Syntheses, Crystal Structures And Properties Of Cu(Ⅰ) Complexes Containing Brdmpzm Or Phpzm

In the past decades, much attention has been devoted to metal coordination complexes with poly(pyrazolyl)alkanes ligands because of their structural diversity, and their potential applications in catalysis, optics and magnetics. We deliberately selected bis(4-bromo-3,5-dimethylpyrazol-1-yl)methane (brdmpzm) and bis(4-phenyl-1H-pyrazol-1-yl)methane (phpzm) as ligands, to react with CuX (X = Cl, Br, I, CN, SCN), resulting in the formation of seven coordination polymers [Cu(μ-X)(brdmpzm)]n (X = Cl (1), Br (2), I (3), CN (4)), [Cu(μ-Br)(μ-phpzm)]n (5), [{Cu(μ-SCN)}2(μ-phpzm)]n (6) and [Cu(μ-CN)(phpzm)]n (7). In the presence of NaOH, reaction of CuI with 5-benzyl-4,6-dimethylpyrimidine-2-thiol (bzdmpymtH) resulted in the formation of complex [Cu(bzdmpymt)]6 (8). These complexes were characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction analysis. The luminescence properties of these complexes at ambient temperature were also investigated.X-ray analysis revealed that 1~3 have a 1D split-stair chain derived from connecting [Cu(brdmpzm)] fragments viaμ-X bridges. Each Cu is tetrahedrally coordinated by twoμ-X atoms and two N atoms of one brdmpzm ligand. Compounds 4 and 7 consists of a zigzag chain formed by linking [Cu(brdmpzm)] (4) or [Cu(phpzm)] (7) fragments viaμ-CN bridges. In 4 or 7, each Cu atom adopts a distorted tetrahedral coordination geometry, coordinated by two N atoms of ligand, one N atom and one C atom from two bridging CN- groups. Compounds 5 and 6 possesses two-dimensional networks in which split-stair [Cu(μ-Br)]n chains (5) or staircase-like [{Cu(μ-SCN)}2]n double chains (6) are linked byμ-phpzm bridges. Each Cu atom in 5 is coordinated by two Br atoms and two N atoms of two phpzm ligands, forming a distorted tetrahedral coordination geometry. In 6, each Cu is tetrahedrally coordinated by one N atom of phpzm, one N atom of SCN, and two S atom of SCN. The formation of different structures in 1-7 showed that the substituent groups on the pyrazolyl ring may exert great impact on the structures of the resulting adducts. In 5 and 6, the phpzm ligand takesμ-η1:η1 coordination mode to link two Cu(I) atoms, while each brdmpzm or phpzm in 1-4 and 7 chelates at each Cu atom. In 8, six Cu(I) atoms are held together by six bzdmpymt ligands through N and S atoms to form a water-wheel-shaped structure. Each Cu atom is coordinated by two S atoms from two bzdmpymt ligands and one N atom from the third bzdmpymt ligand, giving a trigonal planar coordination geometry. In 9·2CH3OH, each Cu atom is coordinated by two O and two N atoms, forming a distorted tetrahedral coordination geometry. The Cu-N and Cu-O distances are 1.984 (?), 2.005 (?), respectively.