Shuo-ping Chen

Supramolecular hydrogen bond framework constructed by 1-aminoethylidenediphosphonic acid and monovalent ions: Li + , Na + , and

Four new monovalent 1-aminoethylidenediphosphonates, [Li(AEDPH3)(H2O)]6 (1), Na2(AEDPH3)2(H2O)8 (2), (NH4)(AEDPH3) (3) and ((CH3)2NH2)(AEDPH3)(H2O) (4) have been synthesized and characterized by elemental analysis, IR, TG together with X-ray single crystal diffraction analysis. Compound 1 is a 24-metallacrown-6 lithium structure, compound 2 is binuclear Na+ bridged by water molecules, and compounds 3 and 4 are proton-transfer salts. All four compounds are further extended to form three-dimensional (3D) supramolecular structures with the aid of water molecules (excluding 3) via various predictable hydrogen bonds.

Self-assembly of organic acid–base compounds from 2-D layered network to 3-D supramolecular framework: synthesis, structure and photoluminescence

The reactions of organophosphonic acids [1-aminoethylidenediphosphonic acid (AEDPH4), 1-aminopropane-1,1,3-triphosphonic acid (APTPH6)] and 2,2′-bipyridyl-like ligands [2,2′-bipyridyl (bipy), 1,10-phenanthroline (phen)] under low temperature hydrothermal conditions yielded four acid–base compounds, namely, (AEDPH3)·(H2bipy)1/2·2H2O (1), (AEDPH3)·(Hphen)·2H2O (2), (APTPH5)·(Hbipy)·2H2O (3) and (APTPH4)·(Hphen)·(H3O)·3H2O (4). These four compounds were characterized by a single crystal X-ray diffraction method, elemental analysis (EA), infrared spectrometry (IR) and thermogravimetric analysis (TGA). They all crystallize in a triclinic system, with a P space group. In particular, the supramolecular structures of organophosphonic acids in these four compounds are different. In compounds 1 and 2, the dimer or dimer chains are formed by hydrogen bonds between adjacent phosphonate groups, while in compounds 3 and 4 two-dimensional (2-D) layered networks are constructed by the hydrogen bonds between the phosphonate groups. The diversity of supramolecular structures is due to the difference of AEDPH4 and APTPH6 ligands. Additionally, their luminescence in the solid state has also been studied at room temperature.

Hydrogen-bonded assembly of aminophosphonic anions: different 1D, 2D and 3D supramolecular architectures

In order to investigate hydrogen-bonded assembly of aminophosphonic anions, six novel organic acid–base compounds including (AEDPH2)·(1,3-pnH2)·H2O (1), (AEDPH2)·(1,2-pnH2)·H2O (2), (AEDPH2)·(pipH2)·H2O (3), (AEDPH3)·(pipH2)0.5·3H2O (4), (APDPH3)·(pipH2)0.5 (5) and (APDPH3)·(enH2)0.5 (6), as well as hydrate compounds (AEDPH3)·H3O (7) and (APDPH3)·H3O (8) (AEDPH4 = 1-aminoethylidenediphosphonic acid, APDPH4 = 1-aminopropane-1,1-diphosphonic acid, 1,2-pn = 1,2-propylenediamine, 1,3-pn = 1,3-propylenediamine, pip = piperazin, en = ethylenediamine), were synthesized and characterized. The aminophosphonic acids in these compounds are deprotonated to form anions with different valences and show various structural aggregates: The AEDPH22− anions form one-dimensional (1D) zigzag supramolecular chains with different chain lengths and angles in compounds 1 and 2, while create 1D linear double supramolecular chain in compound 3. The monovalent aminophosphonic anions generate two-dimensional (2D) supramolecular layers with different layer to layer distances in compounds 4–6, but display 3D supramolecular framework in compounds 7 and 8. In particular, compound 4 contains a 1(1)3(1)R4 water cluster. The factors which influence hydrogen-bonded assembly of aminophosphonic anions, including structure of diamine, C: A ratio and substitutional group of aminophosphonic acid, are all discussed in detail.

Synthesis and structures of three triphosphonate compounds containing d10 transition metal ions

Three new triphosphonate compounds, [Zn(APTPH4)(2,2′-bipy)(H2O)] · 2H2O (1), [Cd(APTPH4)(2,2′-bipy)(H2O)] · 2H2O (2), and [Zn(APTPH4)(phen)2] · phen · 4H2O (3) (APTPH6 = 1-aminopropane-1,1,3-triphosphonic acid, 2,2′-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline), are synthesized by a low-temperature hydrothermal method. Compounds 1 and 2 are isomorphous, both one-dimensional (1D) coordination polymers expanded into three-dimensional (3D) supramolecular structures by hydrogen bonds and π–π stacking interactions. Compound 3 is a molecular complex and forms a 3D network through an S-shaped water hexamer. Crystal data for 1: Triclinic, space group P 1, a = 6.6814(5) Å, b = 10.0929(7) Å, c = 15.438(2) Å, α = 81.544(2)°, β = 79.066(2)°, γ = 82.278(2)°, Z = 2; for 2: Triclinic, space group P 1, a = 6.9380(8) Å, b = 10.043(2) Å, c = 15.681(2) Å, α = 81.357(2)°, β = 78.510(2)°, γ = 81.902(2)°, Z = 2; Crystal data for 3: Triclinic, space group P 1, a = 12.540(2) Å, b = 12.596(2) Å, c = 14.997(2) Å, α = 100.795(2)°, β = 113.328(2)°, γ = 101.358(2)°, Z = 2.

Hydrogen-bonded assembly of [Ni(Im)6]2+ ion and phosphorus anions: Different sandwiched-type/tessellate-type supramolecular architectures and 1D water chains

Four new [Ni(Im)6]2+-phosphorus compounds, namely, [Ni(Im)6](PO4)·ImH·4 H2O (1), [Ni(Im)6][Ni(AEDPH)(Im)3]2 (2) [Ni(Im)6][Ni(AEDP)(Im)3]·Im·3 H2O (3), [Ni(Im)6][Ni(Im)3(APTPH)]·Im·ImH·8 H2O (4), (AEDPH4 = 1-aminoethylidenediphosphonic acid, APTPH6 = 1-aminopropane-1,1,3-triphosphonic acid), are synthesized and characterized. These compounds illustrate various three-dimensional (3D) supramolecular structures. Compounds 1 and 2 both contain a two-dimensional (2D) packing arrangement of [Ni(Im)6]2+ ions however they feature different sandwich-type structures: in 1, PO43− ions and ImH+ ions are self-assembled to form a one-dimensional (1D) zigzag supramolecular chain; while a 2D pillared layer structure is generated by the interconnection of [Ni(AEDPH)(Im)3]− ions in 2. Compounds 3 and 4 both comprise a 1D packing arrangement of [Ni(Im)6]2+ ions however they form dissimilar tessellate-type architectures: in 3, 1D double chain structure is constructed by [Ni(AEDPH)(Im)3]2− ions and Im molecules, whereas in 4, [Ni(Im)3(APTPH)]3− ions, Im molecules and ImH+ ions are integrated to generate a 3D supramolecular network with extended 1D channels. Moreover, compounds 1, 3 and 4 all contain diverse 1D water chain structures: C8 helix water chain in 1, C4 zigzag water chain in 3, and 1(1)8(1)C14 wavelike water chain in 4. The effects of phosphorus counterions on the structural types of the final products, as well as the hydrogen bond motifs, are also discussed in detail.

Manganese(II) enhanced fluorescent nitrogen-doped graphene quantum dots: a facile and efficient synthesis and their applications for bioimaging and detection of Hg2+ ions

Manganese ion (Mn2+) bonded nitrogen-doped graphene quantum dots (Mn(II)-NGQDs) with water solubility have been successfully synthesized by a simple, one-pot hydrothermal carbonization, using sodium citrate, glycine and manganese chloride as raw materials. The photoluminescence (PL) characteristics of Mn(II)-NGQDs were studied in detail. The resulting Mn(II)-NGQDs show a remarkably enhanced PL intensity and quantum yield (QY = 42.16%) compared with the product without Mn(II)-doped (named as NG, QY = 27.06%) and the product doped with other metal ions. The Mn(II)-NGQDs not only display low toxicity and high cellular uptake efficiency for fluorescence live cell imaging in biological evaluations but also exhibit a fast, highly selective and sensitive fluorescence quenching effect toward Hg2+ ions, with a detection limit of 3.4 × 10−8 mol L−1.

Hydrous salts of 1-aminoethylidenediphosphonic acid and piperazidine: temperature induced reversible structural transformation in a humid environment

A series of hydrous salts constructed using 1-aminoethylidenediphosphonic acid (AEDPH4) and piperazidine (pip) were synthesized and structurally characterized, namely (AEDPH3)·(pipH2)0.5·0.5H2O (1), (AEDPH3)·(pipH2)0.5·2H2O (2), and (AEDPH3)·(pipH2)0.5·3H2O (3). Compounds 1–3 all contain porous [(AEDPH3)·(pipH2)0.5]n supramolecular hosts with the same components, but illustrate different host structures, which allow different numbers of water molecules to lie inside. Moreover, a reversible structural transformation circle is observed among the single crystals of the three hydrous salts, that is, compounds 1–3 through changing the temperature, can transform into each other in a humid environment.

(AEDPH3)·(8-OQH)·(H2O): a yellow supramolecular plaster with ammonia adsorption and ammonia-induced discoloration properties

A novel supramolecular plaster, namely (AEDPH3)·(8-OQH)·(H2O) (1), is synthesized and characterized. This plaster is an organic acid–base compound, which shows a three-dimensional (3D) sandwich-type supramolecular network. It is a yellow gelling material with excellent mechanical properties superior to that of gypsum plaster. Moreover, the plaster can adsorb ammonia (NH3) effectively, and exhibits an interesting ammonia-induced discoloration property.

A novel organic salt with water/humidity-induced fluorescence switching and heat-induced coloration performance

A novel organic salt, namely (H2PO3)2·(H3PO3)·(phenH)2·H2O (1), is synthesized and characterized, and shows a 3D tessellate-type supramolecular structure containing 1D [(phenH+)·(H2PO3−)]n supramolecular chains. Compound 1 is a multifunctional material: it displays infrequent water/humidity-induced fluorescence switching performance at room temperature, whose fluorescent color can be reversibly changed between blue, cyan and violet by placing at different relative humidities or adding various amounts of water; moreover, compound 1 shows interesting heat-induced coloration at high temperature, whereby its color can be changed from colorless to red by heat. The mechanisms of the fluorescence switching and coloration are also investigated.

Two new nickel phosphonate compounds: different supramolecule structures constructed by 1-aminoethylidenediphosphonic acid and ammonium counterions

Hydrothermal reactions of 1-aminoethylidenediphosphonic acid (AEDPH4), Ni(OH)2 and ammonium counterions afforded two nickel phosphonate compounds, (enH2)3[Ni(AEDP)2] · 6H2O (1) and (NH4)6[Ni(AEDP)2] · 4H2O (2) (en = ethylenediamine). Compounds 1 and 2 both contain [Ni(AEDP)2]6− while having different three-dimensional (3-D) supramolecular structures. In 1, the [Ni(AEDP)2]6− anion and cations interconnected via various hydrogen bonds and form a 3-D porous supramolecular network with extended one-dimensional channels, in which an interesting T4(2)6(2) water tape penetrates. Compared to 1, the [Ni(AEDP)2]6− anion and cations in 2 constitute an enclosed 3-D supramolecular framework without obvious channels; two water-ammonium clusters with different structural motifs are observed. The magnetism of 1 exhibits weak antiferromagnetic interaction via the hydrogen bonds. The effect of protonated ammonium counterions on the structural types of the final products is also discussed.