A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489（4）,b=14.234（5）,c=14.484（5）,α=82.848（4）,β=79.399（4）,γ=73.646（4）°,V=2421.2（13） 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F（000）=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I 2σ（Ⅰ）.In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.
Two new metal-organic complexes,{[Co2（bptc）（DPPZ）2（H2O）2]·H2O}n 1 and {[Co2（ccm）2（DPPZ）2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co（NO3）2·6H2O with chelating ligand dipyrido[3,2-a：2＇,3＇-c]phenazine（DPPZ） and the corresponding carboxylic acid,namely,3,3＇,4,4＇-benzophenonetetracarboxylic acid（H4bptc） or 2-carboxycinnamic acid（H2ccm）,respectively.The complexes were structurally characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra,and thermal gravimetry.1 presents unique chiral chain structures,which are further consolidated into three-dimensional supramolecular frameworks via noncovalent bonds,such as hydrogen bonding and π-π interactions.2 features infinite double-chain structures,which are connected by strong π-π interactions to result in three-dimensional supramolecular architectures.
High response organic ultraviolet photodetectors（UV-PDs） were demonstrated with 4,4＇,4”- tris[3-methyl-pheny（phenyl）amino]triphenylamine（m-MTDATA） and two Re（Ⅰ） complexes, （bathocuproine）- Re（CO）3CI（Re-BCP） and （bathophenanthroline）Re（CO）3Cl（Re-Bphen） to act as the electron donor and acceptor, re- spectively. UV-PDs have the configuration of indium tin oxide（ITO）/m-MTDATA（25 nm）/m-MTDATA：Re-complex （25-35 nm）/Re-complex（20 nm）/LiF（l nm）/Al（200 nm） with different blend layer thicknesses of 25, 30 and 35 nm. The optimized PD based on Re-Bphen offers a corrected-dark photocurrent up to 760μA/cm^2 at -10 V, corresponding to a response of 310 mA/W which is among the best values reported for organic UV-PDs. Excellent electron transport ability makes for such high photo-to-electron conversion.
LIU Chun-boWANG LongLIU MinLI Chuan-biLI Chun-meiCHE Guang-boSU Bin
