Jun-Ming Yue

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.

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.

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.

Syntheses, Crystal Structures, and Fluorescent Properties of Two Cation-induced Complexes: [(CdI4)(BPHX)] and [(Ag2I4)(BPHX)]

In this article, the solution-phase reaction of metal iodides with BPHX yields two novel organic-inorganic hybrid mental iodides [(CdI4)(BPHX)] and [(Ag2I4)(BPHX)] (BPHX = 1, 6-bis(pyridinium)hexane dication), which are characterized by X-ray crystallography and IR spectroscopy. The title mononuclear compound 1 crystallizes in monoclinic, space group P2(1)/c with a = 9.7050(17) Å, b = 15.426(3)Å, c = 15.992(3) Å, α = 90○, β = 105.653(4), γ = 90○. Compound 2 crystallizes in orthorhombic, space group Fddd with a = 13.8931(10) Å, b = 22.2368(16) Å, c = 31.330(3) Å, α = 90○, β = 90○, γ = 90○. In the anion, each monovalent Ag atom is tetrahedrally coordinated by four μ2-I atom ligands to constitute an infinite 1D (Ag2I2− 4) anion chain with the organic dication BPHX ([C16H22N2]2+) trapped in it.

Synthesis, Structure and Fluorescence Properties of a Coordination Polymer [Cu2(SCN)4(BPX)]n with 1D Ladder-Shaped Structure

A coordination polymer, [Cu2(SCN)4(BPX)]n(BPX = 1,4-bis(pyridinium) xylol) was synthesized and characterized by IR spectrum, fluorescence spectrum and single crystal X-ray diffraction. Crystal structure revealed that the title compound crystallized in monoclinic system with space group P2(1)/c, a = 5.7540(7)Å, b = 12.7203(15) Å, c = 17.598(2) Å, β = 94.9940(10)°. Two SCN−ions served as bridging ligands to link two Cu(I) ions, giving rise to an eight-member ring. Furthermore, copper atom and sulfur atom of the eight-member ring bonded sulfur atom and copper atom of adjacent eight-member ring through the formation of Cu-S to form a small four-member ring. Thus, innumerable eight-member rings alternately linked four-member rings each other to form an infinite one-dimensional ladder-shaped structure.

Syntheses, Crystal Structures, and Ultraviolet Properties of a Coordination Polymer [(Ag2I4)(EV)]n

In this article, we describe the synthesis of a novel one-dimensional (1D) polymer {[(Ag2I4)(EV)]} 1 by the reaction of metal iodides with ethyl viologen dibromide (EV), and the results are characterized by x-ray crystallography and infrared (IR) spectroscopy. The compound 1 crystallizes in a tetragonal space group P4(2)/mnm with a = 12.5133(8) Å, b = 12.5133(8) Å, c = 7.1014(9) Å, α = 90°, β = 90°, γ = 90°. In the anion, each monovalent Ag atom is tetrahedrally coordinated by four μ2-I atom ligands to constitute an infinite 1D (Ag2I4 2−) anion chain with the organic dication EV ([C14H18 N2]2+) trapped in it.

Reactivity of Polyiodide Toward 1,6-Bis(pyridinium)hexane (bphx): Syntheses and Structures of Two Organic-Inorganic Hybrid Clusters [(bphx)3·(Pb3I8Br4)] and [(bphx)2·(Cu4I8)]

In this article, the solution-phase reaction of metal iodides with bphx yields two novel organic-inorganic hybrid clusteric halides: [(bphx)3(Pb3I8Br4)] and [(bphx)2(Cu4I8)] (bphx = 1, 6-bis(pyridinium)hexane dication), which are characterized by X-ray crystallography and IR spectroscopy. The title trinuclear compound 1 crystallizes in Orthorhombic, space group Pccn with a = 29.077(10)Å, b = 12.030(4)Å, c = 19.749(7)Å. Tetranuclear oligomer 2 crystallizes in Monoclinic, space group P2(1)/c with a = 10.1630(5)Å, b = 15.2477(7)Å, c = 15.3222(7)Å. Both compounds exhibit unusual supramolecular organization wherein bphx dications reside in the channels as an efficient template. The complex 2 gives a fluorescence center at 567 nm under excitation at 450 nm, which is considered to mainly arise from the [Cu4I8]4− unit.

Synthesis and Structural Characterization of [(Pb6I22)(DMF)2(DPB)5] Directed by 1,1′-dipentyl-4,4′-bipyridinium Cation

In this study, one novel hexanuclear black crystals, namely [(Pb6I22)(DMF)2(DPB)5] were obtained from the solution-phase reaction of PbI2 in the present of excess KI directed by viologen-based linear templates in MeOH/DMF (DPB= 1,1′-dipentyl-4,4′-bipyridinium). Single-crystal X-ray diffraction analysis showed that this supramolecular compound crystallized in the monoclinic system with the space group P2(1)/c. Electrostatic interactions between the organic dications and inorganic moieties and hydrogen-bond interactions between structural unit are present and contribute to the crystal packing. IR spectroscopy was performed to further characterize title compound.

CCDC 628783: Experimental Crystal Structure Determination

Related Article: Yong-Zhen Qiao, Wen-Zhen Fu, Jun-Ming Yue, Xiu-Cun Liu, Yun-Yin Niu, Hong-Wei Hou|2012|CrystEngComm|14|3241|doi:10.1039/c2ce06687d