Construction And Properties Of W/Cu/S-based Inorganic-organic Hybrid Materials

Heterothiometallic Mo(W)/Cu/S clusters are of importance not only for theirsynthesis and structure interests, but also for their potential applications in biologicalsystems and optoelectronic materials. In the past decades, we have chose the reactiveproducts of thiometallate anions [ME_xS_4-x]^2-,[Cp^*MS₃]-(M=Mo, W; E=O, S; x=0-3)with copper(I) complexes as precursor clusters. These precursors react with bridgingligands to form1D,2D or3D cluster-based supramolecules. Compared with precursorclusters, some resulting coordination polymers show enhanced the third-order nonlinearoptical (NLO) properties, but due to poor solubility, the properties of many compoundscan't be investigated in solution. In this thesis, we deliberately chose[Et₄N][Tp*W(μ₃-S)₃(CuCl)₃](1) as a precursor cluster, which has better solubility inorganic solvents, to react with different ligands and third-order nonlinear opticalproperties of some compounds were also investigated. The main results were brieflysummarized as follows:1Solvothermal reactions of [Et₄N][Tp*WS₃(CuCl)₃](1) with CuCN andKCu(CN)₂respectively afforded two [Tp*WS₃Cu₃]-based coordination polymers[Tp*WS₃Cu₃(μ₃-DMF){Cu(CN)3}]₂(2) and K[Tp*WS₃Cu₃(μ₃-DMF){Cu₂(CN)4.5}]₂(3).The third-order NLO and PL responses of1were activated and greatly amplifiedthrough its assembly via the [Cu(CN)3]₂-and [Cu4(CN)9]5-species in2and3.2Reactions of [Et₄N][Tp*WS₃(CuCl)₃](1) with CuCN in different solvents andconditions formed six cluster-based polymers: the reactive precipitations of1and CuCNin DMF/acetonitrile were recrystallized respectively in pyridine or aniline to get[Tp*W(μ₃-S)(μ-S)₂Cu₂(μ-CN)₂Cu(py)₃]·1.5py (4·1.5py) and[Tp*W(μ₃-S)₃Cu₃(μ₃-DMF)(μ-CN)3Cu]·4aniline (5·4aniline). Reactions of1with CuCNin the mixed solvent of DMF/acetonitrile/toluene or DMF/acetonitrile/aniline insolvothermal conditions to form [Tp*W(μ₃-S)₃Cu₃(μ₃-DMF)(μ-CN)₃Cu]·3DMF·MeCN(6·3DMF·MeCN) and [Tp*W(μ₃-S)₃Cu₃(μ₃-DMF)(μ-CN)₃Cu]·2aniline (7·2aniline), respectively. At room temperature,1react with CuCN in DMF/acetonitrile/pyridine orDMF/acetonitrile/α-tolunitrile mixed solvent to obtain[Tp*W(μ₃-S)₃Cu₃(μ₃-DMF)(μ-CN)3Cupy]·DMF (8·DMF) and[Tp*W(μ₃-S)₃Cu₃(μ₃-DMF)(μ-CN)3Cu(α-tolunitrile)]·2MeCN (9·2MeCN). Reactions of[Et4N][Tp*WS3(CuCl)3](1) with CuCN and tpt(2,4,6-tri(4-pyridyl)-1,3,5-triazine)afforded1D supermolecular polymer3{Tp*W(μ₃-S)₃Cu₃(μ₃-MeCN)(μ-CN)3Cu}tpt]·6MeCN (10·6MeCN).3Reactions of the precursor cluster1with2equiv of AgSCN produced one1D[Tp*W(μ₃-S)₃Cu₃]-based coordination polymer[Tp*W(μ₃-S)₃Cu2Cu(μ-SCN)(μ₃-SCN)]2·Et2O (11·Et2O) while analogous reactions of1with Nadca (dca=dicyanamide) formed one2D [Tp*W(μ₃-S)₃Cu₃]-based coordinationpolymer [Tp*W(μ₃-S)₃Cu₃(μ_1,5-dca)(μ_1(3),5-dca)]₂·CH₂Cl₂(12·CH₂Cl₂). Througheffective assemblise, the NLO properties of compounds11and12significantlyenhanced compared to the precursor cluster1.4Reaction of [Ni(acac)2(H2O)2](13) with sodium dicyanamide (dca) inDMF/acetone gave rise to [Ni(acac)₂Na₂(dca)₂(μ-DMF)₂]_n(14) while analogous reactionof13with Na(dca) in MeCN/MeOH formed [Ni(acac)₂Na(dca)(MeCN)]_n(15). Solventeffects may be attributed to the remarkable structural change from the2D layer of14tothe3D net of15. Magnetic studies revealed that14and15possess the ferromagneticinteractions between paramagnetic Ni(II) ions.