Investigation of nitrogen‐rich energetic polymers based on alkylbridged bis‐(1‐methyl‐tetrazolylhydrazines)

Nitrogen‐rich energetic polymers were synthesized by the polyaddition reaction of 1,2‐bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane ( 1a ), 1‐methyl‐1,2‐bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane ( 1b ), and 1,4‐bis(5‐mono‐methylhydrazinyl‐1H‐tetrazolyl)butane ( 1c ) with hexamethylene diisocyanate. The experiments showed that neither a polymerization from solution or bulk was possible. Therefore, a new method for the polymerization of tetrazolyl hydrazines had to be developed. The formed polymers were characterized by vibrational spectroscopy (IR) and elemental analysis. The energetic properties were investigated by bomb calorimetric measurements along with calculations using the EXPLO5 software. The thermal stability was investigated by DSC measurements. The properties render the polymers into promising compounds regarding an application as energetic binder. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 122–127, 2010     

NMR analysis of a series of 1,2‐bis(1‐R‐5‐oxo‐2,3‐dihydro‐1H‐pyrrol‐4‐ylidene)ethanes and X‐ray crystal structure analysis of the R = mesityl compound

Four tetramethyl 4,4′‐(ethane‐1,2‐diylidene)bis[1‐R‐5‐oxo‐4,5‐dihydro‐1H‐pyrrole‐2,3‐dicarboxylate] compounds, denoted class (1), are a series of conjugated buta‐1,3‐dienes substituted with a heterocyclic group. The compounds can be used as dyes and pigments due to their long‐range conjugated systems. Four structures were studied using ¹H NMR, ¹³C NMR and mass spectroscopy, viz. with R = 2,4,6‐trimethylphenyl, (1a), R = cyclohexyl, (1b), R = tert‐butyl, (1c), and R = isopropyl, (1d). A detailed discussion is presented regarding the characteristics of the three‐dimensional structures based on NMR analysis and the X‐ray crystal structure of (1a), namely tetramethyl 4,4′‐(ethane‐1,2‐diylidene)bis[5‐oxo‐1‐(2,4,6‐trimethylphenyl)‐4,5‐dihydro‐1H‐pyrrole‐2,3‐dicarboxylate], C₃₆H₃₆N₂O₁₀. The conjugation plane and stability were also studied via quantum chemical calculations.     

Adducts of 1,1,1‐tris(4‐hydroxy­phenyl)­ethane with 1,2‐bis(4‐pyridyl)­ethane and 1,2‐bis(4‐pyridyl)­ethene: continuously interwoven structures in three dimensions

In the adduct 1,2‐bis(4‐pyridyl)­ethane–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2), C₁₂H₁₂N₂·2C₂₀H₁₈O₃, the bipyridyl component lies across an inversion centre in P. The tris‐phenol mol­ecules [systematic name: 4,4′,4′′‐(ethane‐1,1,1‐triyl)­triphenol] are linked by O—H?O hydrogen bonds to form sheets built from R(38) rings, and symmetry‐related pairs of sheets are linked by the bipyridyl mol­ecules via O—H?N hydrogen bonds to form open bilayers. Each bilayer is interwoven with two adjacent bilayers, forming a continuous three‐dimensional structure. In the adduct 1,2‐bis(4‐pyridyl)­ethene–1,1,1‐tris(4‐hydroxy­phenyl)­ethane–methanol (1/1/1), C₁₂H₁₀N₂·C₂₀H₁₈O₃·CH₄O, the mol­ecules are linked by O—H?O and O—H?N hydrogen bonds into three interwoven three‐dimensional frameworks, generated by single spiral chains along [010] and [001] and a triple‐helical spiral along [100].     

Hydrogen bonding and π–π interactions in the cocrystal salt [Fe(bpe)2(H2O)4](TCEP)2·2(bpe) [bpe is trans‐1,2‐bis(pyridin‐4‐yl)ethene and TCEP is 1,1,3,3‐tetracyano‐2‐ethoxypropenide]

The cocrystal salt tetraaquabis[trans‐1,2‐bis(pyridin‐4‐yl)ethene‐κN]iron(II) bis(1,1,3,3‐tetracyano‐2‐ethoxypropenide)–trans‐1,2‐bis(pyridin‐4‐yl)ethene (1/2), [Fe(C₁₂H₁₀N₂)₂(H₂O)₄](C₉H₅N₄O)₂·2C₁₂H₁₀N₂, is a rare example of a mononuclear Fe^II compound with trans‐1,2‐bis(pyridin‐4‐yl)ethane (bpe) ligands. The complex cation resides on a crystallographically imposed inversion center and exhibits a tetragonally distorted octahedral coordination geometry. Both the symmetry‐independent bpe ligand and the cocrystallized bpe molecule are essentially planar. The 1,1,3,3‐tetracyano‐2‐ethoxypropenide counter‐ion is nonplanar and the bond lengths are consistant with significant electron delocalization. The extended structure exhibits an extensive O—H…N hydrogen‐bonding network with layers of complex cations joined by the cocrystallized bpe. Both the coordinated and the cocrystallized bpe are involved in π–π interactions. Hirshfeld and fingerprint plots reveal the important intermolecular interactions. Density functional theory was used to estimate the strengths of the hydrogen‐bonding and π–π interactions, and suggest that the O—H…N hydrogen bonds enhance the strength of the π‐interactions by increasing the polarization of the pyridine rings.     

Asymmetric structure of cis‐[N‐(9‐anthracenylmethyl)‐1,2‐ethanediamine]dipyridineplatinum(II) dinitrate

Platinum antitumour agents, containing aromatic rings, which are used for targeting DNA in effective therapies for the treatment of cancer. We have synthesized the title metallocomplex with an aromatic ligand and determined its crystal structure. In many cases, complexes of platinum and other metals have a symmetrical structure. In contrast, the platinum(II) complex with pyridine and N‐(9‐anthracenylmethyl)‐1,2‐ethanediamine as ligands (systematic name: cis‐{N‐[(anthracen‐9‐yl)methyl]ethane‐1,2‐diamine‐κ²N ,N ′}bis(pyridine‐κN )platinum(II) dinitrate), [Pt(C₅H₅N)₂(C₁₇H₁₈N₂)](NO₃)₂, is asymmetric. Of the two pyridine ligands, only one is π‐stacked with anthracene, resulting in an asymmetric structure. Moreover, the angle of orientation of each pyridine ligand is variable. Further examination of the packing motif confirms an intermolecular edge‐to‐face interaction.     

Study of Six Green Insensitive High Energetic Coordination Polymers Based on Alkali/Alkali‐Earth Metals and 4,5‐Bis(tetrazol‐5‐yl)‐2 H‐1,2,3‐triazole

Constructing insensitive high‐performance energetic coordination polymers (ECPs) with alkali/alkali‐earth metal ions and a nitrogen‐rich organic backbone has been proved to be a feasible strategy in this work. Six diverse dimensional novel ECPs (compounds 1 – 6 ) were successfully synthesized from Na^I, Cs^I, Ca^II, Sr^II, Ba^II ions and a nitrogen‐rich triheterocyclic 4,5‐bis(tetrazol‐5‐yl)‐2 H ‐1,2,3‐triazole (H₃BTT). All compounds show outstanding stability and low sensitivity, the thermal stability of these ECPs are significantly improved as the structural reinforcement increases from 1D to 3D, in which the decomposition temperature of 3D Ba^II based compound 6 is as high as 397 °C. Long‐term storage experiments show that compounds 5 and 6 are stable enough at high temperature. Moreover, the six compounds hold considerable detonation performances, in which Ca^II based compound 5 possesses the detonation velocity of 9.12 km s⁻¹, along with the detonation pressure of 34.51 GPa, exceeding those of most energetic coordination polymers. Burn tests further certify that the six compounds can be versatile pyrotechnics.     

Pd(0)‐catalyzed polyaddition of bifunctional vinyloxiranes with 1,3‐dicarbonyl compounds: The synthesis of polymers containing hydroxy and carbonyl groups

The palladium(0)‐catalyzed polyaddition of bifunctional vinyloxiranes [1,4‐bis(2‐vinylepoxyethyl)benzene ( 1a ) and 1,4‐bis(1‐methyl‐2‐vinylepoxyethyl)benzene ( 1b )] with 1,3‐dicarbonyl compounds [methyl acetoacetate ( 4 ), dimethyl malonate ( 6 ), and Meldrum's acid ( 8 )] was investigated under various conditions. The polyaddition of 1 with 4 was carried out in tetrahydrofuran with phosphine ligands such as PPh₃ and 1,2‐bis(diphenylphosphino)ethane (dppe). Polymers having hydroxy, ketone, and ester groups in the side groups ( 5 ) were obtained in good yields despite the kinds of ligands employed. The number‐average molecular weight value of 5b was higher than that of 5a . The polyaddition of 1b and 6 was affected by the kinds of ligands employed. The corresponding polymer 7b was not obtained when PPh₃ and 1,2‐bis(diphenylphosphino)ferrocene were used. The polyaddition was carried out with dppe as the ligand and gave polymer 7b in a good yield. The molecular weight of the polymer obtained from 1b and 8 was much higher than those of polymers 5b and 7b . The polyaddition with Pd₂(dba)₃ · CHCl₃/dppe as a catalyst (where dba is dibenzylideneacetone) produced polymer 9b in a 92% yield (number‐average molecular weight = 45,600). The stereochemistries of all the obtained polymers were confirmed as an E configuration by the coupling constant of the vinyl proton. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2487–2494, 2002     

Copper(II) succinate complexes with 1,2‐di‐4‐pyridylethane and 1,3‐di‐4‐pyridylpropane

The compounds poly[di‐μ₄‐succinato‐μ₂‐1,2‐di‐4‐pyridylethane‐dicopper(II)], [Cu₂(C₄H₄O₄)₂(C₁₂H₁₂N₂)]_n, (I), and poly[di‐μ₄‐succinato‐μ₂‐1,3‐di‐4‐pyridylpropane‐dicopper(II)], [Cu₂(C₄H₄O₄)₂(C₁₃H₁₄N₂)]_n, (II), exhibit polymeric structures with the dicopper units doubly bridged by bis‐bidentate succinate groups and crosslinked by the separator bis(pyridyl) molecules. In (I), the molecule exhibits a centre of inversion located midway between the core Cu‐dimer atoms and another that relates half of the bis(pyridyl)ethane ligand to the other half. Compound (II) has a similar molecular packing but with a doubled lattice constant and noncentrosymmetric core units. An antiferromagnetic interaction due to the dinuclear copper units was deduced from magnetic subsceptibility measurements, and spin triplet signals were detected in the electron paramagnetic resonance spectra for both compounds.     

Structurally Different Calcium(II) Complexes with 5‐Substituted Tetrazole Ligands

Three different tetrazole‐carboxylate ligands, Hpymtza, Hpytza, and H₂dtzeda were chosen to be reacted with Ca(NO₃)₂ · 4H₂O, resulting in the formation of three coordination compounds, [Ca(pymtza)₂(H₂O)₄] ( 1 ), [Ca(pytza)₂(H₂O)₂] ( 2 ), and [Ca(dtzeda)(H₂O)₂] ( 3 ) [Hpymtza = 5‐(2‐pyrimidyl)tetrazole‐1‐acetic acid, Hpytza = 5‐(3‐pyridyl)tetrazole‐2‐acetic acid, and H₂dtzeda = 1, 2‐bis(tetrazol‐5‐yl)ethane‐N1, N1′‐diacetic acid]. X‐ray diffraction analysis revealed that compound 1 displays a mononuclear structure, compound 2 is a one dimensional zigzag chain structure, whereas 3 shows a three‐dimensional structure. The structures were controlled by not only the different substituents of the tetrazolyl ring, but also the complementary hydrogen bonds. Furthermore, the luminescence properties of compounds 1 – 3 were investigated at room temperature in the solid state. These emissions can be tentatively attributed to the ligand centered emission.     

3D Luminescent Copper(I) Iodide Coordination Polymer Based on Cu4I4 Clusters and an Ethyl‐bridging Bis(triazole) Ligand

The copper‐iodine based coordination polymer [Cu₄I₂(bmte)]_n ( 1 ) [H₂bmte = 1,2‐bis(5‐methyl‐1H‐1,2,4‐triazol‐3‐yl)ethane] was synthesized using cuprous iodide and a flexible 3‐substituted, ethyl‐bridging bis(triazole) ligand under solvothermal conditions. X‐ray diffraction analysis reveals that compound 1 shows a 3D framework containing Cu₄I₄ clusters and alternating left‐ and right‐handed [Cu(triazole)] helices, which result in a (4,8)‐connected fluorite (flu) topological network. Moreover, compound 1 exhibits orange phosphorescence with the emission maxima at 590 nm in the solid state at room temperature.     

One Dimensional Coordination Polymer Constructed by1,2—Bis（4—pyridinecarboxamido）ethane and Copper（Ⅱ）

The ligand [1,2‐bis(4‐pyridinecarboxamido)ethane] (L) and the coordination polymer |[Cu(L)₂(H₂O)]‐(NO₃)₂·6H₂O|·(1) haw been synthesized and characterized by ER and ¹H NMR spectra. Their molecular structures and the packing of 1 have been determined by single‐crystal X‐ray diffraction analysis. The Cu(n) in 1 is bridged by two ligands forming an infinite one‐dimensional chain like structure and L in 1 adopts a different conformation from its free state. 1 belongs to monoclinic, space group P2₁/n, a = 1.2896(3) nm, b = 1.2552(8) nm, c = 2.2903(19) nm, β = 93.04(5)°, Z = 4, V = 3.702(4) nm³. The TG and DTG experiments showed that the uncoordinated H₂O can be removed at low temperature by heating, and it does not decompose until 250 °C.     

[Hg2(μ‐bpe)(μ‐OAc)2(μ‐SCN)2]n,a New Two‐Dimensional Coordination Polymer Involving Three Simultaneously Bridging Ligands: 1,2‐Bis(4‐pyridyle)ethene,Acetate, and Thiocyanate

A new mercury(II) complex of 1,2‐bis(4‐pyridyle)ethene (bpe) with anionic acetate and thiocyanate ligands has been synthesized and characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. The single crystal X‐ray analysis shows that the complex is a two‐dimensional polymer with simultaneously bridging 1,2‐bis(4‐pyridyle)ethane, acetate and thiocyanate ligands and basic repeating dimeric [Hg₂(μ‐bpe)(μ‐OAc)₂(μ‐SCN)₂] units. The two‐dimensional system forms a three‐dimensional network by packing via π‐π stacking interactions.     

μ‐1,2‐Bis(4‐pyridyl)ethene‐κ2N:N′‐bis(tetraaqua­{4‐[2‐(4‐pyridinio)­ethenyl]pyridine‐κN}cobalt(II)) hexaaqua­cobalt(II) tetrakis(sulfate) octahydrate

The title compound, [Co₂(C₁₂H₁₁N₂)₂(C₁₂H₁₀N₂)(H₂O)₈][Co(H₂O)₆](SO₄)₄·8H₂O, consists of bis(4‐pyridyl)ethenedicobalt(II) cations, hexaaqua­cobalt cations, sulfate anions and water solvent molecules that are linked by hydrogen bonds into a network structure. In the hexaaquacobalt cation, the six water molecules are coordinated in an octahedral geometry to the Co atom, which lies on an inversion centre. The other cation is a 1,2‐bis(4‐pyridyl)ethene‐bridged centrosymmetric dimer, consisting of protonated 1,2‐bis(4‐pyridyl)­ethene cations, a bridging 1,2‐bis(4‐pyridyl)ethene ligand and tetraaqua­cobalt cations. Each Co atom is six‐coordinated by four water molecules and two N atoms from a protonated 1,2‐bis(4‐pyridyl)ethene cation and the bridging 1,2‐bis(4‐pyridyl)­ethene ligand, and the geometry around each Co atom is octahedral.     

A new two‐dimensional managnese(II) coordination polymer constructed by 2,2′‐(1,2‐phenylene)bis(1H‐imidazole‐4,5‐dicarboxylate)

In recent years, N‐heterocyclic carboxylate ligands have attracted much interest in the preparation of new coordination polymers since they contain N‐atom donors, as well as O‐atom donors, and have a rich variety of coordination modes which can lead to polymers with intriguing structures and interesting properties. A new two‐dimensional coordination polymer, namely poly[[μ₃‐2,2′‐(1,2‐phenylene)bis(4‐carboxy‐1H‐imidazole‐5‐carboxylato)‐κ⁶O⁴,N³,N^3′,O^4′:O⁵:O^5′]manganese(II)], [Mn(C₁₆H₈N₄O₈)]_n or [Mn(H₄Phbidc)]_n, has been synthesized by the reaction of Mn(OAc)₂·4H₂O (OAc is acetate) with 2,2′‐(1,2‐phenylene)bis(1H‐imidazole‐4,5‐dicarboxylic acid) (H₆Phbidc) under solvothermal conditions. In the polymer, each Mn^II ion is six‐coordinated by two N atoms from one H₄Phbidc²⁻ ligand and by four O atoms from three H₄Phbidc²⁻ ligands, forming a significantly distorted octahedral MnN₂O₄ coordination geometry. The Mn^II ions are linked by hexadentate H₄Phbidc²⁻ ligands, leading to a two‐dimensional structure parallel to the ac plane. In the crystal, adjacent layers are further connected by N—H…O hydrogen bonds, forming a three‐dimensional structure in the solid state.     

Synthesis and Characterization of 3,3′‐Bis(Dinitromethyl)‐5,5′‐Azo‐1H‐1,2,4‐Triazole

The synthesis of 3,3′‐bis(dinitromethyl)‐5,5′‐azo‐1H‐1,2,4‐triazole ( 5 ) using the readily available starting material 2‐(5‐amino‐1H‐1,2,4‐triazol‐3‐yl)acetic acid ( 1 ) is described. All compounds were characterized by means of NMR, IR, and Raman spectroscopy. The energetic compound 5 was additionally characterized by single‐crystal X‐ray diffraction and DSC measurements. The sensitivities towards impact, friction and electrical discharge were determined. In addition, detonation parameters (e.g. heat of explosion, detonation velocity) of the target compound were computed using the EXPLO5 code based on the calculated (CBS‐4M) heat of formation and X‐ray density.     

Linkage isomeric oxamate chelates: rac‐bis(ethane‐1,2‐diamine)oxamatocobalt(III) bis(trifluoromethanesulfonate) dihydrate and Λ(+)578‐bis(ethane‐1,2‐diamine)[oxamato(2−)]cobalt(III) trifluoromethanesulfonate

The structures of rac‐bis(ethane‐1,2‐diamine)(oxamato‐κ²O¹,O²)cobalt(III) bis(trifluoromethanesulfonate) dihydrate, [Co(C₂H₂NO₃)(C₂H₈N₂)₂](CF₃SO₃)₂·2H₂O, (I), and Λ(+)₅₇₈‐bis(ethane‐1,2‐diamine)[oxamato(2−)‐κ²N,O¹]cobalt(III) trifluoromethanesulfonate, [Co(C₂HNO₃)(C₂H₈N₂)₂]CF₃SO₃, (II), are compared. Together, the two complexes constitute the first pair of linkage isomers of bidentate oxamate available for structural comparison.     

The three‐dimensional coordination polymer poly[[aqua[μ4‐2,2′‐(diazene‐1,2‐diyl)dibenzoato]lead(II)] 1,2‐bis(pyridin‐4‐yl)ethylene hemisolvate]

A novel three‐dimensional coordination polymer, {[Pb(C₁₄H₈N₂O₄)(H₂O)]·0.5C₁₂H₁₀N₂}_n, has been synthesized by hydrothermal reaction of Pb(OAc)₂·3H₂O (OAc is acetate), 2,2′‐(diazene‐1,2‐diyl)dibenzoic acid (H₂L) and 1,2‐bis(pyridin‐4‐yl)ethylene (bpe). The asymmetric unit contains a crystallographically independent Pb^II cation, one L²⁻ ligand, an aqua ligand and half a bpe molecule. Each Pb^II centre is seven‐coordinated by six O atoms of bridging–chelating carboxylate groups from L²⁻ ligands and by one O atom from a coordinated water molecule. The Pb^II cations are bridged by L²⁻ ligands, forming [PbO₂]_n chains along the a axis. These chains are further connected by L²⁻ ligands along the b and c axes to give a three‐dimensional framework with a 4¹²6³ topology. The channel voids are occupied by bpe molecules.     

Synthesis of diallyl‐containing polyimide and the effect of allyl groups on properties

A diallyl‐containing bisphenol, 1,1‐bis(3‐allyl‐4‐hydroxyphenyl)‐1‐(6‐oxido‐6H ‐dibenzo [c,e][1,2] oxaphosphorin‐6‐yl) ethane ( 1 ), was prepared by a two‐step procedure. Then, a diallyl‐containing diamine, 1,1‐bis(3‐allyl‐4‐(4‐aminophenoxy)‐phenyl)‐1‐(6‐oxido‐6H‐dibenzo [c,e][1,2] oxaphosphorin‐6‐yl)ethane ( 3 ), was prepared from the nucleophilic substitution of ( 1 ) with 4‐fluoronitrobenzene, followed by the reduction by Fe/HCl. A flexible polyimide ( 4 ) with curable diallyl linkages was prepared from the condensation of ( 3 ) and 4,4′‐oxydiphthalic anhydride in m‐cresol in the presence of isoquinoline. Curing polyimide ( 4 ) at 300 °C leads to thermosetting polyimide ( 5 ). We discussed the amounts of allyl group on T_g, coefficient of thermal expansion, and thermal stability of thermosetting polyimides, and found that thermal properties and dimensional stability of thermosetting polyimides increase with the amounts of cured allyl moieties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 513–520     

A fourfold interpenetrating diamondoid three‐dimensional coordination polymer: poly[[[μ2‐1,2‐bis(pyridin‐4‐yl)ethene‐κ2N:N′](μ2‐5‐hydroxyisophthalato‐κ2O1:O3)zinc(II)] 1,2‐bis(pyridin‐4‐yl)ethene hemisolvate]

In the title compound, {[Zn(C₈H₄O₅)(C₁₂H₁₀N₂)]·0.5C₁₂H₁₀N₂}_n or {[Zn(HO‐BDC)(bpe)]·0.5bpe}_n [HO‐H₂BDC is 5‐hydroxyisophthalic acid and bpe is 1,2‐bis(pyridin‐4‐yl)ethene], the asymmetric unit contains a Zn^II atom, one HO‐BDC ligand, one coordinated bpe ligand and half a noncoordinating bpe molecule with crystallographic inversion symmetry. Each Zn^II centre is four‐coordinated by two O atoms from two distinct HO‐BDC ligands and two N atoms from two different bpe ligands in a ZnO₂N₂ coordination environment. The three‐dimensional topology of the title compound corresponds to a fourfold interpenetrating diamondoid coordination polymer network, with the uncoordinated bpe ligands located in the cavities, hydrogen bonded to the main network via the hydroxy group of the HO‐H₂BDC ligand.     

C—H…Cl Hydrogen Bond and π-π Interaction Based Two 3D Supramolecular Architectures of Cu(II) and Co(II) Complexes with Chiral 1,2-Bis(benzimidazol-2-yl) ethane Ligand Containing 2D Grids

合成了两个新的配合物CuLCl₂•2EtOH(1) 和CoLCl₂ (2) [L是( S , S )－1,2－二N－甲基苯并咪唑－1,2－二甲氧基－乙烷],并通过单晶X衍射确定它们的结构。配合物1中,L作为三齿[N, N, O]配体,而配合物2 中,L作为二齿[N, N]配体。这两个配合物共同的结构特点都是通过分子内氢键形成2维的格子结构,然后通过分子间的C－H···Cl型氢键和π–π堆积作用形成3维结构。