Neutral Molecular Iron(II) Complexes Showing Tunable Bistability at Above, Below, and Just Room Temperature by a Crystal Engineering Approach: Ligand Mobility into a Three-Dimensional Flexible Supramolecular Network

2017 ◽  
Vol 17 (11) ◽  
pp. 6006-6019 ◽  
Author(s):  
Hiroaki Hagiwara ◽  
Takuya Masuda ◽  
Takuya Ohno ◽  
Mika Suzuki ◽  
Taro Udagawa ◽  
...  
Keyword(s):  
Crystal Engineering ◽  
Room Temperature ◽  
Three Dimensional ◽  
Supramolecular Network ◽  
Engineering Approach

scholarly journals The synthesis, structure and photoluminescence property of a novel 3D supramolecular compound based on mixed ligands of 8-hydroxy-quionline-5-sulfonate and ethylenediamine

2011 ◽  
Vol 76 (11) ◽  
pp. 1497-1504 ◽  
Author(s):  
Ying Wang ◽  
Changfu Zhuang ◽  
Chunhua Wu ◽  
Jiayan Zhang ◽  
Wang Li ◽  
...  
Keyword(s):  
Room Temperature ◽  
Three Dimensional ◽  
Photoluminescence Property ◽  
Supramolecular Network ◽  
X Ray Diffraction ◽  
X Ray ◽  
Mixed Ligands ◽  
Structure Solution ◽  
Hydroxy Quinoline ◽  
Hybrid Coordination

A new organic-inorganic hybrid coordination compound ZnQS (en)?2H2O (1) in which two different organic ligands, ethylenediamine (en) and 8-hydroxy-quinoline-5-sulfonic acid (H2QS) coordinate with zinc ions, has been synthesized via the evaporation method and characterized by single crystal X-ray diffraction analysis, IR spectroscopy and thermogravimetric analysis (TGA). The structure solution showed that compound 1 displays a three-dimensional supramolecular network by synergic linkage of hydrogen and coordinated bonds. Moreover, compound 1 exhibits intense photoluminescence at 513 nm excited at 396 nm in the solid state at room temperature.

Hydrogen-bonded assemblies in the molecular crystals of 2,2′-thiodiacetic acid with ethylenediamine ando-phenylenediamine

2017 ◽  
Vol 73 (2) ◽  
pp. 97-103 ◽  
Author(s):  
V. Gomathi ◽  
C. Theivarasu
Keyword(s):  
Crystal Engineering ◽  
Mechanical Stability ◽  
Three Dimensional ◽  
Molecular Crystals ◽  
Charge Transfer Complexes ◽  
Supramolecular Network ◽  
One Dimensional ◽  
Supramolecular Networks ◽  
Supramolecular Chains ◽  
Hydrogen Bonded

Carboxylate molecular crystals have been of interest due to the presence of hydrogen bonding, which plays a significant role in chemical and crystal engineering, as well as in supramolecular chemistry. Acid–base adducts possess hydrogen bonds which increase the thermal and mechanical stability of the crystal. 2,2′-Thiodiacetic acid (Tda) is a versatile ligand that has been widely explored, employing its multidendate and chelating coordination abilities with many metals; however, charge-transfer complexes of thiodiacetic acid have not been reported. Two salts, namely ethylenediaminium 2,2′-thiodiacetate, C2H10N22+·C4H4O4S22−, denoted Tdaen, and 2-aminoanilinium 2-(carboxymethylsulfanyl)acetate, C6H9N2+·C4H5O4S−, denoted Tdaophen, were synthesized and characterized by IR,1H and13C NMR spectroscopies, and single-crystal X-ray diffraction. In these salts, Tda reacts with the aliphatic (ethylenediamine) and aromatic (o-phenylenediamine) diamines, and deprotonates them to form anions with different valencies and different supramolecular networks. In Tdaen, the divalent Tda2−anions form one-dimensional linear supramolecular chains and these are extended into a three-dimensional sandwich-type supramolecular network by interaction with the ethylenediaminium cations. However, in Tdaophen, the monovalent Tda−anions form one-dimensional zigzag supramolecular chains, which are extended into a three-dimensional supramolecular network by interaction with the 2-aminoanilinium cations. Thus, both three-dimensional structures display different ring motifs. The structures of these diamines, which are influenced by hydrogen-bonded assemblies in the molecular crystals, are discussed in detail.

A Silver(I) Coordination Polymer Based on a Schiff Base Ligand: Synthesis, Crystal Structure and Luminescence Properties

2013 ◽  
Vol 68 (3) ◽  
pp. 284-288 ◽  
Author(s):  
Lin Yu Jin ◽  
Meng Meng Li ◽  
Dong Bin Dang ◽  
Yan Bai ◽  
Yan Ning Zheng
Keyword(s):  
Coordination Polymer ◽  
Room Temperature ◽  
Three Dimensional ◽  
Chain Structure ◽  
Luminescence Properties ◽  
Tridentate Ligand ◽  
Supramolecular Network ◽  
Zigzag Chain ◽  
X Ray Diffraction ◽  
X Ray

A new Ag(I) coordination polymer [AgL(NO3)]n 1 (L=4-(pyridine-2-yl)methyleneamino-1,2,4- trizaole) has been synthesized and characterized by IR spectroscopy, elemental analysis, powder and single-crystal X-ray diffraction. The Ag(I) atom has a seesaw environment with an N3O donor set from three N atoms of two ligands and one O atom of one NO-3 anion. Each twisted tridentate ligand is bound to two silver centers, and each silver atom is coordinated by two ligands thereby generating a zigzag chain structure. The chains interact with each other featuring a three-dimensional supramolecular network through multiple weak C-H···π interactions and C-H···O hydrogen bonds. The luminescence properties of the polymer 1 were investigated in the solid state at room temperature.

Reliability of π–π Stacking Interactions in Crystal Engineering: Synthesis and Structure of a Hemidirected Lead Complex

2008 ◽  
Vol 2008 (10) ◽  
pp. 578-580
Author(s):  
Tao Li ◽  
Hai-bin He ◽  
Mao-Sheng Jiang ◽  
Ming-Jie Huang ◽  
Xiang-Yang Cai
Keyword(s):  
Crystal Engineering ◽  
Three Dimensional ◽  
Lone Pair ◽  
Supramolecular Network ◽  
Aromatic Rings ◽  
One Dimensional ◽  
The One ◽  
Lead Complex ◽  
Single Crystal Analysis ◽  
Polymeric Framework

A new three-dimensional polymeric supramolecular PbII complex, {[Pb3(bpy)3(ip)3](H2O)}n, (bpy = 2,2′-bipyridine and ip = isophthalate), has been synthesised and characterised. Single-crystal analysis shows that {[Pb3(bpy)3(ip)3](H2O)}n contains a one-dimensional chain polymeric framework and all the Pb centres with a coordination number of six possess an electron lone pair. The coordination sphere is hemidirected which gives a highly distorted geometry. The arrangement of O- and N- atoms towards Pb atoms suggests a gap or hole in the coordination geometry around these atoms. Moreover, there are three types of π–π interactions between aromatic rings and the one-dimensional chains, which are connected by these interactions to form a three dimensional supramolecular network with the channels occupied by water molecules.

scholarly journals High-temperature Spin Crossover of a Solvent-Free Iron(II) Complex with the Linear Hexadentate Ligand [Fe(L2-3-2Ph)](AsF6)2 (L2-3-2Ph = bis[N-(1-Phenyl-1H-1,2,3-triazol-4-yl)methylidene-2-aminoethyl]-1,3- propanediamine)

2019 ◽  
Vol 5 (1) ◽  
pp. 10 ◽  
Author(s):  
Hiroaki Hagiwara
Keyword(s):  
Room Temperature ◽  
Spin Crossover ◽  
Variable Temperature ◽  
Spin Transition ◽  
Three Dimensional ◽  
Solvent Free ◽  
Supramolecular Network ◽  
Scanning Calorimetry ◽  
Mononuclear Iron ◽  
3D Network

A novel mononuclear iron(II) complex with a linear hexadentate N6 ligand, containing two 1,2,3-triazole moieties, [Fe(L2-3-2Ph)](AsF6)2 (1), was synthesized (L2-3-2Ph = bis[N-(1-Phenyl-1H-1,2,3-triazol-4-yl)methylidene-2-aminoethyl]-1,3-propanediamine). Variable-temperature magnetic susceptibility measurements revealed a gradual one-step spin crossover (SCO) between the high-spin (HS, S = 2) and low-spin (LS, S = 0) states above room temperature (T1/2 = 468 K). The spin transition was further confirmed by differential scanning calorimetry (DSC). A single-crystal X-ray diffraction study showed that the complex was in the LS state (S = 0) at room temperature (296 K). In the crystal lattice, a three-dimensional (3D) supramolecular network was formed by intermolecular CH⋯ and – interactions of neighboring complex cations [Fe(L2-3-2Ph)]2+. AsF6− ions were located interstitially in the 3D network of complex cations, with no solvent-accessible voids. The crystal structure at 448 K (mixture of HS and LS species) was also successfully determined thanks to the thermal stability of the solvent-free crystal.

Two novel lead(II) complexes of 2-(hydroxymethyl)pyridine: a threefold diamondoid supramolecular network based on Pb4O4cores and a two-dimensional (4,4) network based on Pb2O2units

2013 ◽  
Vol 69 (4) ◽  
pp. 394-399 ◽  
Author(s):  
Ting Liu ◽  
Yu-Peng Pan ◽  
Suna Wang ◽  
Jian-Min Dou
Keyword(s):  
Room Temperature ◽  
Three Dimensional ◽  
Supramolecular Network ◽  
Stacking Interactions ◽  
Two Dimensional ◽  
Compound I ◽  
Π Stacking ◽  
Compound Ii ◽  
Nitrate Anions

Reactions of 2-(hydroxymethyl)pyridine (Hhmp) with PbCl2and Pb(NO3)2at room temperature led to the formation of two novel compounds, namely tetrakis[μ3-(pyridin-2-yl)methanolato]-tetrahedro-tetrakis[chloridolead(II)], [Pb4(C6H6NO)4Cl4], (I), and poly[(μ2-nitrato)[μ2-(pyridin-2-yl)methanolato]lead(II)], [Pb(C6H6NO)(NO3)]n, (II). Compound (I) exhibits a tetranuclear Pb4O4cubane structure, which is connected through π–π stacking interactions between the pyridine groups of the (pyridin-2-yl)methanolate (hmp−) ligands and through C—H...Cl interactions to form an interesting threefold diamondoid network. Compound (II) possesses two-dimensional (4,4)-sql topology based on a Pb2O2unit, which is further extended into a three-dimensional supramolecular network through π–π stacking interactions between adjacent pyridine rings and through C—H...O interactions between the pyridine C atoms of the hmp−ligands and the nitrate anions.

scholarly journals Trapping liquid drugs inside crystals

2014 ◽  
Vol 70 (a1) ◽  
pp. C984-C984
Author(s):  
Alessia Bacchi ◽  
Davide Capucci ◽  
Paolo Pelagatti
Keyword(s):  
Human Health ◽  
Crystal Engineering ◽  
Room Temperature ◽  
The Body ◽  
New Materials ◽  
Active Molecule ◽  
Crystalline Materials ◽  
Pharmaceutical Ingredients ◽  
Solid Dosage ◽  
Intellectual Properties

The objective of this work is to embed liquid or volatile pharmaceuticals inside crystalline materials, in order to tune their delivery properties in medicine or agrochemistry, and to explore new regulatory and intellectual properties issues. Liquid or volatile formulations of active pharmaceutical ingredients (APIs) are intrinsically less stable and durable than solid forms; in fact most drugs are formulated as solid dosage because they tend to be stable, reproducible, and amenable to purification. Most drugs and agrochemicals are manufactured and distributed as crystalline materials, and their action involves the delivery of the active molecule by a solubilization process either in the body or on the environment. However some important compounds for the human health or for the environment occur as liquids at room temperature. The formation of co-crystals has been demonstrated as a means of tuning solubility properties of solid phases, and therefore it is widely investigated by companies and by solid state scientists especially in the fields of pharmaceuticals, agrochemicals, pigments, dyestuffs, foods, and explosives. In spite of this extremely high interest towards co-crystallization as a tool to alter solubility, practically no emphasis has been paid to using it as a means to stabilize volatile or labile or low-melting products. In this work we trap and stabilize volatile and liquid APIs and agrochemicals in crystalline matrices by engineering suitable co-crystals. These new materials alter the physic state of the active ingredients allowing to expand the phase space accessible to manufacturing and delivery. We have defined a benchmark of molecules relevant to human health and environment that have been combined with suitable partners according to the well known methods of crystal engineering in order to obtain cocrystals. The first successful results will be discussed; the Figure shows a cocrystal of propofol, a worldwide use anesthetic.

scholarly journals Crystal structure of K[Hg(SCN)3] – a redetermination

2014 ◽  
Vol 70 (9) ◽  
pp. i46-i46 ◽  
Author(s):  
Matthias Weil ◽  
Thomas Häusler
Keyword(s):  
Crystal Structure ◽  
Room Temperature ◽  
Three Dimensional ◽  
Lattice Parameters ◽  
Bond Lengths ◽  
Dimensional Network ◽  
Anisotropic Displacement Parameters ◽  
Precision And Accuracy ◽  
Standard Deviations ◽  
Atomic Coordinates

The crystal structure of the room-temperature modification of K[Hg(SCN)3], potassium trithiocyanatomercurate(II), was redetermined based on modern CCD data. In comparison with the previous report [Zhdanov & Sanadze (1952).Zh. Fiz. Khim.26, 469–478], reliability factors, standard deviations of lattice parameters and atomic coordinates, as well as anisotropic displacement parameters, were revealed for all atoms. The higher precision and accuracy of the model is, for example, reflected by the Hg—S bond lengths of 2.3954 (11), 2.4481 (8) and 2.7653 (6) Å in comparison with values of 2.24, 2.43 and 2.77 Å. All atoms in the crystal structure are located on mirror planes. The Hg2+cation is surrounded by four S atoms in a seesaw shape [S—Hg—S angles range from 94.65 (2) to 154.06 (3)°]. The HgS4polyhedra share a common S atom, building up chains extending parallel to [010]. All S atoms of the resulting1∞[HgS2/1S2/2] chains are also part of SCN−anions that link these chains with the K+cations into a three-dimensional network. The K—N bond lengths of the distorted KN7polyhedra lie between 2.926 (2) and 3.051 (3) Å.

scholarly journals Crystal Engineering Approach for Fabrication of Inverted Perovskite Solar Cell in Ambient Conditions

Energies ◽  
2021 ◽  
Vol 14 (6) ◽  
pp. 1751
Author(s):  
Inga Ermanova ◽  
Narges Yaghoobi Nia ◽  
Enrico Lamanna ◽  
Elisabetta Di Bartolomeo ◽  
Evgeny Kolesnikov ◽  
...  
Keyword(s):  
Solar Cell ◽  
Crystal Engineering ◽  
High Performance ◽  
Perovskite Solar Cells ◽  
Perovskite Solar Cell ◽  
Layer By Layer ◽  
Ambient Conditions ◽  
Sequential Method ◽  
Engineering Approach ◽  
Hole Transporting

In this paper, we demonstrate the high potentialities of pristine single-cation and mixed cation/anion perovskite solar cells (PSC) fabricated by sequential method deposition in p-i-n planar architecture (ITO/NiOX/Perovskite/PCBM/BCP/Ag) in ambient conditions. We applied the crystal engineering approach for perovskite deposition to control the quality and crystallinity of the light-harvesting film. The formation of a full converted and uniform perovskite absorber layer from poriferous pre-film on a planar hole transporting layer (HTL) is one of the crucial factors for the fabrication of high-performance PSCs. We show that the in-air sequential deposited MAPbI3-based PSCs on planar nickel oxide (NiOX) permitted to obtain a Power Conversion Efficiency (PCE) exceeding 14% while the (FA,MA,Cs)Pb(I,Br)3-based PSC achieved 15.6%. In this paper we also compared the influence of transporting layers on the cell performance by testing material depositions quantity and thickness (for hole transporting layer), and conditions of deposition processes (for electron transporting layer). Moreover, we optimized second step of perovskite deposition by varying the dipping time of substrates into the MA(I,Br) solution. We have shown that the layer by layer deposition of the NiOx is the key point to improve the efficiency for inverted perovskite solar cell out of glove-box using sequential deposition method, increasing the relative efficiency of +26% with respect to reference cells.

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