The luminescence dynamics of a polypyridyl ruthenium II [Ru(phen)2(ip)]2+ and 5,10,15,20-tetraphenylporphyrin (H2TPP) dyad have been measured by using time-resolved fluorescence spectroscopy. The transient luminescent spectra of the dyad show an ultrafast energy transfer within 300 ps after photoexcitation of the [Ru(phen)2(ip)]2+ at 453 nm. However, no energy transfer has been observed as the excitation wavelength is 400 nm, corresponding to the absorption peak of H2TPP. The origin of the energy transfer from [Ru(phen)2(ip)]2+ to H2TPP has been analyzed according to the Frster energy-transfer theory.
Two new ruthenium(Ⅱ) complexes, [Ru(btz)3](ClO4)2 (1) and [Ru(btz)(dppz)2](ClO4)2 (2) (btz = 4,4′-bithi-azole, dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysis, 1H NMR, ES-MS and X-ray crystallography. The DNA binding behaviors of two complexes have been studied by spectroscopic and viscosity measurements. The results suggest that complex 1 binds to CT-DNA via an electrostatic mode, while complex 2 via an intercalative mode. Under irradiation at 365 nm, both complexes were found to promote the cleavage of plasmid pBR 322 DNA from supercoiled form Ⅰ to nicked form Ⅱ. The mechanism studies reveal that singlet oxygen 1O2 and hydroxyl radical (OH-) play a significant role in the photocleavage process.
YU HuiJuan, HUANG ShuMei, KOU JunFeng, LI LvYing, JIA HaiNa, CHAO Hui & JI LiangNian MOE Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China
Three Ru(Ⅱ) complexes [Ru(bpy)2(1-IQTNH)](ClO4)2 (1), [Ru(bpy)2(2-QTNH)](ClO4)2 (2) and [Ru(bpy)2(3-IQTNH)](ClO4)2 (3) (bpy = 2,2′-bipyridine, 1-IQTNH = 6-(isoquinolin-1-yl)-1,3,5-triazine-2,4-diamine, 2-QTNH = 6-(quinolin-2-yl)-1,3,5-triazine-2,4-diamine, 3-IQTNH = 6-(isoquinolin-3-yl)-1,3,5-triazine-2,4-diamine) have been synthesized and characterized by elemental analysis, 1H NMR spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The electrochemical and spectroscopic properties of the complexes differ from those of [Ru(bpy)3]2+ owing to the structural differences between the ligands and their complexes.
CHEN Yu, XU WenChao, KOU JunFeng, WEI XuHui, YU BoLe, CHAO Hui & JI LiangNian MOE Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China
Three new cadmium or zinc arenedisulfonate complexes [Zn(bpp)2(L)]n 1, {[Cd(bpp)2(1,5-NDS)(H2O)2]·4H2O}n 2 and {[Cd(bpp)2(H2O)2]·(1,5-NDS)}n 3 (L = 4,4'-bis(2-sulfo- natostyryl)biphenyl, bpp = 1,3-di(4-pyri-dyl)propane and 1,5-NDS = 1,5-Naphthalenedisulfonate) have been synthesized from aqueous solution and structurally characterized by infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction. Crystal data for complex 1: space group P21/n, a = 10.559(3), b = 13.138(4), c = 17.623(5) , β = 100.852(3)o, V = 2400.9(12) 3, Z = 2, Dc = 1.351 g/cm3, F(000) = 1016, μ = 0.654 mm–1, the final R = 0.0412 and wR = 0.0994; Crystal data for complex 2: space group P1, a = 8.5642(19), b = 10.076(3), c = 12.114(3) , α = 81.623(7), β = 77.149(8), γ = 82.787(7)o, V = 1003.6(4) 3, Z = 1, Dc = 1.495 g/cm3, F(000) = 466, μ = 0.713 mm-1, the final R = 0.0241 and wR = 0.0713; Crystal data for complex 3: space group C2/c, a = 21.6024(15), b = 9.4608(5), c = 18.4656(11) , β = 107.359(3)o, V = 3602.0(4) ?3, Z = 4, Dc = 1.533 g/cm3, F(000) = 1704, μ = 0.780 mm–1, the final R = 0.0229 and wR = 0.0572. The X-ray single diffraction reveals that 1 exhibits a 3D metal-organic framework formed from 2D Zn(bpp)22+ networks connected by L in the third dimension; 2 and 3 possess 3D and 2D architectures constructed from 1D polymeric chains through H-bond. Complexes 1～3 display photoluminescent emissions at 452 and 335 nm, respectively.
The self-assembly reactions of [MOS3]2– (M = W, Mo) with CuS2COCH3 in DMF produced two novel dodecanuclear Mo(W)/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- (CuS2COCH3)3]·H2O (1: M = W; 2: M = Mo). Cluster 1 crystallizes in hexagonal, space group P-62c with a = 16.5612(3), b = 16.5612(3), c = 16.4660(5) , Z = 2, V = 3911.13(16) 3, Dc = 1.935 g/cm3, μ(MoKα) = 7.269 mm–1, F(000) = 2192, the final R = 0.0289 and wR = 0.0789 for 2425 observed reflections (I > 2σ(I)). Cluster 2 is isomorphous to 1 with similar crystal parameters. X-ray analysis reveals that both clusters consist of three incomplete cubane-like cluster units {MOS3Cu3S2COCH3}, which are linked together by two μ3-S atoms.
Solvothermal reaction of [WS4]2-with CuCN and trithiocyanuric acid(L1) in orga-nic solvents gave rise to a new W/Cu/S polymer with a 2D anionic network,namely [Et4N]2[WS4Cu3(C3N3S3H1.5)2](1).The anionic layer of 1 is constructed by the T-shaped {WS4Cu3} subunits as nodes and L1 as linkers and features a(4,4) topology.Both 1 and its isomorphous compound [Et4N]2[MoS4Cu3(C3N3S3H1.5)2](2) have been fully characterized by X-ray crystal analysis,IR and microanalyses.Compounds 1 and 2 show optical transitions with band gaps of 2.17 and 1.84 eV,respectively.
