Synthesis,Conductivity and Photosensitivity of 2-D Conjugated Polymers of Metal-porphyrazine with Sulfur Bridges

The title polymers PMS 8Pz,M=Mn Ⅱ,Fe Ⅱ,Co Ⅱ,Ni Ⅱ,Cu Ⅱ,Zn Ⅱ,were synthesized by teaction of 2,3,5,6 tetracyano 1,4 dithiin with corresponding metal salts ,respectively.The styucture and properties of these polyers were characterized by elemental analysis,transmission electron microscope,DTA,IR, UV Vis,fluorescence and EPR spectra. It has been found that these conjugated polymers have the property of intrinsic semiconductor. The conductivity σ 298K of these polymers is in the range of 10 -9 ￣10 -3 S · cm -1 under pressure 10.63 MPa and incremental in the metal orderMn < Co<Fe<Zn<Cu<Ni.\ The photosensitivity of the MS 8Pz to the CdS PVA films is incremental in the metal order Zn < Mn < Co < Fe < Cu < Ni.

Synthesis and Luminescence Properties of Three High-dimensional Coordination Polymers:Zn(Ⅱ) with Imidazole or Benzimidazole Ligand

A novel 2D coordination polymer [Zn2（bim）4]n（1）（Hbim=benzimidazole） based on dihydrated- [N,N＇-bis（2-aminophenl）-oxalamide]（L1·2H2O） with zinc nitrate has been synthesized. Previously we have synthesized complexes [In：Zn3（im）12]n（2）（Him= imidazole） and [Zn（im）2]n（3） successfully. In complex 1, each Zn（Ⅱ） coordinated with four ligands adopts a distorted tetrahedron coordination mode, and the 2D grid structure is built by the Zn（bim）4 as the secondary building unit（SBU）. The luminescence properties of the three complexes were investigated for the first time. The emissions with maxima for complexes 1, 2 and 3 are at 379, 469 and 392 nm, respectively.

Synthesis and Crystal Structure of a 2D Sm(Ⅲ) Coordination Polymer: {[Sm_2L_3(H_2O)_4]·(4,4?-bpy)·3H_2O}_n

A new compound, {[Sm^2L3（H2O）4]·（4,4＇-bpy）·3H2O}n（1, H2 L = 5-（3-pyridyl methoxy） isophthalic acid, 4,4＇-bpy = 4,4A-dipyridyl）, has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 11.266（2）, b = 15.530（3）, c = 16.711（3） A, α = 112.803（3）, β = 90.526（1）, γ = 94.006（3）°, V = 2686.6（9） A3, Z = 2, Dc = 1.727 g/cm^3, μ = 2.251 mm-1, F（000） = 1392, S = 0.999, the final R = 0.0296 and wR = 0.1058. In the title compound, two crystallographically independent Sm^3＋ cations are bridged by the carboxyl group of L2- ligands to form two different {Sm^2} binuclear subunits which are further connected by two distinct L2- ligands to shape a 1D chain, and such 1D chains are linked up to generate a 2D coordination polymer by another crystallographically unique L2- ligand. The thermogravimetric analysis and luminescent property of the title compound were also investigated.

One New 3D Pillared-layer Ag(Ⅰ)-Coordination Framework Based on a Unique 1D Ag2O2 Ribbon： Synthesis,Crystal Structure and Luminescent Properties

A new 3D Ag（I） coordination polymer {[Ag（AZDB）（0.5）（bpe）（0.5）]·H2O}n（1） has been papared by azobenzene-3,3？-dicarboxylicate（H2AZDB）, 1,2-bis（4-pyridyl）ethylene（bpe） and silver salts via hydrothermal method. The compound was fully characterized by single-crystal X-ray diffraction, elemental analyses, infrared spectrum（IR）, powder X-ray diffraction（PXRD） and thermogravimetric analysis（TGA）. The strucrural analysis indicate that compound 1 shows a 3D pillared-layer framework constructed from a unique 1D Ag2O2 ribbon and pyridyl/carboxylicate mixed system, which features a 2-nodal（4, 6）-connected fsc net with a（4^4·6^10·8）（4^4·6^2） topology.Moreover, the photoluminescent properties have also been discussed.

Topology modulation of tetraphenylethylene graphdiyne at a liquid-liquid interface

Monomers with low symmetries can form different topological structures in the preparation of organic two-dimensional(2D)materials.However,it remains challenging to modulate the topologies in practical synthesis.Leveraging theoretical insights into the formation energy of potential structural configurations,we report the topology modulation of a graphdiyne(GDY)derivative constructed from two-fold symmetric tetrakis(4-ethynylphenyl)ethene precursor by changing solvent combinations in a liquid-liquid interfacial system.An aqueous-organic(water-dichloromethane)interface afforded GDY with a kagome topology while a rhombic topology was formed at an organic-organic(hexane-acetonitrile)interface.A comprehensive evaluation of their structures and optoelectronic properties was conducted through various characterization techniques and theoretical computations.Our study provided new insights to modulate the topology of not only GDY but also other framework structures and obtain topologically pure materials in situations where different topologies are possible during practical synthesis.

Two-dimensional polymer nanosheets for efficient energy storage and conversion

As a promising graphene analogue,two-dimensional(2D)polymer nanosheets with unique 2D features,diversified topological structures and as well as tunable electronic properties,have received extensive attention in recent years.Here in this review,we summarized the recent research progress in the preparation methods of 2D polymer nanosheets,mainly including interfacial polymerization and solution polymerization.We also discussed the recent research advancements of 2D polymer nanosheets in the fields of energy storage and conversion applications,such as batteries,supercapacitors,electrocatalysis and photocatalysis.Finally,on the basis of their current development,we put forward the existing challenges and some personal perspectives.

Spectrum-dependent photonic synapses based on 2D imine polymers for power-efficient neuromorphic computing

2D polymers(2DPs)have attracted increasing interests in sensors,catalysis,and gas storage applications.Furthermore,2DPs with unique band structure and tunable photophysical properties also have immense potential for application in photonic neuromorphic computing.Here,photonic synaptic transistors based on 2DPs as the light-tunable charge-trapping medium are developed for the first time.The resulted organic transistors can successfully emulate common synaptic functions,including excitatory postsynaptic current,pair-pulse facilitation,the transition of short-term memory to long-term memory,and dynamic filtering.Benefitting from the high photosensitivity of the 2DP,the devices can be operated under a low operating voltage of0.1 V,and achieve an ultralow energy consumption of~0.29 pJ per event.In addition,the heterostructure formed between the 2DP and organic semiconductor enables spectrum-dependent synaptic responses,which facilitates the simulation of visual learning and memory processes in distinct emotional states.The underlying mechanism of spectrum-dependent synaptic-like behaviors is systematically validated with in situ atomic force microscopy based electrical techniques.The spectrum-enabled tunability of synaptic behaviors further promotes the realization of optical logic functions and associative learning.This work inspires the new application of 2DPs in photonic synapses for future neuromorphic computing.

Synthesis and Crystal Structure of a 2D Honeycomb-like Polymeric Cluster （Et4N）3{[MoS4Cu2（μ-CN）]2（μ＇-CN）}·2MeCN

Reaction of a preformed cluster （Et4N）2[MoS4（CuCN）2]·H2O（1） with acetic acid in MeCN gave rise to an interesting 2D polymeric cluster （Et4N）3 {[MoS4Cu2（μ-CN）]2（μ^1-CN）}·2MeCN （2）. Compound 2 was characterized by elemental analysis, IR spectrum, and single crystal X-ray crystallography. In the structure of 2, the cluster core MoS4Cu2 of the cluster precursor 1 is retained and serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D （6,3） （honeycomb-like） network. The acetic acid induced aggregation of supramolecular compound 2 from the cluster precursor 1 suggests that this simple synthetic strategy be likely applicable to many related systems.

Recent advances in single-crystalline two-dimensional polymers:Synthesis,characterization and challenges

Two-dimensional polymers(2DPs)are emerging crystalline 2D organic material comprising free-standing,single-atom/monomer-thick,planar,and covalent networks with long-ranging structural order.Benefiting from their intrinsic porosity,crystallinity,and electrical properties,2DPs have displayed great potential for separation,energy conversion and electronic fields.In this mini review,we aim to provide the recent progress in crystalline 2DPs films form synthesis strategies to characterization methods,as well as the future trends.We first present the synthesis strategy of single-crystalline 2DPs films including crystal engineering approaches and surface science.Also,we summarize the characterization methods of 2DPs films and highlight the advantages and limitations of different methods focusing on chemical bonding,morphology,and crystal structure.Finally,we will present the current challenges and trends regarding the future developments of crystallinity,monomer design,synthesis strategy and characterization.

Interfacial synthesis of crystalline quasi-two-dimensional polyaniline thin films for high-performance flexible on-chip micro-supercapacitors

Quasi-two-dimensional(q2 D)conducting polymer thin film synergizes the advantageous features of longrange molecular ordering and high intrinsic conductivity,which are promising for flexible thin film-based micro-supercapacitors(MSCs).Herein,we present the high-performance flexible MSCs based on highly ordered quasi-two-dimensional polyaniline(q2 D-PANI)thin film using surfactant monolayer assisted interfacial synthesis(SMAIS).Owing to high electrical conductivity,rich redox chemistry,and thin-film morphology,the q2 D-PANI MSCs show high volumetric specific capacitance(ca.360 F/cm^(3))and energy density(17.9 m Wh/cm^(3)),which outperform the state-of-art PANI thin-film based MSCs and promise for future flexible electronics.

Transport and selectivity of indium through polymer inclusion membrane in hydrochloric acid medium

In the present paper, a polymer inclusion membrane （PIM） containing polyvinyl chloride （PVC）, and bis-（2-ethylhexyl） phosphate （D2EHPA） which was used as extracting agent was used for the recovery of In（Ⅲ） ions in hydrochloric acid medium. The effects of carrier concentration, feed phase pH, strip phase HCI concentration, temperature on the transport, and the membrane＇s stability and thickness were examined. And the conditions for the selective separation of In（Ⅲ） and CU（Ⅱ） were optimized. The results showed that the transport of In（Ⅲ） across PIM was consistent with the first order kinetics equation, and also it was controlled by both the diffusion of the metal complex in the membrane and the chemical reaction at the interface of the boundary layers. The transport flux （J0） was inversely proportional to the membrane thickness, however, the transport stability improved as the membrane thickness increased. The transport flux of In（Ⅲ） and CU（Ⅱ） was decreased by excessive acidity of feed phase and high concentration of Cl^- . The selectivity separation coefficient of In（Ⅲ）/Cu（Ⅱ） was up to 34.33 when the original concentration of both In（Ⅲ） and Cu（Ⅱ） was 80 mg· L^ -1 as well as the pH of the feed phase and the concentration of Cl^- in the adjusting context were 0.6 and 0.5 mol· L^-1, respectively. Within the range of pH = 1-3, the separation selectivity of In（Ⅲ）/Cu（Ⅱ） reached the peak in the case when the Cl^- concentration was 0.7 mol·L^ -1.