1,10‐Diaza‐18‐crown‐ether,Modified by Phosphonate Pendant Arms – Synthesis,Structure, and Picrate Extraction Properties

Reaction of O,O′‐diisopropyl‐3‐methyl‐1,2‐butadienylphosphonate with 1,10‐diaza‐18‐crown‐6 in the presence of a catalytic amount of iPrONa leads to the new crown‐ether derivative, containing phosphonate pendant arms ( L ). The structure of the compound obtained was investigated by single crystal X‐ray diffraction analysis, IR, ¹H and ³¹P{¹H} NMR spectroscopy, and microanalysis. In the crystal structure the side arms of L are in an anti disposition relative to the macrocyclic cavity. It was established that phosphorylation of 1,10‐diaza‐18‐crown‐6 by allenylphosphonate results in an increase of extraction of NaPic and KPic, whereas LiPic and NH₄Pic are extracted practically in the same level.     

新型侧基含磷共聚酯的合成、表征及性能

以精制对苯二甲酸（TPA）、乙二醇（EG）和含磷反应型阻燃剂9,10-二氢-9-氧杂-10-[2,3-二（2-羟基乙氧基）羰基丙基]-10-磷杂菲-10-氧化物为原料,利用熔融缩聚法合成了含磷量分别为0．35％、0．65％的阻燃聚酯。通过熔融纺丝法将聚酯制成纤维及织物,研究了纤维的染色性能,并通过极限氧指数法和垂直燃烧法研究了织物的阻燃性能。FT-IR和NMR研究结果表明：阻燃共聚酯含磷量为0．35％时,其氧指数（LOI）达31．5％,并无熔滴、烟雾产生,具有优异的阻燃性能和抗熔滴性能。DSC、TG和XPS的研究结果表明：侧基舍磷单元的引入降低了聚酯的Tg和Tm,较低的Tm将有利于材料加工性能的改善;阻燃聚酯侧基上的P-C、P-O键易断裂并挥发至气相中,从而降低了聚酯热稳定性,阻燃聚酯可能以气相阻燃机理为主发挥阻燃作用。此外,含磷共聚酯纤维具有较优异的染色性能。     

Characterization of Defined Metal‐Containing Supramolecular Block Copolymers

The characterization of metal‐containing supramolecular polymers by gel permeation chromatography (GPC) or matrix‐assisted laser desorption ionisation time‐of‐flight mass spectrometry (MALDI‐TOF MS) is complicated because of the interaction of the charged materials with the GPC column material in the first case and fragmentation due to the applied laser energy in the latter case. In this contribution we report recent advances made for the characterization of supramolecular polymers based on terpyridine metal complexes utilizing GPC and MALDI‐TOF MS. In particular for GPC analysis, the choice of solvent and additive was found to be crucial for a successful characterization. Furthermore, MALDI‐TOF MS spectra of these compounds are not straightforward to interpret. Both aspects are discussed in detail with the result of a better understanding and improved analysis possibilities of the mentioned supramolecular polymers.

A GPC‐coupled in‐line diode array spectrum of one of the complexes investigated here.     

Synthesis,Structures, and Properties of Crystalline Salts with Radical Anions of Metal‐Containing and Metal‐Free Phthalocyanines

Radical anion salts of metal‐containing and metal‐free phthalocyanines [MPc(3?)]^.?, where M=Cu^II, Ni^II, H₂, Sn^II, Pb^II, Ti^IVO, and V^IVO ( 1 – 10 ) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long C?N_imine bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1 – 10 show new bands at 833–1041 nm in the NIR range, whereas the Q‐ and Soret bands are blue‐shifted by 0.13–0.25 eV (38‐92 nm) and 0.04–0.07 eV (4–13 nm), respectively. Radical anions with Ni^II, Sn^II, Pb^II, and Ti^IVO have S=1/2 spin state, whereas [Cu^IIPc(3?)]^.? and [V^IVOPc(3?)]^.? containing paramagnetic Cu^II and V^IVO have two S=1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal‐free phthalocyanine radical anions [H₂Pc(3?)]^.? (linewidth of 0.08–0.24 mT), broad EPR signals are manifested (linewidth of 2–70 mT) with g‐factors and linewidths that are strongly temperature‐dependent. Salt 11 containing the [Na^IPc(2?)]^? anions as well as previously studied [Fe^IPc(2?)]^? and [Co^IPc(2?)]^? anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of [MPc(3?)]^.? in 1 – 10 .     

Synthesis,Structure, and Characterization of a Microporous Metal‐Organic Framework with PtS Topology

The microporous metal‐organic framework Cd₂(ABTC)(H₂O)(DMA)₂ · H₂O · 3DMA ( 1 ) (H₄ABTC = 3, 3′,5, 5′‐azobenzenetetracarboxylic acid; DMA = N,N′‐dimethylacetamide) was prepared by solvothermal reaction and characterized. X‐ray structure analysis revealed that compound 1 is a three‐dimensional (3D) open framework with 2D channels. The topology is based on a PtS net, constructed of 4‐connected rectangular ABTC^4– units with 4‐connected tetrahedral dinuclear Cd₂(CO₂)₄(H₂O)(DMA)₂ secondary building units (SBUs). The solid‐state excitation‐emission spectra showed that the strongest emission peak is at 403 nm upon excitation at λ = 287 nm.     

Synthesis,Structure, and Photoluminescent Properties of a New 3D Metal‐Organic Framework with Unusual AgI Chains

A new 3D metal‐organic framework {[Ag₄(btc)(bix)₂] · H₂O}_n ( 1 ) [H₄btc = biphenyl‐2, 2′,4, 4′‐tetracarboxylic acid, bix = 1, 4‐bis(imidazol‐1‐ylmethyl)benzene] was synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, infrared (IR) spectroscopy, thermal gravimetric analysis (TGA), and luminescence studies. The most remarkable structural feature of 1 is that the 1D chain and 2D network interpenetrated structures are further linked by parallel aligned 1D Ag^I chains to generate 3D metal‐organic framework.     

两种含有十二元环的层状稀土硫酸盐的合成、结构表征及性质研究

通过溶剂热合成技术,我们得到了两种新的二维层状稀土硫酸盐:[Tb₂(SO₄)₅][(CH₃)₂NH₂]₄(1)和[Y₂(SO₄)₅][(CH₃)₂NH₂]₄(2),并通过X-射线衍射、元素分析及红外、热重对化合物进行了表征。两种化合物都属于三斜晶系,P1空间群。其中化合物1:a=0.9887(3)nm,b=1.1061(3)nm,c=1.5354(4)nm,α=70.45(0)°,β=75.12(0)°,γ=67.11(0)°,Z=2;化合物2:a=0.9816(5)nm,b=1.1001(5)nm,c=1.5286(8)nm,α=70.44(1)°,β=75.45(1)°,γ=67.48(1)°,Z=2。通过对晶体结构进行表征我们发现两种化合物都含有二维层状无机骨架结构,该层由2种不同类型的双链和十二元环构成。我们还对化合物1的荧光性质进行了研究,其在369nm的激发波长下表现出了Tb³⁺ 的特征发射。     

Synthesis,Structure and Luminescent Property of Two New 2D Metal‐organic Frameworks containing Lanthanide Ions

Two novel lanthanide‐based coordination polymers with 2D lattice‐type motif, [Ln₂(CAM)₃(H₂O)₄]·2H₂O (CAM = 4‐Hydroxypyridine‐2,6‐dicarboxylate; Ln = Tb( 1 ), Pr( 2 )), have been prepared by hydrothermal reaction of Ln(OH)₃, CAM and water at 160 °C and characterized by single‐crystal X‐ray diffraction analysis, IR and TGA. The investigation of luminescent property reveals that 1 exhibits characteristic green emission of Tb³⁺ ions.     

Synthesis,Characterization, and an ab initio Study of a Manganese(II) Macrocyclic Schiff-Base Complex with Two 2-Aminoethyl Pendant Arms

The cyclocondensation of 2,6-diformylpyridine with N,N,N,N-tetrakis(2-aminoethyl)ethane-1,2-diamine (pentene) in the presence of Mn^II forms the [1 + 1] pendant arm Schiff-base macrocyclic complex, [MnL³]²⁺. The ligand is a 15-membered pentaaza macrocycle having two 2-aminoethyl pendant arms {L³= 6,9-bis(aminoethyl)-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentene}. The complex, investigated by analytical, spectroscopic and magnetic techniques, supports the formation of a highly symmetrical pentagonal bipyramid complex with the Mn^II ion located within a pentaaza macrocycle and two pendant amines coordinating on opposite sides of a plane defined by the macrocycle and the metal ion. The structure of the complex was also verified by ab initio HF-MO calculations using a standard 3-21G basis set.     

Metal‐Sensitive Hydrothermal Synthesis and Structural Characterization of a Mixed‐Metal and Porous Coordination Polymer Containing 2,3‐Pyridinedicarboxylate

The hydrothermal reaction of 2,3‐pyridinedicarboxylic acid (2,3‐H₂pda) with a mixture of Cd(NO₃)₂ and Ni(NO₃)₂ afforded a coordination polymer, [CdNi(2,3‐pda)₂(H₂O)₃]_∞ ( 1 ); in contrast, that with a mixture of Cd(NO₃)₂ and Zn(NO₃)₂ surprisingly produced a discrete molecule, trans‐[Cd(3‐pa)₂(H₂O)₄] ( 2 ) (3‐pa^? = 3‐pyridinecarboxylate). Since a direct reaction between a single metal salt, Cd(NO₃)₂ or Zn(NO₃)₂, and 3‐pyridinecarboxylic acid (3‐Hpa) under similar hydrothermal conditions yielded different coordination polymers containing 3‐pa^?, it appears that the apparently thermal decarboxylation from ligated 2,3‐pda^2? to 3‐pa^? occurs after complexation of both metal cations, Cd(II) and Zn(II). A new coordination mode, formed for 2,3‐pda^2? in structure 1 , appears to help formation of microporous channels by piling up the observed 2D hydrogen‐bonded heteropolynuclear layers. Each channel apparently consists of two interpenetrating 6³ Cd(II) and Ni(II) nets.     

Synthesis and Structure Characterization of Metal‐organic Frameworks with a Triple Iron Helical Complex

Metal‐organic frameworks were achieved from triple metal helical iron complex [(Fe₂L₃)·(H₂O)₄] (L = bis[2‐hydroxybenzaldehyde]hydrazonate). The phenyl rings of the helical units contact the neighbors via π‐π and C‐H···π interactions to form two‐dimensional channeled frameworks in which four solvent water molecules are included in the channels of the structure. Thermogravimetric analyses reveal that the solvent water molecules can be evacuated from the pores without loss of the framework periodicity. The crystal lattice is thermally stable up to 339.9 °C, and water can be re‐included by putting the heated material in water.     

Synthesis, Structure and Properties of Two Photochromic Compounds Containing A Pyrazolone-ring

IntroductionThe investigation of organic photochromic materials has increased considerably in recentyears because of their potential commercial application in several areas,such as high-densityoptical storage media,optical switching,etc.[1 ,2 ] .Though numerous organic photochromicmolecular systems or photoactive devices have been explored so far,those systems classifiedaccording to the photochromic structural units mainly belong to a small number of families:fulgides,spiropyrans and spiroxazi…     

Synthesis and Characterization of a Metal‐Organic Coordination Polymer

A novel energetic microporous metal‐organic coordination polymer {[Ni(tnbpdc)(bpy)(H₂O)₂] · 1.5(DMF)}_n ( 1 ) (tnbpdc = 2, 2′,6, 6′‐tetranitro‐4, 4′‐biphenyl dicarboxylate, bpy = 4, 4′‐bipyridine) was prepared solvothermally and characterized by elemental, IR spectroscopic, and single‐crystal X‐ray diffraction analyses. The X‐ray crystal structure of 1 revealed a rectangular‐shaped grid constructed with tnbpdc linkers and bpy linkers, with the free tunnel size estimated as 11 × 15 Ų. The thermal stability of the compound was evaluated by differential scanning calorimetry and thermogravimetric analysis. Such complexes may find application as novel heat‐resistant energetic materials.     

Metal‐Ion Metathesis and Properties of Triarylboron‐Functionalized Metal–Organic Frameworks

An anionic metal–organic framework, H₃[(Mn₄Cl)₃ L ₈]?30 H₂O?2.5 DMF?5 Diox ( UPC‐15 ), was successfully prepared by the reaction of MnCl₂ with tris(p‐carboxylic acid)tridurylborane (H₃ L ) under solvothermal conditions. UPC‐15 with wide‐open pores (～18.8 Å) is constructed by packing of octahedral and cuboctahedral cages, and exhibits high gas‐sorption capabilities. Notably, UPC‐15 shows selective adsorption of cationic dyes due to the anion framework. Moreover, the catalytic and magnetic properties were investigated, and UPC‐15 can highly catalyze the cyanosilylation of aromatic aldehydes. UPC‐15 exhibits the exchange of metal ions from Mn to Cu in a single‐crystal‐to‐single‐crystal manner to generate UPC‐16 , which could not be obtained by the direct solvothermal reaction of CuCl₂ and H₃ L. UPC‐16 exhibits similar properties for gas sorption, dye separation, and catalytic activity. However, the magnetic behaviors for UPC‐15 and UPC‐16 are distinct due to the metal‐specific properties. Below 47 K, UPC‐15 exhibits a ferromagnetic coupling but UPC‐16 shows a dominant antiferromagnetic behavior.     

Synthesis,Characterization, and Crystal Structure of a New Coordination Polymer of Lead(II) Containing 2,6‐Pyridinedicarboxylic Acid

The reaction of solution 2,6‐pyridinedicarboxylic acid ( 1 ) and 2,2′‐Bipyridine with Pb(NO₃)₂ led to the coordination polymer [Pb(pydc)]_n ( 2 ) (pydcH₂ is 2,6‐pyridinedicarboxylic acid). This complex was characterized by elemental analysis, IR spectroscopy and single‐crystal structure of 2 . Crystal data for 2 at ?80 °C: monoclinic, space group P2₁/n, a = 977.2(1), b = 554.0(1), c = 1425.3(2) pm, β = 104.75(1)°, Z = 4, R₁= 0.0261. The units [Pb(pydc)] form infinite chains along [010].     

含氟侧基聚芳醚酮的合成与表征

聚芳醚酮具有优异的化学、物理和机械性能 ,被广泛用于结构材料、高分子膜、航空航天和电子工业中所需的涂敷材料 [1,2 ] .传统的聚芳醚酮由于主链的规整性和刚性 ,使其难熔难溶 ,给加工和应用带来一定的困难 .许多研究者对其进行了大量的改性研究 [3,4 ] .氟元素具有较强的电负性 ,尺寸较小 ,可以形成强化学键和具有较好的电性能等 ,使其在化学物质的分子设计中成为极有价值的取代基 .含氟聚合物可以影响聚合物的溶解性、阻燃性、热稳定性、玻璃化转变温度、颜色、结晶性、介电常数和吸水性等性能 [5,6 ] .为了改善聚芳醚酮的溶解性、结晶…     

两种有机磺酸配合物的合成、表征及与DNA键合性质

合成了2个新型有机磺酸配合物,[Cd(phen)₂(ans)₂]·H₂O (1)和[Pb(phen)₂(ans)₂]·H₂O (2) (phen=1,10-邻菲咯啉,ans=4-氨基-1-萘磺酸根),通过元素分析、红外光谱等对配合物进了表征,用X-射线单晶衍射方法测定了配合物的单晶结构。应用紫外-可见吸收光谱、荧光光谱及粘度测定方法研究了配合物与ctDNA的作用,发现2个配合物均以插入和氢键两种模式与ctDNA发生作用。