5,5′‐Hydrazinebistetrazole: An Oxidation‐stable Nitrogen‐rich Compound and Starting Material for the Synthesis of 5,5′‐Azobistetrazolates

All 5,5′‐hydrazinebistetrazoles reported in the literature are sensitive to oxidation and react with atmospheric oxygen to yield the corresponding 5,5′‐azobistetrazolates on time. Herewith, we report on the synthesis of the free acid 5,5′‐hydrazinebistetrazole (HBT) which showed to be stable on air for extended periods of time. The compound was fully characterized by analytical and spectroscopic methods and its X‐ray structure was determined by diffraction techniques. Besides, we determined its explosive properties by BAM methods and calculated its heat of formation (+414 kJ mol^?1), detonation velocity (8523 m s^?1) and detonation pressure (27.7 GPa). HBT proved to be very safe to handle (impact sensitivity: >30 J, friction sensitivity: ～108 N) and was used as a starting material for the synthesis of some already reported 5,5′‐azobistetrazolates: NH₄⁺, NH₂NH₃⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.     

Two Energetic Salts based on 5,5′‐Bitetrazole‐1,1′‐diolate: Syntheses,Characterization, and Properties

Two salts based on 1H,1′H‐5,5′‐bitetrazole‐1,1′‐diolate (BTO) anion with pyrazole ( 1 ) and imidazole ( 2 ) cations were synthesized with metathesis reactions. Structural characterization was accomplished for them by using the element analysis, Fourier transform infrared spectroscopy (FT‐IR), NMR and mass spectrum, and X‐ray single crystal diffraction. Thermal analysis for the title salts were determined by means of differential scanning calorimetry (DSC) and thermogravimetry‐derivative thermogravimetry (TG‐DTG) as well as the calculation of non‐isothermal kinetic parameters. Consequently, both salts shown acceptable thermal stabilities as the decomposition temperatures were over 200 °C. The enthalpies of formation were calculated for these salts using the measured combustion energies with a result of 70.6 kJ · mol^–1 for 1 and –47.8 kJ · mol^–1 for 2 , respectively. Impact and friction sensitivities were also tested and the results indicated that these salts both have low sensitivities (>40 J, 120 N). The title energetic salts possess acceptable performance, they can therefore be applied in the field of energetic materials.     

Five Coordinated Zinc(II) and Tris‐Chelate Cadmium(II) Complexes with 2,2′‐Diamino‐5,5′‐dimethyl‐4,4′‐bithiazole – Syntheses,Spectroscopic Characterization,and Crystal Structure

The new synthesized ligand (DADMBTZ = 2,2′‐diamino‐5,5′‐dimethyl‐4,4′‐bithiazole), which is mentioned in this text, is used for preparing the two new complexes [Zn(DADMBTZ)₃](ClO₄)₂. 0.8MeOH.0.2H₂O ( 1 ) and [Cd(DADMBTZ)₃](ClO₄)₂ ( 2 ). The characterization was done by IR, ¹H, ¹³C NMR spectroscopy, elemental analysis and single crystal X‐ray determination. In reaction with DADMBTZ, zinc(II) and cadmium(II) show different characterization. In 2 , to form a tris‐chelate complex with nearly C₃ symmetry for coordination polyhedron, DADMBTZ acts as a bidentate ligand. In 1 , this difference maybe relevant to small radii of Zn²⁺ which make one of the DADMBTZ ligands act as a monodentate ligand to form the five coordinated Zn²⁺ complex. In both 1 and 2 complexes the anions are symmetrically different. 1 and 2 complexes form 2‐D and 3‐D networks via N‐H···O and N‐H···N hydrogen bonds, respectively.     

Two Bulky Conjugated 4′‐(4‐Hydroxyphenyl)‐4,2′:6′,4′′‐terpyridine‐based Layered Complexes: Synthesis,Structure, and Photocatalytic Hydrogen Evolution Activity

Two new layered complexes with the formulas of {[Cu(H₂O)(HL)₂Cl](NO₃)}_n ( 1 ) and {[Cu(H₂O)₂(HL)₂](NO₃)₂}_n ( 2 ) were solvothermally synthesized by the reactions of the bulky conjugated 4′‐(4‐hydroxyphenyl)‐4,2′:6′,4′′‐terpyridine ligand (HL) with different Cu^II salts, which were further used as photocatalysts to achieve hydrogen production from water splitting. Single‐crystal structural analyses reveal that both complexes feature coplanar (4 4) layers with different connection manners between the HL extended Z‐shaped chains. More interestingly, 1 possessing more negative conduction band potential and higher structural stability exhibits a large hydrogen production rate of 2.43 mmol · g^–1 · h^–1, which is four times higher than that of 2 . Thus, the Cu^II‐based coordination polymers modified by the bulky conjugated organic ligand can become potentially promising non‐Pt photocatalysts for hydrogen production from water splitting.     

Improved conditions for fluorescent staining of proteins with 4,4′‐dianilino‐1,1′‐binaphthyl‐5,5′‐disulfonic acid in SDS‐PAGE

A simple and sensitive fluorescent staining method for the detection of proteins in SDS‐PAGE, namely IB (improved 4,4′‐dianilino‐1,1′‐binaphthyl‐5,5′‐disulfonic acid) stain, is described. Non‐covalent hydrophobic probe 4,4′‐dianilino‐1,1′‐binaphthyl‐5,5′‐disulfonic acid was applied as a fluorescent dye, which can bind to hydrophobic sites in proteins non‐specifically. As low as 1 ng of protein band can be detected briefly by 30 min washing followed by 15 min staining without the aiding of stop or destaining step. The sensitivity of the new presented protocol is similar to that of SYPRO Ruby, which has been widely accepted in proteomic research. Comparative analysis of the MS compatibility of IB stain and SYPRO Ruby stain allowed us to address that IB stain is compatible with the downstream of protein identification by PMF.     

Highly Fluorescent Conjugated Copolymers Containing Dithieno[3,2‐b:2′,3′‐d]pyrrole

Three copolymers that incorporate dithieno[3,2‐b:2′,3′‐d]pyrrole with fluorene, carbazole, or pyridine have been prepared by Suzuki reaction and characterized by NMR spectroscopy and GPC. A new homopolymer of dithieno[3,2‐b:2′,3′‐d]pyrrole was also synthesized for the comparison of their structure–property relationships. Their thermal, optical, and electrochemical properties have been investigated. All the polymers exhibit good thermal stability with decomposition temperatures around 400 °C. The fluorescence quantum efficiencies of all these polymers in solution are in the range of 33.5–55.5%. The copolymers also show high film fluorescence quantum efficiencies of about 20% while the fluorescence of the homopolymer film is almost quenched.

     

Syntheses,Structures and Characterization of Four Metal‐Organic Frameworks constructed by 2,2′,6,6′‐Tetramethoxy‐4,4′‐biphenyldicarboxylic Acid

Four metal‐organic frameworks (MOFs), {[Mn_3.5L(OH)(HCOO)₄(DMF)] · H₂O} ( 1 ), {[In_2.5L₂O(OH)_1.5(H₂O)₂] · DMF · CH₃CN · 2H₂O} ( 2 ), {[Pb₄L₃O(DMA)] · CH₃CN} ( 3 ), and {[LaL(NO₃)(DMF)₂] · 2H₂O} ( 4 ) were synthesized by utilizing the ligand 2,2′,6,6′‐tetramethoxy‐4,4′‐biphenyldicarboxylic acid (H₂L) via solvothermal methods. All MOFs were characterized by single‐crystal X‐ray diffraction, powder X‐ray diffraction, thermogravimetric analysis, and infrared spectroscopy. In 1 , the Mn²⁺ ions are interconnected by formic groups in situ produced via DMF decomposition to form a rare 2D macrocyclic plane, which is further linked by L^2– to construct the final 3D network. In 2 , 1D zip‐like infinite chain is formed and then interconnected to build the 3D framework. In 3 , a [Pb₆(μ₄‐O)₂(O₂C)₁₀(DMA)₂] cluster with a centrosymmetric [Pb₆(μ₄‐O)₂]⁸⁺ octahedral core is formed in the 3D structure. In 4 , the La³⁺ ions are connected with each other through carboxylate groups of L^2– to generate 1D zigzag chain, which is further linked by L^2– to construct a 3D network with sra topology. Solid photoluminescence properties of 3 and 4 were also investigated.     

Preparation,Crystal Structure and Properties of a New Crystal Form of Diammonium 5,5′‐bistetrazole‐1,1′‐diolate

A new crystal form of diammonium 5,5′‐bistetrazole‐1,1′‐diolate ( 1 ) was prepared by two novel methods and fully characterized by using IR, NMR spectroscopy, elementary analysis, single crystal X‐ray crystallography and thermal gravity/differential thermal analysis (TG/DTA). Crystalline 1 was found as monoclinic and space group of P21/c (14). The TG/DTA analysis showed that the decomposition temperature of 1 was 287.8°C with a mass loss of 91.2% in the range of 220–300°C at a heating rate of 5°C/min. The sensitivities test towards impact, friction of 1 indicated that 1 has much lower sensitivities than those of RDX/HMX and is comparable to those of TNT, which suggested that 1 could be used as a good candidate of new insensitive energetic compound.     

One‐dimensional CuII coordination polymers containing C2h‐symmetric 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate linkers

Two new one‐dimensional Cu^II coordination polymers (CPs) containing the C_2h‐symmetric terphenyl‐based dicarboxylate linker 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate (3,3′‐TPDC), namely catena‐poly[[bis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ⁴O,O′:O′′:O′′′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂]·H₂O}_n, (I), and catena‐poly[[aquabis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ²O³:O^3′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂(H₂O)]·H₂O}_n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4‐diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X‐ray crystallography. The 3,3′‐TPDC bridging ligands coordinate the Cu^II ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one‐dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one‐dimensional coordination polymer chains, forming a two‐dimensional network in (I) and a three‐dimensional network in (II).     

A three‐dimensional CdII coordination polymer constructed from 1,1′‐biphenyl‐2,2′,5,5′‐tetracarboxylate and 1,4‐bis(1H‐imidazol‐1‐yl)benzene ligands

The title coordination polymer, poly[[aqua(μ₅‐1,1′‐biphenyl‐2,2′,5,5′‐tetracarboxylato)bis[μ₂‐1,4‐bis(1H‐imidazol‐1‐yl)benzene]dicadmium(II)] dihydrate], {[Cd₂(C₁₆H₆O₈)(C₁₂H₁₀N₄)₂(H₂O)]·2H₂O}_n, was crystallized from a mixture of 1,1′‐biphenyl‐2,2′,5,5′‐tetracarboxylic acid (H₄bpta), 1,4‐bis(1H‐imidazol‐1‐yl)benzene (1,4‐bib) and cadmium nitrate in water–dimethylformamide. The crystal structure consists of two crystallographically independent Cd^II cations, with one of the Cd^II cations possessing a slightly distorted pentagonal bipyramidal geometry. The second Cd^II centre is coordinated by carboxylate O atoms and imidazole N atoms from two separate 1,4‐bib ligands, displaying a distorted octahedral CdN₂O₄ geometry. The completely deprotonated bpta⁴⁻ ligand, exhibiting a new coordination mode, bridges five Cd^II cations to form one‐dimensional chains viaμ₃‐η¹:η²:η¹:η² and μ₂‐η¹:η¹:η⁰:η⁰ modes, and these are further linked by 1,4‐bib ligands to form a three‐dimensional framework with a (4².6⁴)(4.6²)(4³.6⁵.7²) topology. The structure of the coordination polymer is reinforced by intermolecular hydrogen bonding between carboxylate O atoms, aqua ligands and crystallization water molecules. The solid‐state photoluminescence properties were investigated and the complex might be a candidate for a thermally stable and solvent‐resistant blue fluorescent material.     

Preparation and physical properties of poly(4,4′‐diamino‐3′‐carbamoylbenzanilide terephthalamide) and poly(4,4′‐diamino‐3′‐carbamoylbenzanilide isophthalamide) films

To prepare thermally stable and high‐performance polymeric films, new solvent‐soluble aromatic polyamides with a carbamoyl pendant group, namely poly(4,4′‐diamino‐3′‐carbamoylbenzanilide terephthalamide) (p‐PDCBTA) and poly(4,4′‐diamino‐3′‐carbamoylbenzanilide isophthalamide) (m‐PDCBTA), were synthesized. The polymers were cyclized at around 200 to 350 °C to form quinazolone and benzoxazinone units along the polymer backbone. The decomposition onset temperatures of the cyclized m‐ and p‐PDCBTAs were 457 and 524 °C, respectively, lower than that of poly(p‐phenylene terephthalamide) (566 °C). For the p‐PDCBTA film drawn by 40% and heat‐treated, the tensile strength and Young's modulus were 421 MPa and 16.4 GPa, respectively. The film cyclized at 350 °C showed a storage modulus (E′) of 1 × 10¹¹ dyne/cm² (10 GPa) over the temperature range of room temperature to 400 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 775–780, 2000     

New organo‐soluble aromatic polyimides based on 3,3′,5,5′‐tetrabromo‐2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and aromatic diamines

New aromatic tetracarboxylic dianhydride, having isopropylidene and bromo‐substituted arylene ether structure 3,3′,5,5′‐tetrabromo‐2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride, was synthesized by the reaction of 4‐nitrophthalonitrile with 3,3′,5,5′‐tetrabromobisphenol A, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). The novel aromatic polyetherimides having inherent viscosities up to 1.04 dL g⁻¹ were obtained by either a one‐step or a conventional two‐step polymerization process starting from the bis(ether anhydride) and various aromatic diamines. All the polyimides showed typical amorphous diffraction patterns. Most of the polyimides were readily soluble in common organic solvents such as N,N‐dimethylacetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), pyridine, and even in less polar solvents like chloroform and tetrahydrofuran (THF). These aromatic polyimides had glass transition temperatures in the range of 256–303°C, depending on the nature of the diamine moiety. Thermogravimetric analysis (TGA) showed that all polymers were stable, with 10% weight loss recorded above 470°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1673–1680, 1999     

Poly(ethylene terephthalate) reinforced by N,N′‐diphenyl biphenyl‐3,3′,4,4′‐tetracarboxydiimide moieties

Starting with 3,3′,4,4′‐biphenyltetracarboxylic dianhydride and methyl aminobenzoate, we synthesized a novel rodlike imide‐containing monomer, N,N′‐bis[p‐(methoxy carbonyl) phenyl]‐biphenyl‐3,3′,4,4′‐tetracarboxydiimide (BMBI). The polycondensation of BMBI with dimethyl terephthalate and ethylene glycol yielded a series of copoly(ester imide)s based on the BMBI‐modified poly(ethylene terephthalate) (PET) backbone. Compared with PET, these BMBI‐modified polyesters had higher glass‐transition temperatures and higher stiffness and strength. In particular, the poly(ethylene terephthalate imide) PETI‐5, which contained 5 mol % of the imide moieties, had a glass‐transition temperature of 89.9 °C (11 °C higher than the glass‐transition temperature of PET), a tensile modulus of 869.4 MPa (20.2 % higher than that of PET), and a tensile strength of 80.8 MPa (38.8 % higher than that of PET). Therefore, a significant reinforcing effect was observed in these imide‐modified polyesters, and a new approach to higher property polyesters was suggested. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 852–863, 2002; DOI 10.1002/pola.10169     

Oligonucleotides Containing 7‐Deaza‐2′‐deoxyxanthosine: Synthesis,Base Protection,and Base‐Pair Stability

Oligonucleotides incorporating 7‐deaza‐2′‐deoxyxanthosine ( 3 ) and 2′‐deoxyxanthosine ( 1 ) were prepared by solid‐phase synthesis using the phosphoramidites 6 – 9 and 16 which were protected with allyl, diphenylcarbamoyl, or 2‐(4‐nitrophenyl)ethyl groups. Among the various groups, only the 2‐(4‐nitrophenyl)ethyl group was applicable to 7‐deazaxanthine protection being removed with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) by β‐elimination, while the deprotection of the allyl residue with Pd⁰ catalyst or the diphenylcarbamoyl group with ammonia failed. Contrarily, the allyl group was found to be an excellent protecting group for 2′‐deoxyxanthosine ( 1 ). The base pairing of nucleoside 3 with the four canonical DNA constituents as well as with 3‐bromo‐1‐(2‐deoxy‐β‐D ‐erythro‐pentofuranosyl)‐1H‐pyrazolo[3,4‐d]pyrimidine‐4,6‐diamine ( 4 ) within the 12‐mer duplexes was studied, showing that 7‐deaza‐2′‐deoxyxanthosine ( 3 ) has the same universal base‐pairing properties as 2′‐deoxyxanthosine ( 1 ). Contrary to the latter, it is extremely stable at the N‐glycosylic bond, while compound 1 is easily hydrolyzed under slightly acidic conditions. Due to the pK_a values 5.7 ( 1 ) and 6.7 ( 3 ), both compounds form monoanions under neutral conditions (95% for 1 ; 65% for 3 ). Although both compounds form monoanions at pH 7.0, pH‐dependent T_m measurements showed that the base‐pair stability of 7‐deaza‐2′‐deoxyxanthosine ( 3 ) with dT is pH‐independent. This indicates that the 2‐oxo group is not involved in base‐pair formation.     

Synthesis,Characterization, Catalytic and Antibacterial Activity of Two Series of Dinuclear Ruthenium Sulphoxide Complexes Using 5,5¢‐Methylenebis(pyridine) as Bis‐chelating Bridging Ligand

The reaction of a new heterocyclic bidentate N containing spacer, (ligand) 5,5′‐methylenebis(pyridine) with ruthenium sulphoxide precursors resulted, dinuclear complexes. We herein report three formulations; [{cis,fac‐RuCl₂(so)₃}₂(μ‐mbp)].3so; [{trans,mer‐RuCl₂(so)₃₂}₂(μ‐mbp)].3so and [{trans‐RuCl₄(so)}₂(μ‐mbp)]^2?[X]₂⁺; where so = dimethyl‐sulfoxide/tetramethylenesulfoxide; mbp = 5,5′‐methylenebis(pyridine) and [X]⁺ = [(dmso)₂H]⁺, Na⁺ or [(tmso)H]⁺. These complexes were characterized on the basis of elemental analyses, molar conductance measurement, magnetic susceptibility, FT‐IR, ¹H‐NMR, ¹³C{¹H}‐NMR, electronic spectroscopy and FAB‐Mass spectrometry. Catalytic activity of these complexes has been investigated in hydrolysis of benzonitrile. All the complexes exhibit good antibacterial activity against gram‐negative bacteria Escherichia coli in comparison to Chloramphenicol.     

Synthesis,crystal structure and magnetic properties of (acetato‐κ2O,O′)bis(5,5′‐dimethyl‐2,2′‐bipyridine‐κ2N,N′)nickel(II) perchlorate monohydrate

The title hydrated ionic complex, [Ni(CH₃COO)(C₁₂H₁₂N₂)₂]ClO₄·H₂O or [Ni(ac)(5,5′‐dmbpy)₂]ClO₄·H₂O (where 5,5′‐dmbpy is 5,5′‐dimethyl‐2,2′‐bipyridine and ac is acetate), (1), was isolated as violet crystals from the aqueous ethanolic nickel acetate–5,5′‐dmbpy–KClO₄ system. Within the complex cation, the Ni^II atom is hexacoordinated by two chelating 5,5′‐dmbpy ligands and one chelating ac ligand. The mean Ni—N and Ni—O bond lengths are 2.0628 (17) and 2.1341 (15) Å, respectively. The water solvent molecule is disordered over two partially occupied positions and links two complex cations and two perchlorate anions into hydrogen‐bonded centrosymmetric dimers, which are further connected by π–π interactions. The magnetic properties of (1) at low temperatures are governed by the action of single‐ion anisotropy, D, which arises from the reduced local symmetry of the cis‐NiO₂N₄ chromophore. The fitting of the variable‐temperature magnetic data (2–300 K) gives g_iso = 2.134 and D/hc = 3.13 cm⁻¹.     

Two CoII coordination polymers of biphenyl‐2,2′,5,5′‐tetracarboxylic acid with flexible N‐donor ligands: syntheses,structures and magnetic properties

Two Co^II‐based coordination polymers, namely poly[(μ₄‐biphenyl‐2,2′,5,5′‐tetracarboxylato){μ₂‐1,3‐bis[(1H‐imidazol‐1‐yl)methyl]benzene}dicobalt(II)], [Co₂(C₁₆H₆O₈)(C₁₄H₁₄N₄)₂]_n or [Co₂(o,m‐bpta)(1,3‐bimb)₂]_n ( I ), and poly[[aqua(μ₄‐biphenyl‐2,2′,5,5′‐tetracarboxylato){1,4‐bis[(1H‐imidazol‐1‐yl)methyl]benzene}dicobalt(II)] dihydrate], {[Co₂(C₁₆H₆O₈)(C₁₄H₁₄N₄)₂(H₂O)₂]·4H₂O}_n or {[Co₂(o,m‐bpta)(1,4‐bimb)₂(H₂O)₂]·4H₂O}_n ( II ), were synthesized from a mixture of biphenyl‐2,2′,5,5′‐tetracarboxylic acid, i.e. [H₄(o,m‐bpta)], CoCl₂·6H₂O and N‐donor ligands under solvothermal conditions. The complexes were characterized by IR spectroscopy, elemental analysis, single‐crystal X‐ray diffraction and powder X‐ray diffraction analysis. The bridging (o,m‐bpta)^4? ligands combine with Co^II ions in different μ₄‐coordination modes, leading to the formation of one‐dimensional chains. The central Co^II atoms display tetrahedral [CoN₂O₂] and octahedral [CoN₂O₄] geometries in I and II , respectively. The bis[(1H‐imidazol‐1‐yl)methyl]benzene (bimb) ligands adopt trans or cis conformations to connect Co^II ions, thus forming two three‐dimensional (3D) networks. Complex I shows a (2,4)‐connected 3D network with left‐ and right‐handed helical chains constructed by (o,m‐bpta)^4? ligands. Complex II is a (4,4)‐connected 3D novel network with ribbon‐like chains formed by (o,m‐bpta)^4? linkers. Magnetic studies indicate an orbital contribution to the magnetic moment of I and II due to the longer Co…Co distances. An attempt has been made to fit the χ_MT results to the magnetic formulae for mononuclear Co^II complexes, the fitting indicating the presence of weak antiferromagnetic interactions between the Co^II ions.     

Water‐Soluble Metallocene‐Containing Polymers

Metallocenes are organometallic compounds with reversible redox profiles and tunable oxidation and reduction potentials, depending on the metal and substituents at the cyclopentadienyl rings. Metallocenes have been introduced in macromolecules to combine the redox‐activity with polymer properties. There are many examples of such hydrophobic polymer materials, but much fewer water‐soluble examples are found scattered across the polymer literature. However, in terms of drug delivery and other biological applications, water solubility is essential. For this very reason, all the synthetic routes to water‐soluble metallocene containing polymers are collected and discussed here. The focus is on neutral ferrocene‐ and ruthenocene‐containing and charged cobaltocenium‐containing macromolecules (i.e., symmetrical sandwich complexes). The synthetic protocols, self‐assembly behavior, and other benefits of the obtained materials are discussed.

     

Pb(II) and Mn(II) Coordination Compounds Involving 5,5′‐(1,4‐Phenylene)bis(1H‐tetrazole):Synthesis,Characterization, and Effect on Thermal Decomposition of Ammonium Perchlorate

Two coordination compounds [Pb₄(BDT)₃(OH)₂(H₂O)₄]·H₂O ( 1 ) and [Mn(H₂O)₆]·(HBDT)₂·2H₂O ( 2 ) [H₂BDT?5,5′‐(1,4‐phenylene)bis(1H‐tetrazole)] had been hydrothermally synthesized. 1 and 2 had been characterized by single‐crystal X‐ray diffraction, IR, elemental and thermal analyses. Structural analysis reveals that 1 exhibits 2D layer structure extended through BDT with two different coordination modes rings in transverse and vertical. 2 consists of [Mn(H₂O)₆]²⁺, free HBDT and water. In addition, 1 and 2 were explored as luminescent materials and additives to promote the thermal decomposition of ammonium perchlorate by differential scanning calorimetry.