Assemblies And Properties Of Supramolecular Systems Constructed By O-contained Small Molecule Ligands

The exploitation of high-performance optical and electrical materials can effectively improve energy efficiency,and promote the comprehensive development of modern science and technology.Novel generation of crystalline materials,which are prepared by the combination of supramolecular chemistry and crystal engineering,can provide good basic raw materials in support of the higher performance breakthrough of the two energy-related domains.O-contained small molecule ligands:sulfate anion and dimethyl sulfoxide(DMSO)were selected as ligands for the construction of a series of open framework copper sulfates?zinc sulfates and Al-based solvento complex material by self-assembling with Zn²⁺,Cu²⁺and Al³⁺,under the presence of template molecules(alkali metal ions and organic amines)as structure-directing agents(SDAs)or by adopting crystallization host-guest inclusion strategy,respectively.Summarized and analyzed the synthesis rules and structural characteristics.The electrochemical activities toward Li+and Na+ insertion-extraction,and long lifetime room temperature phosphorescence(RTP)properties of the related materials were investigated.The main research contents and results are as follows:(1)Four high dimensional open-framework copper sulfates have been synthesized by using sulfate group and Cu²⁺ion as inorganic building units in the presence of Na+and K+as structural directing agents.The electrochemical activities of the compounds toward Li+and Na+insertion-extraction were investigated.Na[Cu₂(OH)(H₂O)(SO₄)₂](2.1)and K[Cu₂(OH)(H₂O)(SO₄)₂](2.2)were isomorphous,both have Natrochalcite typed two-dimensional anionic layer structure.Na₂[Cu(SO₄)₂](2.3)and K₂[Cu(SO₄)₂](2.4)have new three-dimensional frameworks with eight-membered ring channels and eight-membered&twelve-membered ring channels respectively.As anode material,2.1 delivered 224 mAh/g and 175 mAh/g in the first discharge in Li-and Na-ion batteries respectively.As anode materials of Na-ion battery,2.2 and 2.4 delivered 97 mAh/g and 62 mAh/g in the first discharge respectively.All of them have Cu²⁺/Cu⁺/Cu redox reactions during the charge-discharge processes.Their initial framework recrystallization recovery abilities in the charge-discharge cycle were weak,resulting in a lower discharge specific capacity recovery rate.The "soft and hard acids and bases theory" was employed to explain the electrochemical cycle stability of the compounds:the Cu⁺ ion involved in the charge-discharge cycle was a soft acid,which was not easy to combine with SO42-group(hard base),resulting in the amorphous deactivation of the electrode materials.(2)Four new inorganic-organic zinc sulfate open frameworks were prepared by using sulfate group and Zn²⁺ ion as inorganic building units in the presence of non-aromatic organic amines as structural directing agents.Their RTP behaviors originated from non-aromatic organic amine molecules/ions were investigated.(C₆H₁₈N₂)[Zn(SO₄)₂](3·1)showed a krohnkite typed one dimensional chain structure.(C₄H₁₂N₂)[Zn₃(?₃-OH)₂(SO₄)₃]·4H₂O(3.2)and(C₅H₁₄N₂)[Zn(SO₄)₂](3.3)displayed two-dimensional layer structures of honeycomb network.(C₆N₄H₁₂)[Zn₄O(SO₄)₃](3.4)was the first perovskite-like structure found in sulfate compounds.Luminescence characterization showed that compounds 3.1-3.4 all have long-lasting RTP behaviors under ambient conditions,and the lifetime can reach the order of 100 milliseconds and more.Among them,3.4 showed the longest lifetime up to 1090.0 ms.According to information of X-ray single crystal diffraction data,the room temperature phosphorescence(RTP)behavior,which arising from the radiative relaxation process of the excited triplet-state in organic amines,was due to the fact that the rigid inorganic framework can effectively immobilize the triplet-state energy of the specific selected light-emitting non-aromatic organic components through non-bonding interactions.Several new frameworks and and efficiently modulated luminescence properties have been gained by changing the species and configurations of organic components,and optimizing the reaction conditions.It provides new perspective and strategy for functionalizing organic-inorganic hybrids with room temperature phosphorescence emission properties.3)On the basis of the inorganic-organic hybrid zinc sulfate RTP materials mentioned above,for further expanding the host-guest phosphorescence induced strategy application,ionic solvento complexes[Al(DMSO)₆]X₃(X=Cl,Br)formed by the coordination of dimethyl sulfoxide and Al³⁺were selected as the guest molecule-friendly host matrices,and a series of long-lasting RTP materials were constructed by doping trace amount of various organic guest molecules into the hosts.Characteristiced with the advantage of facile prepatation and good host-guest compatibility,this method can efficiently avoid organic configuration limitation and aggregation caused emission quenching,providing a good platform for exploring high-performance organic-based long-lasting phosphorescent materials.The host matrix provided a rigid environment to immobilize the guest molecules through weak interactions,and promoted the intersystem crossing between singlet-triplet states through the external heavy atom effect of the halogen counter-anions,efficiently improving their RTP performance.Besides,a photophysical performance controlling of these composite materials from ultralong afterglow to high luminescence quantum yield was realized by adjusting the halogen counter-anion of the host matrix.The prepared composite materials show ultralong lifetime up to 1811.7 ms or phosphorescence efficiency up to 17.4%.Furthermore,a dual-mode,tetra-emitting homogenerous fluorescence/phosphorescence composite was achieved by a multi-component co-loading method,which demonstrateed its potential value in advanced anti-counterfeiting applications.