Reaction of AgNO 3 with one tetraphosphine ligand, 1,4- N , N , N ′, N ′-tetra(diphenylphosphanylmethyl) benzene diamine (dpppda), gave rise to a Ag(I)/tetraphosphine coordination polymer [Ag 4 (NO 3 ) 4 (dpppda)] n ( 1 ). Compound 1 has a one-dimensional (1D) chain structure in which the chair-like [Ag 4 (NO 3 ) 4 ] cores are linked by the dpppda ligands using a Z-shaped μ - η 2 : η 2 side-by-side mode. Compound 1 exhibited good catalytic activity towards the photodegradation of nitrobenzene (NB), paranitrophenol (PNP) and 2,4-dinitrophenol (2,4-DNP) in aqueous solution under UV light irradiation. The kinetics and the mechanism of such catalytic photodegradation reactions were also investigated. The present work provided some new insight into the design and preparation of new coordination polymers as catalyst for high-performance photodegradation of toxic and persistent organic species existed in industrial wastewaters.

One silver(I)/tetraphosphine coordination polymer showing good catalytic performance in the photodegradation of nitroaromatics in aqueous solution

Three new coordination polymers, [Ag4(H2bpz)4(SO4)2]·H2O (1), [Ag2(H2bpz)2(SO4)]·3H2O (2), and [Ag3(H2bpz)4](SO4)2/3(OH)5/3·4H2O (3) have been solvothermally synthesized with Ag2SO4 and flexible ligand 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (H2bpz) in different solvents and temperatures. Complex 1 is a 2-fold interpenetrated three-dimensional (3D) framework with an uncommon (3,5)-connected hms topology. Complex 2 is a structural isomer of 1 and shows a three-connected 2D ths net consisting of interesting 3-fold and 2-fold heterochiral helical chains. Complex 3 discloses a grid layer structure, containing heterochiral helical chains and an unusual meso-helix. More interestingly, three sets of layers in 3 stack in different directions, affording an unprecedented 2D + 2D + 2D → 3D polycatenating cationic framework with 1D + 3D porous systems. In 1–3, H2bpz exhibit exobidentate bridging fashions with wide-ranged interpyrazole tilting angles and changeable coordination configurations, such as cis and trans fash...

Solvent or temperature induced diverse coordination polymers of silver(I) sulfate and bipyrazole systems: syntheses, crystal structures, luminescence, and sorption properties.

Solvothermal reactions of LnCl3·6H2O (Ln = Nd, Eu, Yb) with equimolar amounts of 5,11,17,23-tetrakis[(m-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]arene (H4L) at 90 or 140 °C gave rise to a set of six lanthanide(III) coordination polymers {[Nd2ClL(HCOO)(DMF)3(H2O)]·0.5DMF·MeCN·1.5H2O}n (1), {[Ln2ClL(HCOO)(DMF)]·sol}n (2: Ln = Eu, sol =0.5MeCN·1.5H2O; 3: Ln = Yb, sol = 1.5H2O), and {[H3O][LnL(H2O)]·DMF·MeCN·H2O}n (4: Ln = Nd; 5: Ln = Eu; 6: Ln = Yb). Complexes 1–6 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Compounds 1–3 have two-dimensional (2D) networks in which [Nd6Cl4L2(DMF)12(H2O)2] units (1) or [Ln6Cl4L2(DMF)2] (Ln = Eu (2), Yb (3)) are interlinked by the carboxyl groups of formates. Compounds 4–6 exhibit 2-fold interpenetrating 2D networks in which each [Ln4L(H2O)4] “four-flier pinwheel” unit works as a planar eight-connecting node to connect its eight equivalents via four L ligands. The formation of 1–6 provided an interestin...

Temperature-Driven Assembly of Ln(III) (Ln = Nd, Eu, Yb) Coordination Polymers of a Flexible Azo Calix[4]arene Polycarboxylate Ligand

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.

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

Solvothermal reactions of HAuCl4·4H2O with a P–S hybrid ligand N,N-bis(diphenylphosphanylmethyl)-amino-thiocarbamide (dppatc) at 80 °C and 115 °C produced two Au–P–S complexes, [Au2(dppatc)2]Cl2 (1) and [Au2(dppmt)2]n (2) (dppmtH = (diphenylphosphino)methanethiol). 1 and 2 were characterized by elemental analyses, IR and UV-vis spectra, thermal-gravity analyses, powder X-ray diffraction and single crystal X-ray diffraction analyses. Compound 1 contains a dinuclear [Au2(dppatc)2]2+ dication, while 2 has a one-dimensional chain formed by Au⋯Au aurophilic interactions. Compounds 1 and 2 exhibited excellent catalytic activity toward the photodegradation of nitrobenzene, p-nitrophenol and 2,4-dinitrophenol in aqueous solutions. The degradation reactions followed the zero-order kinetic model, in which the three nitroaromatics could be converted into CO2 and H2O in 92–96% yields.

Syntheses and structures of two gold(I) coordination compounds derived from P–S hybrid ligands and their efficient catalytic performance in the photodegradation of nitroaromatics in water

Reactions of N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy) with K[Ag(CN)(2)], Ag(dca) (dca = dicyanamide), AgSCN, AgCl, AgBr or AgI gave rise to six [Ag(2)X(2)]-based (X = CN(-), dca, SCN(-), Cl(-), Br(-) and I(-)) compounds, [{Ag(2)(CN)(2)(dppmapy)}.0.5CHCl(3)](n) (1), [Ag(2)L(2)(dppmapy)(2)](n) (2: L = dca; 3: L = SCN), [{Ag(2)L(2)(dppmapy)(2)}.sol](n) (4: L = Cl, sol = 0.5MeOH.0.5CH(2)Cl(2); 5: L = Br, sol = 2CHCl(3)), and [Ag(2)I(2)(dppmapy)(4)].3MeOH (6). Complexes 1-6 were characterized by elemental analysis, IR, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction. Compound 1 has a one-dimensional (1D) spiral chain constructed by bridging the [(CN)Ag(mu-CN)Ag] fragments via dppmapy ligands. In 2, 3 and 4, each [Ag(2)X(2)] (X = dca, SCN, Cl) fragment is linked by dppmapy bridges to the other two equivalent ones to form a 1D chain containing 16-membered rings (2) or a 1D double chain containing 20-membered rings (3) or a 1D spiral chain containing 20-membered rings (4). Compound 5 possesses a two dimensional (2D) (4,4) network consisting of 36-membered metallomacrocycles in which each [Ag(2)Br(2)] fragment acts as a unique planar four-connecting node to link the other four equivalent ones via dppmapy bridges. Complex 6 has a [Ag(2)I(2)] unit with a pair of monodentate dppmapy ligands coordinated at each Ag center. The photoluminescent properties of 1-6 in the solid state at ambient temperature were also investigated.

Construction of [Ag2X2]-based complexes from reactions of Ag(I) salts with N-diphenylphosphanylmethyl-4-aminopyridine: isolation, structures, and luminescent properties

Ni-Ya Li

Papers

Construction of [Ag2X2]-based complexes from reactions of Ag(I) salts with N-diphenylphosphanylmethyl-4-aminopyridine: isolation, structures, and luminescent properties