π-CONJUGATED OLIGOMERS IN SUPRAMOLECULAR CRYSTALS AND THEIR OPTOELECTRONIC FUNCTIONS

Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance of these devices relies on the understanding and optimization of several complementary processes. Our goal is to discuss the relationship between the molecular stacking structures and their optoelectronic properties that are of importance in all these areas. The concept of intermolecular interaction should be taken here in the special sense that is inter-dipole coupling. Specifically, we will address the impact of inter-dipole interaction between adjacent molecules in aggregate state on the solid-state emission properties.

Organic Melt Crystallization as a Method for Synthesis of Supramolecular Complexes

The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.

One Novel Mn(Ⅱ)Complex with 1-Substituted-1H-1,2,3-triazole-4-carboxylic Acid:Crystal Structure,Fluorescence and Hirshfeld Surface Analysis

The crystal structure of one novel Mn（II） complex, [Mn（pmta）_3]_2[Mn（H_2O）_6]·4H_2O（1）, is reported（Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid）. In the title compound, the asymmetric unit consists of a [Mn（pmta_）3]ˉ anion, half [Mn（H_2O）_6]^（2＋） counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.

Supramolecular Network Obtained from the Interaction of Dihydrophosphate Anions and Thiourea-based Receptors

Two crystals of receptor 1, C（42）H（52）N（10）O4S2（anthracene-9,10-dicarbaldehyde bis-（phenyl-semithiocarbazone）） and-1-H2PO4, C（68）H（114）N（10）O（10）P2S2 were obtained at room temperature successfully, and their structures were characterized by X-ray crystallography diffraction. X-ray diffraction reveals that, receptor 1 crystallizes in monoclinic, space group P21/c, with a = 9.487（3）,b = 20.674（6）, c = 11.821（4）A, β = 113.416（8）o, Mr = 825.06, V = 2127.5（12） A^3, Z = 2, Dc = 1.288g/cm^3, μ = 0.18 mm^-1, F（000） = 876, MoK α radiation（λ = 0.71073 A）, the final R = 0.0472 and wR = 0.0930. A total of 3758 unique reflections were collected, of which 3313 with I 〉 2σ（I） were observed. Compound 1-H2PO4^-crystallizes in triclinic, space group P21/n, with a = 8.767（1）, b =13.6190（15）, c = 16.615（2） ？, α = 98.727（14）, β = 103.061（14）, γ = 91.382（16）°, Mr = 1357.75, V =1906.6（4） A^3, Z = 1, Dc = 1.183 g/cm^3, μ = 0.17 mm-（-1）, F（000） = 734, MoK α radiation（λ = 0.71073？）, the final R = 0.0769 and wR = 0.1884. A total of 6699 unique reflections were collected, of which 2989 with I 〉 2σ（I） were observed. As it was observed in the crystal structure of 1-H2PO4^-, 1bound H2PO4^-at a 1：2 ratio by intermolecular interaction of N-H···O hydrogen bond obviously.Another interesting feature was that H2PO4--groups assembled chains themselves via intramolecular hydrogen bond O-H···O and connected the 1 molecules together through the interaction of H-bonds,which improved the planarity of 1 and increased the stability of the entire structure.

Synthesis, Crystal Structure and Thermal Stability of a New Cadmium(II) Polymer Based on 1H-pyrazole-3-carboxylic Acid Ligand

A novel Cd（Ⅱ） coordination polymer, [CdCI（Hpc）H2O]n （1, H2pc = 1H-pyrazole-3- carboxylic acid）, was synthesized by the reaction of CdCl2·2.5H2O with H2pc, and structurally characterized by IR spectrum, UV-Vis spectrum, elemental analysis, single-crystal X-ray diffraction, as well as thermal analysis. Compound 1 crystallizes in monoclinic, P21/n space group with α = 7.0304（3）, b = 10.3047（3）, c = 10.6446（4） A, β= 107.174（4）°, F = 736.78（5） A^3, Z = 4, C4HsCdClN2O3, Mr = 276.95, Dc = 2.497 g/cm%3, F（000） = 528.0,μ= 3.281 mm^-1, R = 0.0169 and wR = 0.0387. The central metals adopt distorted octahedral geometry. Carboxyl groups of the ligand connect Cd（Ⅱ） into a one-dimensional chain, which further constructs a two-dimensional network by halogen bridging. Such two-dimensional structures are finally connected into a three-dimensional supramolecular architecture due to the hydrogen bonds and intermolecular π…π interactions. In addition, complex 1 has high thermal stability.

Supramolecular liquid crystals from the dimer of L-shapedmolecules with tertiary amide end groups

Supramolecular liquid crystals(SLCs)are attractive materials for fabricating devices with new optoelectronic functions.Conventional SLCs are made from hydrogen-bonded mesogens.However,these mesogens suffer from high melting points,and the types of formable aggregates are limited owing to the directionality of the hydro-gen bonding.Therefore,to fabricate non-hydrogen-bonded SLCs,we hypothesized that the introduction of tertiary amide groups into calamitic molecules would be advantageous because they have an L-shaped structure with N-or C-alkyl side chains not aligned along the long axis and theflexibility to undergo cis–trans isomeriza-tion.In this study,we developed a novel non-hydrogen-bonded SLC by assembling an L-shaped dimer composed of calamitic molecules(phenyltolanes)with tertiary amides at their ends.These molecules exhibited a smectic B phase.The phase tran-sition temperature of the SLCs from crystal to liquid crystal phase was low despite the longπ-conjugated core.Wide-angle X-ray diffraction and variable-temperature Fourier-transform infrared measurements revealed dimer formation by weak inter-molecular interactions,that is,the molecular recognition of L-shaped molecules,and mobility of the alkyl groups attached to amide driven by cis–trans isomerization in the liquid crystal phase.Thus,cis–trans isomerization of tertiary amides contributed enormously to the formation and lower clearing points of this SLC.The developed method can be used not only to develop non-hydrogen-bonded SLCs but also to develop novel soft matter with controlled properties by incorporating the SLCs,as the aggregates can be controlled to impart desired functionalities.

超分子体系移位[2+2]环加成制备高分子的研究进展

综述了光催化下移位[2+2]环加成制备高分子的研究进展,总结了在有机超分子和金属-有机配位超分子结晶体系中完成光聚合的条件,内容包括分子结构、晶格数据、实验及表征等。该方法借助现代技术手段,具有先进、绿色、高效等优点,是制备具有精确微观结构的新颖高分子的首选策略。

Bio-organic adaptive photonic crystals enable supramolecular solvatochromism

Photonic crystals(PCs)exhibit promising structural coloration properties and possess extensive application prospects in diverse optical fields.However,state-of-the-art inorganic or polymeric PCs show limited adaptivity as their configurations are fixed once formed.Herein,bio-organic adaptive PCs are fabricated via drop-casting of amphiphilic guanine-based peptide nucleic acid selfassembled microspheres.The high formation activation energy of up to 81.8 kJ·mol−1 suggests that the self-assembly step dominates the entire process.Therefore,the configurations along with the structural coloration of the supramolecular PCs are sensitive to self-assembly influencing parameters,showing temperature-encoded structural color evolution and solvent polaritydependent solvatochromism.Our findings demonstrate that the supramolecular PCs are adaptive,thus showing promising potential for detection of organic solvents of different polarities in a visual and real-time manner for environmental protection or optical applications.

Synthesis and Characterization of a Manganese(Ⅱ) Coordination Compound with Two-dimensional Layer Structure: {[Mn_2(IP)_2(1,4-bdc)_2]·H_2O}n

A new complex {[Mn2（IP）2（1,4-bdc）2]·H2O}n（1）（IP = 1H-imidazo[4,5-f][1,10]-phenanthroline, 1,4-H2 bdc = 1,4-benzendicarboxylic acid）, have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group Cc with a = 20.326（2）, b = 24.249（2）, c = 7.621（1）A, β = 108.546（6）, V = 3561.2（7）A3, Z = 4, Dc = 1.672 g/cm^3, μ = 0.785 mm^-1, F（000） = 1824, S = 1.067, the final R = 0.0299 and wR = 0.0752. Compound 1 possesses a 2D structural motif, in which two crystallographically independent 1,4-bdc dianions adopt the alternative mode of mixed bis（bidentate） and monodentate-bidentate coordination modes to bridge neighboring Mn（II） centers. And the 2D layers are linked up by hydrogen bonding and π···π stacking interactions to form a 3D network. The title compound has good thermal stability and exhibits photoluminescent emission maximum at 518 nm.

Nano-Hybrid Liquid Crystals from the Self-Assembly of Surfactant-Encapsulated Polyoxometalate Complexes

The construction of nano-hybrid liquid crystals(LCs)has been intensively pursued because the unique traits of nano-objects together with the self-assembly features of LCs allow the development of novel anisotropic materials.Self-assembly of surfactant-encapsulated polyoxometalate(SEP)complexes,consisting of nano-sized cores and organic shells,provides particularly important contribution in this area.The main motivation for developing those nano-hybrid liquid crystals originates from the added-value combination between anionic polyoxometalates and cationic surfactants.This account describes recent work in our group to develop thermotropic SEP complexes that result from the sophisticated molecular design.Since the polyoxometalates possess well-defined topology,strictly mono-dispersed size,and precise surface charges,it is possible to get more insight into understanding of the influ-ence of nature of components on the thermal property of nano-hybrid LCs.We briefly describe the general impor-tance and advantage of nano-hybrid LCs.We then highlight the synthesis and characterization of thermotropic liquid crystals based on polyoxometalate nano-clusters.The driving forces behind the molecular self-assembly are discussed in depth.The various factors,including chain length,surfactant density and the size-matching effect,affecting the interfacial curvature and the LC properties are summarized.We expect that the structure-property rela-tionships are virtually helpful for the design of new nano-hybrid LC materials.