Yun-Yin Niu

Role of cooperative templates in the self-assembly process of microporous structures: syntheses and characterization of 12 new silver halide/thiocyanate supramolecular polymers

12 new cation-templated complexes, {(BMPB)[AgI3]} (BMPB = 1, 4-bis (methylpyridinium) benzene) (1), {(BPE)2[Ag2I6]} (BPE = 1, 2-bis (pyridinium) ethane) (2), {(BPB)[Ag2I4]} (BPB = 1, 4-bis (pyridinium) butane) (3), {(BPH)[Ag2I4]} (BPH = 1, 7-bis (pyridinium) heptane) (4), {(DIBP)[Ag2I4]} (DIBP = 1, 1′-diisopropyl-4, 4′-bipyridinium) (5), {(BPB)[Ag2Br4]} (6), {(BPP)[Ag2Br4]} (=1, 5-bis (pyridinium) pentane) (7), {(DEBP)[Ag2Br4]} (DEBP = 1, 1′-diethyl-4, 4′-bipyridinium) (8), {(BDMLB)[Ag2Br4]} (BDMLB = 1, 4-bis (dimethylimidazolium) butane) (9), {(BPIB·Br)[Ag(NCS)2]} (BPIB·Br = butane phenanthroline bromide) (10), {(DABP)[Ag4I6]} (DABP = 1, 1′-diamyl-4, 4′-bipyridinium) (11), {(BMLB)[Ag2Br2(NCS)2]} (BMLB = 1, 4-bis (methylimidazolium) butane) (12), have been synthesized via the self-assembly reaction in solution. Owing to the cooperative template effects from organic cations and halide/thiocyanate anion compounds 1–11 contain a mononuclear anion structure [AgI3]2− (1), a dimeric anion [Ag2I6]4− (2), linear chain [Ag2X4]2− (3–10) and a cubane-like based one-dimensional anionic chain [Ag4I6]2− (11) that are enclosed into the different cationic channels formed from the pyridinium, phenanthrolinium and imidazolium. While for 12, the compound possesses an infinite 2D supramolecular polypseudorotaxane penetrated by geminal dicationic groups.

Four novel metal coordination polymers directed by 1,1′-dibutyl-4,4′-bipyridinium dibromide (BBP) and their framework dependent luminescent properties

In our effort to systematically investigate the influence of spacers and terminal groups in structure-directing agent BBP on Ag/I, Pb/I and Cu/SCN inorganic frameworks, four coordination polymers, {[(Ag2I6)(BBP)2]} (1), {[(Pb6I22)(DMF)2(BBP)5]} (2), {[Cu2(SCN)4(BBP)]}n (3) and {[Cu4(SCN)6(BBP)]}n (4) have been synthesized in polar organic solvents. Compound 1 is a dimer of [Ag2I6]2−; compound 2 is a hexanuclear oligomer of [Pb6I22]10−; both compound 3 and 4 are infinite Cu(I) supramolecular polymers linked by bridging thiocyanate groups; whereas compound 3 possesses a 1D chain structure, compound 4 exhibits a two-dimensional cubane-based polypseudorotaxane network. All compounds were further characterized with elemental analysis, IR spectra, thermal analysis, and fluorescence properties.

The syntheses, crystal structures and optical limiting effects of HgI2 adduct polymers bridged by bipyridyl-based ligands

Abstract Two novel coordination polymers incorporating mercury(II) iodide, [Hg (tmp)I2]n (1) (tmp=4,4′-trimethylene dipyridine) and [Hg(azobpy)I2]n (2) (azobpy=3,3′-azobispyridine), have been synthesized via the self-assembly reaction in solution. Their structures were characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 is the first 1D wave-shaped adduct containing HgI2. Complex 2 is a 3D supramolecular framework constructed from HgI2–azobpy zigzag chains linked mutually through Hg⋯I interaction. The optical limiting effects were studied by Z-scan technology with an 8 ns-pulsed laser at 532 nm. Their limiting thresholds were determined to be 0.8 J cm−2 for 1 and 0.4 J cm−2 for 2, which are comparable to those of many heterothiometallates.

The anion exchange reaction of bis(isoquinoline) ionic liquids: self-assembly, crystal structures and thermal properties of ten novel d10 metal (Cu, Ag) halide/thiocyanate supramolecular polymers

Ten novel cation-induced complexes, {(BIQPT)2[Ag2I6]} (1), {[(BIQBT)CuI3]} (2), {(BIQHX)2[Cu4I8]·DMF} (3), {(BIQBT)1.5[MoOS3Cu3I4]·DMF} (4), {(BIQHX)[Ag4Br6]}n (5), {[(BIQHX)Ag4I6]}n (6), {(BIQHX)[Cu2(SCN)4]}n (7), {(BIQBT)[Cu2(SCN)4]}n (8), {(BIQPP)[Cu2(SCN)4]}n (9), {(BIQEH)[Cu2(SCN)4]}n (10) {BIQPT = 1,5-bis(isoquinoline)pentane, BIQBT = 1,4-bis(isoquinoline)butane, BIQHX = 1,6-bis(isoquinoline)hexane, BIQPP = 1,3-bis(isoquinoline)propane, BIQEH = 1,2-bis(isoquinoline)ethane} have been constructed via anion exchange reaction of bis(isoquinoline) ionic liquids. In these ten compounds, the anion structures ranged from mononuclear (2), dimer (1), tetranuclear oligomer (3 and 4), to 1D chain (5, 6,7 and 8) and 2D polymeric architectures (9 and 10). These results indicated that anion exchange reaction is an efficient approach for the preparation of cluster-functionalized ILs or IL-functionalized MOFs.

Construction and isomeric transformation of polyoxometalates directed by 1,ω-bis(pyridinium)alkane templates

Ten novel inorganic–organic hybrid polyoxometalates, namely, [1,3-bis(pyridinium) propane]2[α-Mo8O26] (1), [1,4-bis(pyridinium)butane]2[1D-Mo8O26] (2), [1,5-bis(pyridinium)pentane]2[θ-Mo8O26] (3), [1,6-bis(pyridinium)hexane]2[1D-Mo8O26] (4), [1,7-bis(pyridinium)heptane]2[β-Mo8O26] (5), [1,8-bis(pyridinium)octane]2[θ-Mo8O26] (6), [1,9-bis(pyridinium)nonane]2[(α + β)-Mo8O26] (7), [1,10-bis(pyridinium)decane]2[β-Mo8O26] (8), [1,11-bis(pyridinium)undecane]2[β-Mo8O26] (9), [1,12-bis(pyridinium)dodecane]2[γ-Mo8O26] (10), (Scheme 1) were synthesized by cation templated self-assembly with octamolybdate anions under hydrothermal reaction conditions. Crystal data analysis revealed that these compounds were all composed of discrete organic cations and polyacid anions [Mo8O26]4− interacting by electrostatic and hydrogen bond interactions. Interestingly in these compounds the anion fraction could take on α-, β-, θ-, γ-[Mo8O26]4− 0D isomers or rare 1D- polymeric frameworks with a simple length modification of the alkane components. Moreover, these polyacid compounds had definite catalytic activities on the oxidation reaction of acetaldehyde to acetic acid and the relationship of structure/catalytic activities were initially demonstrated.

Three novel cation-templated metal thiocyanates with 1-2D polypseudorotaxane frameworks

Three novel cation-templated complexes, {(BPE)3[Ag4Br4(SCN)6]}n (1), {(DEBP) [Cu2(SCN)4]}n (2) and {(DIBP) [Cu2(SCN)4]}n (3) [BPE = 1, 2-bis (pyridinium) ethane; DEBP = 1, 1′-diethyl-4, 4′-bipyridinium dibromide; DIBP = 1, 1′-diisopentyl-4, 4′-bipyridinium], have been synthesized viaself-assembly reaction in solution. Complex 1 possesses a one-dimensional polyrotaxane architecture with the organic cation BPE trapped in it, whereas both compounds 2 and 3 are infinite 2D supramolecular polypseudorotaxane, linked by bridging thiocyanate groups. All compounds were further characterized with IR spectra, thermal analysis, ultraviolet and fluorescence properties.

Counteranion's effects on the structures of supramolecular silver coordination compounds of one asymmetric and one biting organic ligands

Reactions of one asymmetric ligand 1,6-dihydro-2-methyl-6-oxo-(3,4′-bipyridine)-5-carbonitrile (L1) with AgX (X = NO3−, BF4−, AsF6−, SbF6−) afforded two 1-D interpenetrating coordination polymers {[Ag2(L1)3]2·(CH3OH)3·(AsF6)4}n (1) and {[Ag2(L1)3]2·(SbF6)4}n (2), and two monomers [Ag(L1)2]·(NO3) (3) and [Ag(L1)2]·(CH3OH) (BF4) (4). The structural similarity between compounds 1 and 2, and the structural difference between compounds 1 and 2 and compounds 3 and 4 give evidences that the sizes of counteranions with the same polyhedron sometimes can not affect the supramolecular structures, but the polyhedra of counteranions sometimes can. The self-assembly of one angular ligand 1,3,4-thiadiazole-2,5-di-2-pyridyl (L2) with AgX (X = BF4−, ClO4−, PF6−, AsF6−, NO3−, SbF6−) produced five di-nuclear and one mono-nuclear silver(I) coordination compounds. In the three dinuclear compounds [Ag2(L2)2](BF4)2 (5), [Ag2(L2)2](ClO4)2 (6), and [Ag2(L2)2](PF6)2 (7), there are medium Ag–Ag interactions between two adjacent dimers, leading to a 1-D supramolecular chain. In the other two dimers [Ag2(L2)2](AsF6)2 (8) and [Ag2(L2)2](NO3)2(CH3OH) (9), however, no Ag–Ag interactions were found. When changing counteranion to the very large one SbF6−, the silver complex of L2 is a monomer [Ag(L2)2](SbF6) (10). The supramolecular structural diversity of compounds 7, 8, and 10, resulting from the volume changes of the octahedral counteranions shows that the sizes of counteranions with the same polyhedron can sometimes affect the supramolecular structures.

Crystal structures and photocatalytic properties of two novel iodoplumbate hybrids templated by multivalent organic cations

Two novel complexes based on multivalent organic cations and PbI2, {(tbp)2[Pb3I12]}n (1) (tbp = 1,3,5-tri(N-pyridinium methyl)benzene tribromide) and {(tbpm)[Pb3I9]·H2O}n (2) (tbpm = 1,3,5-tri(4-methylpyridiniummethyl) benzene tribromide), have been synthesized and characterized by X-ray diffractometry. Compound 1 has a trinuclear structure and compound 2 presents a new 1D iodoplumbate. Photochemical studies reveal the good photocatalytic performances of the two iodoplumbate hybrids. Furthermore, the side chains effect on the fabrication of the iodoplumbate and the photocatalytic performances was also investigated.

External template-assisted self-assembly: design and synthesis of the [MoOS3Cu3]+ based supramolecular polymeric clusters

Four novel heterothiometallic cluster polymers based on a [MoOS3Cu3] unit have been synthesized by the solution self-assembly of 4,4′-bipy (4,4′-bipy = bpy) with [NH4]2MoS2O2 and CuX (X = I, Br, or SCN) in the presence of different organic cation-templates [DMI]·I, [C6(Mim)2]·Br2, [C3(Mim)2]·Br2, and [BBP]·Br2: Compounds {[MoOS3Cu3I(μ-bpy)2.5]·2.5DMF}∞ (1), {[MoOS3Cu3I(μ-bpy)2.5] ·DMF}∞ (2), and {[MoOS3Cu3Br(μ-bpy)2.5]·2.5DMF}∞ (3) are isomorphous neutral 3D 4-fold interpenetrating architectures with a (6, 4) node, while polymer [MoOS3Cu3(NCS)(μ-bpy)2.5]∞ (4) is a 3D architecture with a (64 82) net displaying self-interpenetrating features. All of them have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and UV-vis. The results may provide fascinating insights into the template effect on the construction of the cluster-based coordination polymers.

Self-assembly, Crystal Structure and Fluorescent Property of a Coordination Polymer [(Cu4I6)(BPE)]n

A novel coordination polymer [(Cu 4 I 6 )(BPE)]n(BPE = 1, 2-bis(pyridinium) ethane dication) is obtained and characterized by X-ray crystallography and IR spectroscopy. The complex crystallizes in monoclinic system, space group C2(1)/c with cell parameters of a = 16.5429(19) Å, b = 10.0645(12) Å, c = 11.7139(13) Å, α = 90.00°, β = 99.0910(10)°, γ = 90.00°. In the polymeric framework, [Cu 4 I 6 ]n dimers are bridged together by the two μ 2 -I ligands to constitute an infinite 1D chain with the organic dication BPE trapped in it. Photoluminescence investigation of the complex reveals that a red shift of 67 nm for the complex takes place, compared with the organic dication.