Photoluminescent properties and electronic structures of monosubstituted polyacetylenes: poly{n-[((4′-cyano-4-biphenylyl)oxy)carbonyl]-1-alkynes}

Poly{n-[((4′-cyano-4-biphenylyl)oxy)carbonyl]-1-alkynes} (PAnCN, where n=2, 8), which is a class of monosubstituted polyacetylenes with biphenyl mesogens and cyano tails in their pendants, can emit strong deep-blue photoluminescence (PL). In this paper we have investigated their optical absorptions, PL evolutions with excitation power and excitation wavelength, electronic structures, and the electric-field effect on the PL of a moderately concentrated PAnCN solution that had been treated by electric fields. Having been treated by an electric-field pulse (6×10⁵ V/m) for about 3 s, the originally featureless PL spectrum of the PAnCN solution becomes structured and transient, which evolves with time and external electric field. Our results have demonstrated that both the absorption and the deep-blue PL originate from the biphenyl mesogens in the side chains rather than from the distorted backbones.     

Synthesis of Co2Pt, Co2Pd and MoPd2 mixed-metal clusters with the P–N–P assembling ligands (Ph2P)2NH (dppa) and (Ph2P)2NMe (dppaMe). Crystal structure of [Co2Pt(μ3-CO)(CO)6(μ-dppa)]

Heterometallic triangular platinum–cobalt, palladium–cobalt and palladium–molybdenum clusters stabilized by one or two bridging diphosphine ligands such as Ph₂PNHPPh₂ (dppa) or (Ph₂P)₂NMe (dppaMe) or by mixed ligand sets Ph₂PCH₂PPh₂ (dppm)/dppa have been prepared with the objectives of comparing the stability and properties of the clusters as a function of the short-bite diphosphine ligand used and of the metal carbonyl fragment they contain. Ligand redistribution reactions were observed during the purification of [Co₂Pd(μ₃-CO)(CO)₄(μ-dppa)(μ-dppm)] (4) by column chromatography with the formation of [Co₂Pd(μ₃-CO)(CO)₄(μ-dppm)₂] and the dinuclear complex [(OC)₂ Cl] (5). The latter was independently prepared by reaction of [Pd(dppa-P,P′)₂](BF₄)₂ with Na[Co(CO)₄]. Attempts to directly incorporate the ligand (Ph₂P)₂N(CH₂)₃Si(OMe)₃ (dppaSi) into a cluster or to generate it by N-functionalization of coordinated dppa were unsuccessful, in contrast to results obtained recently with related clusters. The crystal structure of [Co₂Pt(μ₃-CO)(CO)₆(μ-dppa)] (1) has been determined by X-ray diffraction.     

In-situ generation of poly(quinolizine)s via catalyst-free polyannulations of activated diyne and pyridines

Science China Chemistry - The development of new polymerization routes to afford N-heterocyclic polymers is of vital importance and highly desired for various practical applications. Herein, a...     

Aggregation-induced emission and aggregation-promoted photochromism of bis(diphenylmethylene)dihydroacenes

Reported herein is a new class of pure polycyclic hydrocarbon molecules, designed through a novel aggregation-induced emission (AIE) strategy, with unexpected photochromic properties. The restriction of intramolecular motion was found as a comprehensive mechanism for the AIE effect. The photochromism mechanism study revealed that the photocyclization reaction of cis-stilbene, the molecular conformation in the single crystal and the tetracene backbone should contribute to the unique photo behavior. In particular, the fast responsive, photo-reversible and thermo-irreversible photochromic effect facilitated in the solid state opens a new field of aggregation-promoted photochromism.     

Steric Effects on Reaction Rates. Part VIII. The Significance of Front Strain Release in Solvolysis of Bridgehead Derivatives

The steric requirements of leaving groups for 14 bridgehead derivatives have been examined using MM2 calculations. The strain varies almost monotonously throughout the series upon variation of the leaving group from H to C1, OH, CH₃, CH₃CH₂O, (CH₃)₃CO, (CH₃)₃C and no significant trends for differential F-strain effects are detected expect for the perhydrophenalene derivative 13 . The experimental rates of solvolysis of bridgehead derivatives correlate well with the calculated steric energy differences between substrate R-X and the corresponding carbenium ion R⊕. However, the strain calculations using the more recent force-fields ( MM2 ) disagree, in part, with those reported in the literature: chloride and p-toluenesulfonate leaving groups correlate with identical slopes, and the perhydrotriquinacene derivative 10 shows no anomalous behavior. The calculations suggest that F-strain and C,C-hyperconjugation should not play any dominant role in bridgehead solvolysis.     

Designing Efficient and Ultralong Pure Organic Room‐Temperature Phosphorescent Materials by Structural Isomerism

Pure organic materials with ultralong room‐temperature phosphorescence (RTP) are attractive alternatives to inorganic phosphors. However, they generally show inefficient intersystem crossing (ISC) owing to weak spin–orbit coupling (SOC). A design principle based on the realization of small energy gap between the lowest singlet and triplet states (ΔE_ST) and pure ππ* configuration of the lowest triplet state (T₁) via structural isomerism was used to obtain efficient and ultralong RTP materials. The meta isomer of carbazole‐substituted methyl benzoate exhibits an ultralong lifetime of 795.0 ms with a quantum yield of 2.1 %. Study of the structure–property relationship shows that the varied steric and conjugation effects imposed by ester substituent at different positions are responsible for the small ΔE_ST and pure ππ* configuration of T₁.     

A λ-Lemma for Partially Hyperbolic Tori and the Obstruction Property

Using a scheme given by Marco, we prove that partially hyperbolic tori along resonant surfaces of near-integrable Hamiltonian systems possess the obstruction property in Arnold's terminology. The proof is based on a specific lambda lemma for these tori.     

Numerical simulations of the polymerization reaction of deuterated diacetylene 2,4‐hexadiynylene bis(p‐toluenesulfonate) crystal

In this paper, we developed two types of programs in order to simulate the polymerization reaction of a fully deuterated crystal of diacetylene 2,4‐hexadiynylene bis(p‐toluenesulfonate) (pTS‐D). The first simulation is based on a modification of Baughman's model, a classical model for simulating the polymerization of diacetylene crystals. The agreement between the simulated and experimental results concerning the reaction kinetics is satisfactory. With this simulation algorithm, we take into account the experimental observation that the polymerization of pTS‐H and pTS‐D crystals is really a random process of formation of polymer chains along the crystallographic axis b . The second simulation is based on the Monte Carlo method, which permits not only to simulate the kinetics of the reaction, but also the chain‐length distribution in the hydrogenated and deuterated compounds. These two types of simulations were already developed for the hydrogenated crystal of diacetylene, named pTS‐H. Two main modifications are applied in the case of pTS‐D for taking into account experimental results: in the first the rate constants of chain‐terminating microscopic processes are different in pTS‐H and pTS‐D which must be considered. The second modification concerns the evolution of the lattice deformation during the course of polymerization. The experimental variation of the b parameter as a function of polymer content X in pTS‐D is different from that in pTS‐H; this result is important to consider when calculating the activation energy of the initiation and propagation microscopic processes.     

Silole-containing linear and hyperbranched polymers: synthesis,thermal stability,light emission,nano-dimensional aggregation,and optical power limiting

Linear polyacetylenes and hyperbranched polyphenylenes carrying 1,2,3,4,5-pentaphenylsilolyl (PS) pendants are designed and synthesized. Homo-polymerization of HC≡CPS, HC≡C(CH₂)₉OPS, and C₆H₅C≡C(CH₂)₉OPS and (co)polycyclotrimerization of (HC≡C)₂PS with 1-octyne are effected by NbCl₅-, WCl₆-, MoCl₅-, and TaCl₅-based catalysts. High molecular weight linear ( 1-3 ) and hyperbranched polymers (6) are obtained in high yields (M_w up to ∼70 × 10³ and yield up to 85%). All the polymers are thermally stable, losing little weight when heated to 350°C. Whereas all the polymers emit faint light when molecularly dissolved, polymers 2 , 3 , and 6 become emissive when aggregated in poor solvents or when cooled to low temperatures. Restricted intramolecular rotations of the phenyl rings upon the axes of the single bonds linked to the silole cores may be responsible for the aggregation- or cooling-induced emission. A multilayer electroluminescent device using 3 as an active layer emits a blue light of 496 nm with maximum brightness, current efficiency, and external quantum yield of 1118 cd/m², 1.45 cd/A, and 0.55%, respectively. Polymers 6 are non-linear optically active and strongly attenuate the optical power of intense laser pulses, whose optical limiting performances are superior to that of C₆₀, a best-known optical limiter.