Reactions　among　Cu(ClO4)2　·　6H2O,　Cu(acac)2/VO(acac)2　and　3-methoxysalicylaldehyde　Picoloylhydrazone　in　different　solvents　give　three　complexes,　[Cu2L(acac)(H2O)2]ClO4　(1),　[Cu4L2(acac)2(py)2](ClO4)2　(2)　and　(VO2)2L2Cu2(acac)2　(3)　(acac　=　acetyl　acetonate　and　py　=　pyridine).　There　is　an　extended　2D　structure　in　complex　1　constructed　by　hydrogen　bonds　between　the　binuclear　complex　cation　and　the　ClO4-　anion,　and　an　extended　1D　structure　in　complex　2　constructed　by　weak　π⋯π　stacking　interactions　between　neighboring　cyclic　tetranuclear　complex　molecules.　Complex　3　is　the　first　oxovanadium-copper　complex　with　a　bridging　oxo　oxygen　atom　between　the　V　atom　and　the　Cu　atom.　The　solid-state　photoluminescent　properties　of　the　three　title　complexes　have　been　studied.　There　is　an　antiferromagnetic　interaction　in　1.　©　2007　Elsevier　Ltd.　All　rights　reserved.