9527(10), b = 10.9558(7), c = 19.2104(10) Å , β = 127.268(2)◦, V = 4514.3(4) Å3 and Z = 4. The copper(I) coordination geometry is tetrahedral, each copper centre being linked to four phthalazine molecules. Dicationic units of 3 which present an unusual paddle wheel-like shape constitute appropriate organometallic building blocks for the construction of a supramolecular solid-state architecture. The analysis of the packing of the molecules of 3 in the crystal revealed an unprecedented 2-dimensional network, resulting from intermolecular π-π and electrostatic interactions.

A novel tetraphenylethylene derivative: 4-methyl-N-[3-(1,2,2-triphenylethenyl)phenyl]benzenesulfonamide with aggregation-induced emission

2019 ◽  
Vol 75 (8) ◽  
pp. 1060-1064
Author(s):  
Lei Jia ◽  
Jun Zhang ◽  
Lin Du
Keyword(s):  
Three Dimensional ◽  
Intermolecular Forces ◽  
Monoclinic Space Group ◽  
The Novel ◽  
X Ray Diffraction ◽  
Aggregation State ◽  
Aggregation Induced Emission ◽  
H Nmr ◽  
Dimensional Network ◽  
Intramolecular Motions

The novel tetraphenylethylene derivative 4-methyl-N-[3-(1,2,2-triphenylethenyl)phenyl]benzenesulfonamide (abbreviated as MTBF), C33H27NO2S, was synthesized successfully and characterized by single-crystal X-ray diffraction, high-resolution mass spectroscopy and 1H NMR spectroscopy. MTBF crystallizes in the centrosymmetric monoclinic space group P21/c. In the crystal structure, the MTBF molecules are connected into a one-dimensional band and then a two-dimensional sheet by hydrogen bonds of the N—H...O and C—H...O types. The sheets are further linked to produce a three-dimensional network via C—H...π interactions. The molecules aggregate via these intermolecular forces, which restrain the intramolecular motions (RIM) and decrease the energy loss in the aggregation state, so as to open the radiative channels, and thus MTBF exhibits excellent fluorescence by aggregation-induced emission (AIE) enhancement.

scholarly journals Synthesis and Characterization of [2-CH3CH2C6H4NH3]6P6O18⋅4H2O

2011 ◽  
Vol 2011 ◽  
pp. 1-6 ◽  
Author(s):  
Houda Marouani ◽  
Salem Slayyem Al-Deyab ◽  
Mohamed Rzaigui
Keyword(s):  
Hydrogen Bonds ◽  
Electrostatic Interactions ◽  
Three Dimensional ◽  
Spectroscopic Studies ◽  
Monoclinic System ◽  
Dimensional Network ◽  
Cell Dimensions ◽  
Unit Cell Dimensions ◽  
Ir Spectroscopic

Single crystals of [2-CH3CH2C6H4NH3]6P6O18⋅4H2O are synthesized in aqueous solution by the interaction of cyclohexaphosphoric acid and 2-ethylaniline. This compound crystallizes in the monoclinic system with P21/c space group the unit cell dimensions are: a=16.220(4) Å, b=10.220(5) Å, c=20.328(4) Å, β=113.24(3)∘, Z=2, and V=3096.5(18) Å3. The atomic arrangement can be described by layers formed by cyclohexaphosphate anions P6O186− and water molecules connected by hydrogen bonds O–H⋯O. These inorganic layers are developed around bc planes at x=1/2 and are interconnected by the H-bonds created by ammonium groups of organic cations. All the hydrogen bonds, the van der Waals contacts and electrostatic interactions between the different entities give rise to a three-dimensional network in the structure and add stability to this compound. The thermal behaviour and the IR spectroscopic studies of this new cyclohexaphosphate are discussed.

Zeolitic Host–Guest Interactions and Building Blocks for the Self-Assembly of Complex Materials

MRS Bulletin ◽  
2005 ◽  
Vol 30 (10) ◽  
pp. 713-720 ◽  
Author(s):  
Thomas Bein
Keyword(s):  
Self Assembly ◽  
Electrostatic Interactions ◽  
Spatial Organization ◽  
Organic Dyes ◽  
Three Dimensional ◽  
Internal Surface ◽  
Building Blocks ◽  
Three Dimensional Objects ◽  
Surface Areas ◽  
Catalyst Systems

AbstractOrdered nanoscale pore systems such as those represented by zeolites offer many opportunities for the design of complex functional systems via self-assembly.With their large internal surface areas and tunable, well-defined crystalline pore structures that allow molecular sieving and ion exchange, zeolites can be adapted for numerous applications. The nanoscale reactors present in zeolite pore systems have been explored as structural templates for the spatial organization of numerous guests. Examples from various fields are discussed, such as the stabilization of organic dyes for the construction of energy transfer and storage systems, the construction of host–guest hybrid catalyst systems, and the encapsulation of conducting or semiconducting nanoscale wires and clusters. More complex, hierarchical forms of nanostructured matter become accessible when zeolite crystals are used as building blocks for the selfassembly of thin films or three-dimensional objects. A combination of weaker and stronger interactions ranging from dispersive forces, hydrogen bonding, and electrostatic interactions to covalent bonding can be used to build functional hierarchical constructs. Several examples and novel applications of such systems will be discussed, including oriented channel systems, chemical sensors, and hierarchical pore systems for catalytic reactions.

scholarly journals Towards Complex Matter: Supramolecular Chemistry and Self-organization

2009 ◽  
Vol 17 (2) ◽  
pp. 263-280 ◽  
Author(s):  
Jean-Marie Lehn
Keyword(s):  
Supramolecular Chemistry ◽  
Self Assembly ◽  
Building Blocks ◽  
Intermolecular Forces ◽  
Self Organization ◽  
Irreversible Processes ◽  
Continuous Change ◽  
Supramolecular Systems ◽  
Molecular Information ◽  
Complex Matter

Chemistry has developed from molecular chemistry, mastering the combination and recombination of atoms into increasingly complex molecules, to supramolecular chemistry, harnessing intermolecular forces for the generation of informed supramolecular systems and processes through the implementation of molecular information carried by electromagnetic interactions. Supramolecular chemistry is actively exploring systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, on the basis of the molecular information stored in the covalent framework of the components and read out at the supramolecular level through specific molecular recognition interactional algorithms, thus behaving as programmed chemical systems. Supramolecular entities as well as molecules containing reversible bonds are able to undergo a continuous change in constitution by reorganization and exchange of building blocks. This capability defines a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels. CDC introduces a paradigm shift with respect to constitutionally static chemistry. It takes advantage of dynamic constitutional diversity to allow variation and selection and thus adaptation. The merging of the features of supramolecular systems – information and programmability; dynamics and reversibility; constitution and structural diversity – points towards the emergence of adaptive chemistry. A further development will concern the inclusion of the arrow of time, i.e. of non-equilibrium, irreversible processes and the exploration of the frontiers of chemical evolution towards the establishment of evolutive chemistry, where the features acquired by adaptation are conserved and transmitted. In combination with the corresponding fields of physics and biology, chemistry thus plays a major role in the progressive elaboration of a science of informed, organized, evolutive matter, a science of complex matter.

scholarly journals Unveiling the Key Templates in the Self-Assembly of Gigantic Molybdenum Blue Wheels

2018 ◽  
Author(s):  
Weimin Xuan ◽  
Robert Pow ◽  
Qi Zheng, ◽  
Nancy Watfa ◽  
De-Liang Long ◽  
...  
Keyword(s):  
Self Assembly ◽  
Electrostatic Interactions ◽  
Structural Evolution ◽  
Functional Materials ◽  
Building Blocks ◽  
Underlying Mechanism ◽  
The Self ◽  
Supramolecular Systems ◽  
Structure Directing Agent ◽  
Molybdenum Blue

Template synthesis is a powerful and useful approach to build a variety of functional materials and complicated supramolecular systems. Systematic study on how templates structurally evolve from basic building blocks and then affect the templated self-assembly is critical to understand the underlying mechanism and gain more guidance for designed assembly but remains challenging. Here we describe the templated self-assembly of a series of gigantic Mo Blue (MB) clusters 1-4 using L-ornithine as structure-directing agent. L-ornithine is essential for the formation of such kind of template⊂host assemblies by providing directional forces of hydrogen bonding and electrostatic interactions. Based on the structural relationship between encapsulated templates of {Mo8} (1), {Mo17} (2) and {Mo36} (4), a plausible pathway of the structural evolution of templates is proposed, thus giving more insight on the templated self-assembly of Mo Blue clusters.

Design and gas sorption study of c-alkylresorcin[n]arene-based cocrystals

2017 ◽  
Author(s):  
◽  
Shan Jiang
Keyword(s):  
Self Assembly ◽  
Guest Molecule ◽  
The Novel ◽  
Gas Sorption ◽  
X Ray Diffraction ◽  
University Of Missouri ◽  
X Ray ◽  
Solvent Systems ◽  
The University ◽  
Sorption Study

[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT AUTHOR'S REQUEST.] Supramolecular chemistry is the study of how to form complexes through molecular self-assembly and intermolecular bonding. Our research group has been doing a lot supramolecular research based on macrocycles such as calixarenes, pyrogallolarenes and resorcinarens. This research is interested in formation of novel C-alkyresorcin[n]arene( n=4,6) based cocrystals. The basic plan is to design and synthesize cocrystals, then analyze the crystal structure via single crystal X-ray diffraction technique, and determine if the novel cocrystal has the ability to absorb gases such as carbon dioxide and nitrogen. Chapter two is about the cocrystallization of six different C-alkylresorcin[4]arene according the chain length and guest molecule 1-(2-pyridylazo)-2-naphthol( PAN) in four solvent systems. Five successfully synthesized cocrystals' structure and synthesis are discussed. Chapter three talks how to use cocrystallization as a separation method to separate C-ethylresocin[6]arene from C-ethylresorcin[4]arene. Three noval C-ethylresorcin[6]arene based cocrystals from three different solvents are discussed. Chapter four investigates the cocrystallization between C-ethylresorcin[n]arene (n=4, 6) with 4, 4'-bipyridine. It discusses how solvent and component concentration affect such cocrystallization. Chapter five uses cocrystal formed from C-ethylresorcin[6]arene and 1,2-bis(4-pyridyl)ethane in acetone as the gas sorption candidate to test its ability to absorb gases after solvent removal. The conditions of removing solvents and gas sorption results are discussed.

Synthesis, crystal structures and magnetic characterisation of two 2p–3d metallic coordination polymers

2017 ◽  
Vol 41 (6) ◽  
pp. 365-369 ◽  
Author(s):  
Chongchong Xue ◽  
Jingwen Shi ◽  
Daopeng Zhang
Keyword(s):  
Magnetic Susceptibility ◽  
Coordination Polymers ◽  
Supramolecular Structure ◽  
Three Dimensional ◽  
Building Blocks ◽  
Chain Structure ◽  
X Ray Diffraction ◽  
One Dimensional ◽  
X Ray ◽  
Dimensional Network

The coordination polymers {Mg[Fe(L)(CN)5]}n·0.5nH2O and {MgCu2(CH3COO)6}n [L = bis( N-imidazolyl)methane] have been synthesised. X-ray diffraction revealed that {Mg[Fe(L)(CN)5]}n·0.5nH2O has a one-dimensional neutral chain structure consisting of alternating [Mg(L)2(H2O)2)]2+ species and [Fe(L)(CN)5]2– building blocks, which can be further linked into a three-dimensional supramolecular structure by inter-chain p–p interactions. {MgCu2(CH3COO)6}n has a three-dimensional network with the [MgCu2(CH3COO)6] unit as neutral core extended by Mg–O bonds. Magnetic susceptibility studies on {MgCu2(CH3COO)6}n revealed antiferromagnetic interactions between adjacent Cu(II) ions.

Simulations of Organic-tethered Silsesquioxane Nanocube Assemblies

2004 ◽  
Vol 847 ◽  
Author(s):  
Xi Zhang ◽  
Elaine R. Chan ◽  
Lin C. Ho ◽  
Sharon C. Glotzer
Keyword(s):  
Self Assembly ◽  
Building Blocks ◽  
The Novel ◽  
Assembly Process ◽  
Molecular Topology ◽  
Inorganic Hybrid ◽  
Cylindrical Structures ◽  
Equilibrium Structures ◽  
Oligomeric Silsesquioxane ◽  
Complex Nanostructures

ABSTRACTPolyhedral oligomeric silsesquioxane (POSS) based materials are a class of organic/inorganic hybrid nanomaterials with many interesting properties. Recent experiments have demonstrated that self-assembly of tethered POSS nanocubes is a promising route to the synthesis of novel materials with highly ordered, complex nanostructures. Using a coarsegrained model developed for tethered POSS, we perform molecular simulations of POSS molecules tethered by short polymers to investigate how the novel architecture of these hybrid building blocks can be exploited to achieve useful structures via self-assembly. We systematically explore the parameters that control the assembly process and the resulting equilibrium structures, including concentration, temperature, tethered POSS molecular topology, and solvent conditions. We report preliminary results of lamellar and cylindrical structures that are typically found in conventional block copolymer and surfactant systems, but with interesting modifications of the phase behavior caused by the bulkiness and cubic geometry of the POSS molecules.

scholarly journals Xanthene[n]arenes: Exceptionally Large, Bowl-shaped Macrocyclic Building Blocks Suitable for Self-Assembly

2021 ◽  
Author(s):  
Jonathan Pfeuffer-Rooschüz ◽  
Alessandro Prescimone ◽  
Konrad Tiefenbacher
Keyword(s):  
Self Assembly ◽  
Building Blocks ◽  
The Novel ◽  
Supramolecular Systems ◽  
Binding Properties ◽  
Molecular Capsules ◽  
New Class ◽  
Guest Binding ◽  
Non Covalent Interactions ◽  
Covalent Interactions

<div>A new class of macrocycles denoted as “xanthene[n]arenes” was synthesized. In contrast to most other macrocycles, they feature a rigid bowl-shape, required for the synthesis of cavitands and for the self-assembly to molecular capsules via non-covalent interactions. The derivatization potential of the novel macrocycles was demonstrated on the xanthene[3]arene scaffold. Beside a deep cavitand, a modified macrocycle was synthesized that self-assembles into a hydrogen-bonded tetrameric capsule. Both supramolecular systems display host-guest binding properties, demonstrating the potential of xanthene[n]arenes as a new set of macrocyclic building blocks.</div>

Polysulfonylamine Polysulfonylamine, CXXXVIII [1], 1.1-Di(organosu!fonyl)-3,3-diorganylharnstoffe: Synthese von acht Vertretern und Kristallstruktur des Prototyps (MeSO2)2N-C(O)-NMe2 / Polysulfonylamines, CXXXVIII [1]. 1.1-Di(organosulfonyl)-3,3-diorganylureas: Synthesis of Eight Representatives and Crystal Structure of the Prototype (MeSO2)2N-C(O)-NMe2

2001 ◽  
Vol 56 (7) ◽  
pp. 680-688 ◽  
Author(s):  
Jörg Dalluhn ◽  
Hans-Heinrich Pröhl ◽  
Armand Blaschette ◽  
Peter G. Jones
Keyword(s):  
Crystal Packing ◽  
Three Dimensional ◽  
Acetonitrile Solution ◽  
X Ray Diffraction ◽  
Dimethylamino Group ◽  
Triclinic Space Group ◽  
H Nmr ◽  
Dimensional Network ◽  
Electrophilic Activation ◽  
High Degree

Eight compounds of the type (RSO2)2N-C(O)-NR'2 , where R = Me or 4-tolyl and R' = Me, Et, iPr or Ph, were obtained in good yields by treating the corresponding carbamoyl chlorides R'2NC(0)C1 with silver salts AgN (SO2R)2 in acetonitrile solution. The pronounced sensitivity of the compounds towards atmospheric moisture is indicative of a high degree of electrophilic activation at the carbonyl centre; bulk hydrolysis rapidly leads to carbon dioxide and the corresponding ammonium salt R'2NH+2'N (SO2R)2. In the 1H and 13C NMR solution spectra, the R4N groups of the ureas give rise to distinct R' resonances at room temperature, reflecting unusually high barriers to rotation about the C(O)-NR'2 bonds. For ( MeSO2)2N-C(O)-NMe2 (1a) and the analogous ditosyl compound, the 1H NMR signals of the dimethylamino group were found to coalesce at 107 °C and 93 °C, respectively, which corresponds to a rotational barrier of ⊿G#c ≈ 80 kJ mol-1. In the crystal of la (triclinic, space group P1̄, Z = 2; X-ray diffraction at -75 °C), the molecule possesses an essentially planar Me2N-C(O)-N moiety (except H atoms), whereas the C-NS2 grouping is pyramidalized to such an extent that N lies 27.8(2) pm out of the plane defined by the carbonyl C atom and the two sulfonyl S atoms [S-N-S 120.52(11)°, C-N-S 115.73(14) and 115.06(14)°]. The most remarkable features of the molecular structure are the exceedingly long C(O)-NS2 bond [148.6(3) pm] and the concomitantly short C-O and C(O)-NC2 bonds [121.4(3) and 132.2(3) pm]. The crystal packing of la is governed by a three-dimensional network of nine intermolecular C-H···O hydrogen bonds originating from the activated M e-S and M e -N donor groups (H···O 230-266 pm, C-H···O 123-173°).

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