用非等温DSC基于Harcourt-Esson方程估算含能材料热爆炸临界温度的一种简单方法

用合理假设,由Semenov热爆炸理论和基于Harcourt-Esson速率表达式非等温动力学方程 ,推导了估算含能材料热爆炸临界温度的一种简单方法。该计算式为 ,比较简单。从非等温DSC曲线上onset温度（ ）通过表达式 可得到 ,由方程 可求得 值,随后算出 。该方法计算结果与Zhang-Hu-Xie-Li方法结果相一致。     

Synthesis of spiro[indoline‐3,3′‐pyrrolizines] by 1,3‐dipolar reactions between isatins,l‐proline and electron‐deficient alkenes

Two spiro[indoline‐3,3′‐pyrrolizine] derivatives have been synthesized in good yield with high regio‐ and stereospecificity using one‐pot reactions between readily available starting materials, namely l ‐proline, substituted 1H‐indole‐2,3‐diones and electron‐deficient alkenes. The products have been fully characterized by elemental analysis, IR and NMR spectroscopy, mass spectrometry and crystal structure analysis. In (1′RS ,2′RS ,3SR ,7a′SR )‐2′‐benzoyl‐1‐hexyl‐2‐oxo‐1′,2′,5′,6′,7′,7a′‐hexahydrospiro[indoline‐3,3′‐pyrrolizine]‐1′‐carboxylic acid, C₂₈H₃₂N₂O₄, (I), the unsubstituted pyrrole ring and the reduced spiro‐fused pyrrole ring adopt half‐chair and envelope conformations, respectively, while in (1′RS ,2′RS ,3SR ,7a′SR )‐1′,2′‐bis(4‐chlorobenzoyl)‐5,7‐dichloro‐2‐oxo‐1′,2′,5′,6′,7′,7a′‐hexahydrospiro[indoline‐3,3′‐pyrrolizine], which crystallizes as a partial dichloromethane solvate, C₂₈H₂₀Cl₄N₂O₃·0.981CH₂Cl₂, (II), where the solvent component is disordered over three sets of atomic sites, these two rings adopt envelope and half‐chair conformations, respectively. Molecules of (I) are linked by an O—H…·O hydrogen bond to form cyclic R ₆⁶(48) hexamers of (S ₆) symmetry, which are further linked by two C—H…O hydrogen bonds to form a three‐dimensional framework structure. In compound (II), inversion‐related pairs of N—H…O hydrogen bonds link the spiro[indoline‐3,3′‐pyrrolizine] molecules into simple R ₂²(8) dimers.     

Synthesis, Crystal Structure, Theoretical Calculation and Thermal Behavior of DNAZ·NTO

DNAZ·NTO was prepared by mixing 3,3‐dinitroazetidine (DNAZ) and 3‐nitro‐1,2,4‐triazol‐5‐one (NTO) in ethanol solution. Single crystals suitable for X‐ray measurement were obtained, which belong to monoclinic, space group P2₁/n with unit cell parameters of a=1.4970(4) nm, b=0.6325(2) nm, c=2.2347(7) nm, β=96.55(1) °, V=2.1022(11) nm³ , D_c=1.752 g·cm^?3, F(000) =1136 and Z=8. Based on the analysis of the molecule structure, the theoretical investigation of the title compound was carried out at B3LYP/6‐311++G** levels, and the natural atomic charge and natural bond orbital analysis were performed. The interaction between the cation and anion was also discussed. The thermal behavior of DNAZ·NTO was carried out by DSC and TG/DTG techniques. The apparent activation energy (E_a) and pre‐exponential constant (A) of the main exothermic decomposition reaction were obtained.     

Different nucleobase orientations in two cyclic 2′,3′‐phosphates of purine ribonucleosides: Et3NH(2′,3′‐cAMP) and Et3NH(2′,3′‐cGMP)·H2O

The crystal structures of triethyl­ammonium adenosine cyclic 2′,3′‐phosphate {systematic name: triethyl­ammonium 4‐(6‐amino­purin‐9‐yl)‐6‐hydroxy­methyl‐2‐oxido‐2‐oxoperhydro­furano[3,4‐c][1,3,2]dioxaphosphole}, Et₃NH(2′,3′‐cAMP) or C₆H₁₆N⁺·C₁₀H₁₁N₅O₆P⁻, (I), and guanosine cyclic 2′,3′‐phosphate monohydrate {systematic name: triethyl­ammonium 6‐hydroxy­methyl‐2‐oxido‐2‐oxo‐4‐(6‐oxo‐1,6‐dihydro­purin‐9‐yl)perhydro­furano[3,4‐c][1,3,2]dioxaphosphole monohydrate}, [Et₃NH(2′,3′‐cGMP)]·H₂O or C₆H₁₆N⁺·C₁₀H₁₁N₅O₇P⁻·H₂O, (II), reveal different nucleobase orientations, viz. anti in (I) and syn in (II). These are stabilized by different inter‐ and intra­molecular hydrogen bonds. The structures also exhibit different ribose ring puckering [₄E in (I) and ³T₂ in (II)] and slightly different 1,3,2‐dioxaphospho­lane ring conformations, viz. envelope in (I) and puckered in (II). Infinite ribbons of 2′,3′‐cAMP⁻ and helical chains of 2′,3′‐cGMP⁻ ions, both formed by O—H⋯O, N—H⋯X and C—H⋯X (X = O or N) hydrogen‐bond contacts, characterize (I) and (II), respectively.     

Crystal Structure of a Trinuclear Titanium(IV) Complex with (rac)‐3,3′‐Bis(methoxymethyl)‐BINOLate

Reaction of (rac)‐3,3′‐bis(methoxymethyl)‐BINOL [H₂(CH₃OCH₂)₂BINO] with excess Ti(OⁱPr)₄ and one equivalent of H₂O in CH₂Cl₂ affords a trinuclear titanium(IV) complex [{(CH₃OCH₂)₂BINO}Ti₃(μ₃‐O)(OiPr)₆(μ₂‐OiPr)₂]. By dissolving it in dichloromethane and hexane and cooling to 0 °C, plate‐like pale yellow single crystals (monoclinic, P2₁/n, a = 12.605(3), b = 21.994(5), c = 19.090(4) Å, β = 92.764(8)°, V = 5286.2(19) ų, T = 293(2) K) were obtained. Each oxygen atom at 2 or 2′ position of the (CH₃OCH₂)₂BINO ligand bonds to only one titanium atom. There is no interaction between the third Ti atom and the two oxygen atoms of 3,3′‐bis(methoxymethyl)‐BINOLate.     

Self‐Assembly,Spectroscopic and Electrochemical Studies of Nickel(II)‐4,8‐Diazaundecanediamide Complex

The self‐assembly of NiCl₂·6H₂O with a diaminodiamide ligand 4,8‐diazaundecanediamide (L‐2,3,2) gave a [Ni(C₉H₂₀N₄O₂)(Cl)(H₂O)] Cl·2H₂O ( 1 ). The structure of 1 was characterized by single‐crystal X‐ray diffraction analysis. Structural data for 1 indicate that the Ni(II) is coordinated to two tertiary N atoms, two O atoms, one water and one chloride in a distorted octahedral geometry. Crystal data for 1: orthorhombic, space group P 21nb, a = 9.5796(3) Å, b = 12.3463(4) Å, c = 14.6305(5) Å, Z = 4. Through NH···Cl–Ni (H···Cl 2.42 Å, N···Cl 3.24 Å, NH···Cl 158°) and OH···Cl–Ni contacts (H···Cl 2.36 Å, O···Cl 3.08 Å, OH···Cl 143°), each cationic moiety [Ni(C₉H₂₀N₄O₂) (Cl)(H₂O)]⁺ in 1 is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chainlike structure. Thermogrametric analysis of compound 1 is consistent with the crystallographic observations. The electronic absorption spectrum of Ni(L‐2,3,2)²⁺ in aqueous solution shows four absorption bands, which are assigned to the ³A_2g → ³T_2g, ³T_2g → ¹Eg, ³T_2g → ³T_1g, and ³A_2g → ³T_1g transitions of triplet‐ground state, distorted octahedral nickel(II) complex. The cyclic volammetric measurement shows that Ni²⁺ is more easily reduced than Ni(L‐2,3,2)²⁺ in aqueous solution.     

Intrinsically microporous polyimides containing spirobisindane and phenazine units: Synthesis,characterization and gas permeation properties

A new diamine containing spirobisindane and phenazine units, namely, 3,3,3′,3′‐tetramethyl‐2,2′,3,3′‐tetrahydro‐1,1′‐spirobi[cyclopenta[b]phenazine]‐7,7′‐diamine (TTSBIDA) was synthesized starting from commercially available 5,5′,6,6′‐tetrahydroxy‐3,3,3′,3′‐tetramethyl‐1,1′‐spirobisindane (TTSBI). TTSBI was oxidized to 3,3,3′,3′‐tetramethyl‐2,2′,3,3′‐tetrahydro‐1,1′‐spirobi[indene]‐5,5′,6,6′‐tetraone (TTSBIQ) which was subsequently condensed with 4‐nitro‐1,2‐phenylenediamine to obtain 3,3,3′,3′‐tetramethyl‐7,7′‐dinitro‐2,2′,3,3′‐tetrahydro‐1,1′‐spirobi[cyclopenta[b]phenazine] (TTSBIDN). TTSBIDN was converted into TTSBIDA by reduction of the nitro groups using hydrazine hydrate in the presence of Pd/C as the catalyst. A series of new polyimides of intrinsic microporosity (PIM‐PIs) were synthesized by polycondensation of TTSBIDA with commercially available aromatic dianhydrides. PIM‐PIs exhibited amorphous nature, high thermal stability (T₁₀ > 480 °C) and intrinsic microporosity (BET surface area = 59–289 m²/g). The gas permeation characteristics of films of selected PIM‐PIs were evaluated and they exhibited appreciable gas permeability as well as high selectivity. The CO₂ and O₂ permeability of PIM‐PIs were in the range 185.4–39.2 and 30.6–6.2 Barrer, respectively. Notably, polyimide derived from TTSBIDA and 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (PIM‐PI‐6FDA) exhibited high CO₂ and O₂ permeability of 185.4 and 30.6 Barrer with CO₂/CH₄ and O₂/N₂ selectivity of 43.1 and 5.1, respectively. The data of PIM‐PI‐6FDA for CO₂/CH₄ and O₂/N₂ gas pairs were located near Robeson upper bound. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 766–775     

Organosoluble polyimides and copolyimides based on 1,1‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐phenylethane and aromatic dianhydrides

1,1‐Bis[4‐(4‐aminophenoxy)phenyl]‐1‐phenylethane (BAPPE) was prepared through nucleophilic substitution reaction of 1,1‐bis(4‐hydroxyphenyl)‐1‐phenylethane and p‐chloronitrobenzene in the presence of K₂CO₃ in N,N‐dimethylformamide, followed by catalytic reduction with hydrazine and Pd/C. Novel organosoluble polyimides and copolyimides were synthesized from BAPPE and six kinds of commercial dianhydrides, including pyromellitic dianhydride (PMDA, I_a ), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA, I_b ), 3,3′,4,4′‐ biphenyltetracarboxylic dianhydride (BPDA, I_c ), 4,4′‐oxydiphthalic anhydride (ODPA, I_d ), 3,3′,4,4′‐diphenylsulfonetetracarboxylic dianhydride (DSDA, I_e ) and 4,4′‐hexafluoroisopropylidenediphthalic anhydride (6FDA, I_f ). Differing with the conventional polyimide process by thermal cyclodehydration of poly(amic acid), when polyimides were prepared by chemical cyclodehydration with N‐methyl‐2‐pyrrolidone as used solvent, resulted polymers showed good solubility. Additional, I_a,b were mixed respectively with the rest of dianhydrides (I_c–f) and BAPPE at certain molar ratios to prepare copolyimides with arbitrary solubilities. These polyimides and copolyimides were characterized by good mechanical properties together with good thermal stability. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2082–2090, 2000     

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).     

Functionalization of [Ge9] with Small Silanes:[Ge9(SiR3)3]– (R = iBu,iPr, Et) and the Structures of (CuNHCDipp)[Ge9{Si(iBu)3}3], (K‐18c6)Au[Ge9{Si(iBu)3}3]2, and (K‐18c6)2[Ge9{Si(iBu)3}2]

Novel silylation reactions at [Ge₉] Zintl clusters starting from the chlorosilanes SiR₃Cl (R = iBu, iPr, Et) and the Zintl phase K₄Ge₉ are reported. The formation of the tris‐silylated anions [Ge₉(SiR₃)₃]^– [R = iBu ( 1a ), iPr ( 1b ), Et ( 1c )] by heterogeneous reactions in acetonitrile was monitored by ESI‐MS measurements. For R = iBu ¹H, ¹³C and ²⁹Si NMR experiments confirmed the exclusive formation of 1a . Subsequent reactions of 1a with CuNHC^DippCl and Au(PPh₃)Cl result in formation of the neutral metal complex (CuNHC^Dipp)[Ge₉{Si(iBu)₃}₃]·0.5 tol ( 2 ·0.5 tol) and the metal bridged dimeric unit {Au[Ge₉{Si(iBu)₃}₃]₂}^– ( 3a ), isolated as a (K‐18c6)⁺ salt in (K‐18c6)Au[Ge₉{Si(iBu)₃}₃]₂·tol ( 3 ·tol), respectively. Finally, from a toluene/hexane solution of 1a in presence of 18‐crown‐6, crystals of the compound (K‐18c6)₂[Ge₉{Si(iBu)₃}₂]·tol ( 4 ·tol), containing the bis‐silylated cluster anion [Ge₉(Si(iBu)₃)₂]^2– ( 4a ), were obtained. The compounds 2 ·0.5 tol, 3 ·tol and 4 ·tol were characterized by single‐crystal structure determination.     

Metal–organic framework assembled from erbium and a tetrapodal polyphosphonic acid organic linker

A three‐dimensional metal–organic framework (MOF), poly[[μ₆‐5′‐pentahydrogen [1,1′‐biphenyl]‐3,3′,5,5′‐tetrayltetrakis(phosphonato)]erbium(III)] 2.5‐hydrate], formulated as [Er(C₁₂H₁₁O₁₂P₄)]·2.5H₂O or [Er(H₅btp)]·2.5H₂O ( I ) and isotypical with a Y³⁺‐based MOF reported previously by our research group [Firmino et al. (2017b). Inorg. Chem. 56 , 1193–1208], was constructed based solely on Er³⁺ and on the polyphosphonic organic linker [1,1′‐biphenyl]‐3,3′,5,5′‐tetrakis(phosphonic acid) (H₈btp). The present work describes our efforts to introduce lanthanide cations into the flexible network, demonstrating that, on the one hand, the compound can be obtained using three distinct experimental methods, i.e. hydro(solvo)thermal (Hy), microwave‐assisted (MW) and one‐pot (Op), and, on the other hand, that crystallite size can be approximately fine‐tuned according to the method employed. MOF I contains hexacoordinated Er³⁺ cations which are distributed in a zigzag inorganic chain running parallel to the [100] direction of the unit cell. The chains are, in turn, bridged by the anionic organic linker to form a three‐dimensional 6,6‐connected binodal network. This connectivity leads to the existence of one‐dimensional channels (also running parallel to the [100] direction) filled with disordered and partially occupied water molecules of crystalization which are engaged in O—H…O hydrogen‐bonding interactions with the [Er(H₅btp)] framework. Additional weak π–π interactions [intercentroid distance = 3.957 (7) Å] exist between aromatic rings, which help to maintain the structural integrity of the network.     

Medium band gap conjugated polymers from thienoacene derivatives and pentacyclic aromatic lactam as promising alternatives of poly(3‐hexylthiophene) in photovoltaic application

Two alternating medium band gap conjugated polymers (PBDT‐TPTI and PDTBDT‐TPTI) derived from 4,8‐bis(4,5‐dioctylthien‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene (BDT‐T) or 5,10‐bis(4,5‐didecylthien‐2‐yl)dithieno[2,3‐d:2′,3′‐d′]benzo[1,2‐b:4,5‐b′]dithiophene (DTBDT‐T) with pentacyclic aromatic lactam of N,N‐didodecylthieno[2′,3′:5,6]pyrido[3,4‐g]thieno[3,2‐c]‐iso‐quinoline‐5,11‐dione (TPTI), are synthesized and characterized. The comparative investigation of the photostabilities of the copolymers revealed that the PDTBDT‐TPTI film exhibited the comparable photostability in relative to P3HT. Meanwhile, the inverted photovoltaic cells (i‐PVCs) from the blend films of PBDT‐TPTI and/or PDTBDT‐TPTI with PC₇₁BM, in which poly[(9,9‐bis(3′‐(N,N‐dimethylamino)propyl)‐2,7‐fluorene)‐alt‐2,7‐(9,9‐dioctylfluorene)] were used as cathode modifying interlayer, presented higher power conversion efficiencies (PCEs) of 5.98% and 6.05% with photocurrent response ranging from 300 nm to 650 nm in contrast with the PCEs of 4.48% for the optimal inverted PVCs from P3HT/PC₇₁BM under AM 1.5 G 100 mW/cm². The PCEs of the i‐PVCs from PBDT‐TPTI and PDTBDT‐TPTI were improved to 7.58% and 6.91% in contrast to that of 0.02% for the P3HT‐based i‐PVCs, and the photocurrent responses of the devices were extended to 300–792 nm, when the ITIC was used as electron acceptor materials. The results indicate that the PBDT‐TPTI and PDTBDT‐TPTI can be used as the promising alternatives of notable P3HT in the photovoltaic application. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 85–95     

Synthesis and Characterization of Fluorinated Polyimide Derived from 3,3′‐Diisopropyl‐4,4′‐diaminodiphenyl‐3′′,4′′‐difluorophenylmethane

A novel aromatic diamine monomer, 3,3′‐diisopropyl‐4,4′‐diaminodiphenyl‐3′′,4′′‐difluorophenylmethane (PAFM), was successfully synthesized by coupling of 2‐isopropylaniline and 3,4‐difluorobenzaldehyde. The aromatic diamine was adopted to synthesize a series of fluorinated polyimides by polycondensation with various dianhydrides: pyromellitic dianhydride (PMDA), 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride (ODPA) and 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) via the conventional one‐step method. These polyimides presented excellent solubility in common organic solvents, such as N,N‐dimethylformamide (DMF), N,N‐dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), N‐methyl‐2‐pyrrolidone (NMP), chloroform (CHCl₃), tetrahydrofuran (THF) and so on. The glass transition temperatures (T_g) of fluorinated polyimides were in the range of 260–306°C and the temperature at 10% weight loss in the range of 474–502°C. Their films showed the cut‐off wavelengths of 330–361 nm and higher than 80% transparency in a wavelength range of 385–463 nm. Moreover, polymer films exhibited low dielectric properties in the range of 2.76–2.96 at 1 MHz, as well as prominent mechanical properties with tensile strengths of 66.7–97.4 MPa, a tensile modulus of 1.7–2.1 GPa and elongation at break of 7.2%–12.9%. The polymer films also showed outstanding hydrophobicity with the contact angle in the range of 91.2°–97.9°.     

Improvement of thermoplasticity for s‐BPDA/PDA by copolymerization and blend with novel asymmetric BPDA‐based polyimides

Asymmetric biphenyl type polyimides (PI) derived from 2,3,3′,4′‐biphenyltetracarboxylic dianhydride (a‐BPDA) and p‐phenylenediamine (PDA) or 4,4′‐oxydianiline (ODA) show higher T_gs, and much better thermoplasticity than the corresponding isomeric PIs from symmetric 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA). In addition, a‐BPDA‐derived PIs are completely amorphous owing to their bent chain structures and highly distorted conformations, whereas the PIs from s‐BPDA are semicrystalline. a‐BPDA‐derived PIs possessing these properties or the a‐BPDA monomer were used as a flexible blend component or a comonomer to improve the insufficient thermoplasticity of semirigid s‐BPDA/PDA homo polymer. The blends composed of s‐BPDA/PDA (80%) with a‐BPDA‐derived PIs (20%), as well as the s‐BPDA/PDA‐based copolymer containing 20% a‐BPDA, showed a certain extent of thermoplasticity above the T_gs without causing a decrease in T_g. In addition, these blends and copolymer provided comparatively low thermal expansion coefficient (ca. 18 ppm). The improved film properties for the blends are related to good blend miscibility. On the other hand, when s‐BPDA/ODA was used as a flexible matrix polymer instead of a‐BPDA‐derived PIs, the 80/20 blend film annealed at 400°C exhibited no prominent softening at the T_g. This result arises from annealing‐induced crystallization of the flexible s‐BPDA/ODA component. Thus, these results revealed that a‐BPDA‐derived PIs are promising candidates as matrix polymers for semirigid s‐BPDA/PDA for the present purpose. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2499–2511, 1999     

Two novel lanthanide(III) organic frameworks based on a biphenyltetracarboxylate ligand: synthesis,structure and magnetic and luminescence properties

Two new two‐dimensional lanthanide coordination polymers, namely poly[[tetra‐μ₂‐acetato‐tetraaquabis(μ₄‐biphenyl‐3,3′,5,5′‐tetracarboxylato)tetrakis(dimethylacetamide)tetraterbium(III)] pentahydrate], {[Tb₄(C₁₆H₆O₈)₂(C₂H₃O₂)₄(C₄H₉NO)₄(H₂O)₄]·5H₂O}_n, (1), and poly[[tetra‐μ₂‐acetato‐tetraaquabis(μ₅‐biphenyl‐3,3′,5,5′‐tetracarboxylato)tetrakis(dimethylacetamide)tetraeuropium(III)] tetrahydrate], {[Eu₄(C₁₆H₆O₈)₂(C₂H₃O₂)₄(C₄H₉NO)₄(H₂O)₄]·4H₂O}_n, (2), have been synthesized from biphenyl‐3,3′,5,5′‐tetracarboxylic acid (H₄bpt) and Ln(NO₃)₃·6H₂O (Ln = Tb and Eu) under solvothermal conditions. Single‐crystal X‐ray structure analysis shows that the two compounds are isostructural and crystallize in the monoclinic P2₁/n space group. The crystal structures are constructed from bpt⁴⁻ ligands (as linkers) and {Ln₂(μ₂‐CH₃COO)₂} building units (as nodes), which topological analysis shows to be a (4,6)‐connected network with sql topology. Compounds (1) and (2) have been characterized by elemental analysis, IR spectroscopy, powder X‐ray diffraction (PXRD), thermogravimetric analysis (TGA) and fluorescence analysis in the solid state. In addition, a magnetic investigation shows the presence of antiferromagnetic interactions in compound (1).     

Unexpected Coordination Modes of the Tris(imidazolyl)phosphane Oxide Ligand 4‐TIPOiPr in the Chloro Complexes of Zinc,Cobalt and Nickel

The coordination chemistry of the water soluble phosphane oxide ligand tris[2‐isopropylimidazol‐4(5)‐yl]phosphane oxide, 4‐TIPO^iPr, has been explored. A variety of 3d‐metal halide complexes have been prepared and the crystal structures of the solvates [(4‐TIPO^iPr)ZnCl₂]·MeOH·¹/₂dioxane ( 1 ·MeOH·¹/₂dioxane), [(4‐TIPO^iPr)CoCl₂]·H₂O·2dioxane ( 2 ·H₂O·2dioxane) and [(4‐TIPO^iPr)₂Ni(MeOH)₂]Cl₂·2MeOH ( 3 ·2MeOH) have been determined. All three structures show unprecedented coordination modes of the 4‐TIPO^iPr ligand. Both zinc and cobalt complexes are coordinated in a bidentate κ²N fashion, whereas the nickel atom is coordinated by two ligands in a κN,O mode using one imidazolyl substituent and the P=O oxygen atom.     

Syntheses and properties of organosoluble polyimides based on 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐4, 7‐methanohexahydroindan

A series of organosoluble aromatic polyimides (PIs) was synthesized from 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐4,7‐methanohexahydroindan (3) and commercial available aromatic dianhydrides such as 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride (ODPA), 4,4′‐sulfonyl diphthalic anhydride (SDPA), or 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropanic dianhydride (6FDA). PIs (III_c–f), which were synthesized by direct polymerization in m‐cresol, had inherent viscosities of 0.83–1.05 dL/g. These polymers could easily be dissolved in N,N′‐dimethylacetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylformamide (DMF), pyridine, m‐cresol, and dichloromethane. Whereas copolymerization was proceeded with equivalent molar ratios of pyromellitic dianhydride (PMDA)/6FDA, 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA)/6FDA, or BTDA/SDPA, or ½ for PMDA/SDPA, copolyimides (co‐PIs), derived from 3 and mixed dianhydrides, were soluble in NMP. All the soluble PIs could form transparent, flexible, and tough films, and they showed amorphous characteristics. These films had tensile strengths of 88–111 MPa, elongations at break of 5–10% and initial moduli of 2.01–2.67 GPa. The glass transition temperatures of these polymers were in the range of 252–311°C. Except for III_e, the 10% weight loss temperatures (T_d) of PIs were above 500°C, and the amount of carbonized residues of the PIs at 800°C in nitrogen atmosphere were above 50%. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1681–1691, 1999     

Inclusion of HNEt3+ in an acyclic tetraphenolate

The acyclic tetraphenolic derivative 2,2′‐methyl­ene­bis[6‐(3‐tert‐butyl‐2‐hydroxy‐5‐methyl­benzyl)‐4‐methyl­phenol] reacts with excess triethyl­amine in aceto­nitrile to form a molecular complex, i.e. triethyl­ammonium 2‐(3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzyl)‐6‐[3‐(3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzyl)‐2‐hydroxy‐5‐methylbenzyl]‐4‐methylphenolate aceto­nitrile sol­vate, C₆H₁₆N⁺·­C₃₉H₄₇O₄^?·­C₂H₃N, where the organic HNEt₃⁺ cation is included in the partial cone defined by the aromatic faces of the acyclic poly­phenolate.     

A Hydrogen‐Bonded Framework Complex without Lattice Solvents: Synthesis Reversible Crystal‐to‐Amorphous Transformation and Chromic Properties

Reaction of Ni(NO₃)₂·6H₂O with H₄BPTC (H₄BPTC = Biphenyl‐3,3′,4,4′‐tetracarboxylic acid) produced a 3D hydrogen‐bonded framework complex 1 , not containing lattice solvents, with empirical formula [Ni(H₂O)₆]·H₂BPTC. The complex exhibits an interesting reversible crystal‐to‐amorphous transformation property unaccompanied by lattice solvents release/loading and shows selective and reversible chromic response to methanol.     

Two‐Dimensional Monovalent Copper Halide Coordination Polymers Incorporating Anti‐Conformation 3,3′‐Bipyridine

Hydrothermal treatment of aqueous mixtures of copper(II) halides and 3,3′‐bipyridine (3,3′‐bpy) has afforded the coordination polymers [CuCl(3,3′‐bpy)]_n ( 1 ) and [Cu₂Br₂(3,3′‐bpy)]_n ( 2 ), which were analyzed via single crystal X‐ray diffraction, infrared spectroscopy, and elemental analysis. The structure of 1 consists of two‐dimensional (2‐D) layers constructed from the linkage of castellated one‐dimensional (1‐D) [CuCl]_n stepped chains through anti‐conformation 3,3′‐bpy tethers. Compound 2 presents a related 2‐D sheet motif, albeit built from infinite 1‐D [Cu₂Br₂]_n ladders strutted by 3,3′‐bpy ligands in anti conformation. In both cases neighboring 2‐D sheets stack into 3‐D via weak C–H···halogen interactions.