Syntheses,Structures And Properties Of [WS₄Cu₄]²⁺ Cluster-Based Coordination Polymers

Coordination polymers(CPs)are a class of inorganic-organic hybrid materials,which are assemblied by metal ions or clusters and organic ligands.They have diverse structures and broad applications in the fileds of drug transport,adsorption/separation,catalysis,sensing and so on.The heterometallic Mo(W)/Cu/S clusters possess multiple coordination sites and tunability,which are the powerful candidates for the preparation of CPs with unique structures and interesting physicochemical properties.In this thesis,the reactions of(NH4)2WS4,Cu(I)salts and some N-donor bridging ligands gave rise to six W/Cu/S cluster-based coordination polymers with different strucrures.Their structures,adsorption and third-order nonlinear optical(NLO)properties were also studied.The main contents are listed as follows:1.The interdiffusion reaction of(NH4)2WS4,CuCN and 1,2-bis(4-pyridyl)ethane(bpea)in DMF afforded a 3D porous CP {[WS4Cu4(μ-CN)2(bpea)2]·1.5DMF}n(1~1.5DMF).The connectivity in its structure is remarkably complicated,and its uncommon topology can be related to both the "lcs" and the diamond networks through CN-and bpea linkers.An intriguing aspect of this structure is the existence of isolated hexagonal channels that run in four distinct directions and allow this compound to serve as a functional host framework.The desolvated sample 1·des displays great iodine adsorption performance,meanwhile,the selective behavior of benzene/toluene adsorption of 1 ·des and the third-order NLO properties of 1 · 1.5 DMF were further investigated.2.The reactions of(NH4)2WS4 with CuCN,CuCN/1,2-bis(4-pyridyl)propane(bppa),Cu(MeCN)4PF6/bppa under differdnt reaction conditions afforded{[Et4N]2[WS4Cu4(μ-CN)2(μ-I)2]}n(2),{[WS4Cu4(μ-CN)2(bppa)2]}n(3)and{[WS4Cu4(bppa)4][PF6]2}n(4),respectively.Compounds 2 and 3 show 2D networks with a "sql" topology,while compound 4 possesses is a 3D porous network with rare"reo" topology.The third-order NLO responses of compounds 2,3 and 4 were gradually increased under the same measurment conditions.3.The reactions of(NH4)2WS4,Cu(MeCN)4PF6 and[PPh4][C(CN)3]without/with 1,2-bis(4-pyridine)(bipy)afforded {[WS4Cu4[μ-C(CN)3)]2[Py]5}·Py(5)and{{[WS4Cu4[ip-C(CN)3]2(bipy)2}·[PPh4][C(CN)3]}n(6),respectively.Compound 5 has a discrete WCu4 saddle-shaped structrue,while compound 6 holds a 2D layer network.The[C(CN)3]-anions in both compounds exhibit different coordination modes.