| Clusters with special frameworks have the potential being one kind of NLO material.Among them,most clusters have homometallic atoms serving as junctions.Very few ones have been reported using heterometallic cluster cores as junctions.Since the structures of iron-molybdenum cofactor?FeMoco?in nitrogenase and carbon monoxide dehydrogenase/acetyl-CoA synthase?CODH/ACS?were determined,heterometallic Mo?W?-M'-S clusters?M'=Fe,Cu,Ag,Au,etc.?have attracted considerable interest.For years,our group has been engaged in constructing Mo?W?-Cu?Ag?-S clusters and exploring their sturctures and the third-order NLO properties in solution.This thesis mainly focuses on the assembly of new W-Cu-S clusters,the clear description of their structures with the proposed cluster modular construction?CMC?approach and their third-order NLO properties.Firstly,we proposed cluster modular construction?CMC?approach to assemble new W-Cu-S clusters with different structrues.Reactions of[Et4N][Tp*WS3]?Tp*=hydridotris?3,5-dimethylpyrazol-1-yl?borate??1?,[Et4N][Tp*WS3?CuCl?3]?2?,[Et4N][?Tp*WS3Cu3Cl?2??-Cl?2??4-Cl?]?3?or[Et4N][Tp*WS3?CuBr?3]?4?with[Cu?MeCN?4]?PF6?,isonitcotinic acid,CsCl,CuCN,CuCl,CuBr,AgOTf?trifluoromethanesulfonic silver?,AgNTf2?bistrifluoromethanesulfonimide silver?and bpp?bpp=1,3-di?4-pyridyl?propane?led to the formation of five new W-Cu-S clusters with high symmetrical structures including tetrahedron[?Tp*WS3Cu3?CN??2(?2-SO42-)0.5CN]2·CHCl3?5·CHCl3?,rectangle[Et4N]2[(Tp*WS3Cu3?CN?0.5)2??-Cl?2??4-Cl?]2?PF6?2?6?,[2]catenane[?Tp*WS3Cu3?2??3-Cl?2?bpp?3]2?OTf?4·2CHCl3?7·2CHCl3?,[2]catenane[?Tp*WS3Cu3?2??3-Cl?2?bpp?3]2?NTf2?4·2CHCl3?8·2CHCl3?and[2]catenane[(Tp*WS3Cu3Cl1.13Br0.87)2?bpp?3]2[(Tp*WS3Cu3Cl1.26Br0.74)2?bpp?3]2?NTf2?6?OTf?2?F3CSO2OOSO2CF3?·2CHCl3?9·2CHCl3?.Their crystal structures were determined by X-ray single-crystal diffraction,and further characterized by IR,UV-Vis and ESI-MS etc.We proposed the cluster modular construction?CMC?approach to facilitate the description of these W-Cu-S clusters with complicated structrues.The third-order NLO properties of 6-9 in solution were examined by Z-scan technique,and they all good third-order NLO responses.Secondly,during the above-mentioned assembly processes,several other W-Cu-S clusters including[?Tp*WS3?CuCl?3?Cs??-MeCN??MeCN?2]2?10?,[?Tp*WS3Cu3?2Cl??-Cl?2??4-Cl??MeCN?]?11?,[?Tp*WS3Cu3Cl?2?pz?5]?PF6?2?12,pz=pyrazine?,[?Tp*WS3?CuCl?3???6-Cl??Tp*WS3Cu3?ani?3?]?13,ani=aniline?and[Tp*WS3Cu3Cl??2-Cl??4,4'-bipy?]n?14?were also isolated.Their structures were also confirmed by X-ray single-crystal diffraction and further characterized by IR,UV-Vis and ESI-MS etc.The third-order NLO properties of 10-14 in solution were also examined by Z-scan technique.Among them,compounds 10,11 and 13 exhibited good third-order NLO responses. |
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