Dai-Zhi Kuang

Syntheses, crystal structures and luminescence of zinc(II) and cadmium(II) complexes with 4′-substituted 2,2′:6′,2″-terpyridines

Four terpyridine coordination complexes, [Zn(meophtpy)2]·(ClO4)2·(H2O) (1), [Cd(meophtpy)2]·(ClO4)2 (2), [Zn(nh2phtpy)2]·(ClO4)2 (3), and [Cd(nh2phtpy)2]·(ClO4)2 (4) (meophtpy = 4′-(p-methoxylphenyl)-2,2′:6′,2″-terpyridine, nh2phtpy = 4′-aminophenyl-2,2′:6′,2″-terpyridine), were synthesized using the solvothermal method. These complexes have been characterized by IR spectra, elemental analyses, and X-ray diffraction. In all these complexes, the metal ions are coordinated by six nitrogens from two terpyridines. 3-D networks have been constructed by hydrogen bonds and π–π interactions. The luminescence of these four complexes has been investigated in the solid state at room temperature. Graphical abstract Four Zn(II) and Cd(II) complexes with two kinds of terpyridines have been synthesized and characterized. All these complexes are six N coordinated with two terpyridines. 3-D networks have been formed with hydrogen bonds and π–π interactions. The luminescence properties have been studied and all these ligands and complexes can be used as luminescence materials.

3-[4-(Dimethyl-amino)phen-yl]-1-(2-pyrrol-yl)prop-2-en-1-one.

The molecule of the title compound, C15H16N2O, is non-planar with a dihedral angle of 16.0 (1)° between the pyrrole and benzene rings. The ketone double-bond displays an s–cis conformation with an O=C—C=C torsion angle of 7.9 (3) and an intramolecular C—H⋯O hydrogen bond. In the crystal structure, adjacent molecules are paired through N—H⋯O hydrogen bonds into centrosymmetric dimers.

Syntheses, Crystal Structures and Biological Activity of the 1D Chain Benzyltin Complexes Based on 2-Oxo-Propionic Acid Benzoyl Hydrazone

Two new 1D Chain benzyltin complexes {[C6H4(O)C=N–N=C(Me)COO](CH3OH)(C6H5CH2)2Sn}n (1), {[C6H4(O)C–NH–N=C(Me)COO](C6H5CH2)3Sn}n (2) were synthesized by the reactions of 2-oxo-propionic acid benzoyl hydrazone with dibenzyltin dichloride or tribenzyltin chloride, respectively. The two complexes were characterized by FT-IR, 1H, 13C and 119Sn NMR spectra, elemental analysis, X-ray single crystal diffraction and TGA. In vitro antitumor activities of both complexes were evaluated by the 3-(4,5-dimethylthiazoly-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay against three human cancer cell lines (NCI-H460, HepG2, MCF7) and human cell line (HL7702). The 1 exhibited strong antitumor activity than 2, then it was expected after further chemical optimization of candidate compounds as anti-cancer drugs. The interaction between complexes and calf thymus DNA were studied by EB fluorescent probe, the interaction of 1 and 2 with calf thymus DNA were intercalation and electrostatic attraction.

Dichlorido(4′-ferrocenyl-2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)zinc acetonitrile monosolvate

The title complex, [FeZn(C5H5)Cl2(C20H14N3)]·CH3CN, is composed of one ZnII atom, one 4′-ferrocenyl-2,2′:6′,2′′-terpyridine (fctpy) ligand, two Cl atoms and one acetonitrile solvent molecule. The ZnII atom is five-coordinated in a trigonal–bipyramidal geometry by the tridentate chelating fctpy ligand and two Cl atoms.

(4′-Ferrocenyl-2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)(1,10-phenanthroline-κ2N,N′)copper(II) bis(perchlorate) acetonitrile solvate

The title complex, [CuFe(C5H5)(C20H14N3)(C12H8N2)](ClO4)2·C2H3N, consists of a mononuclear [Cu(C12H8N2)(C25H19FeN3)]2+ cation, two ClO4 − anions (one of which is disordered over two positions with equal occupancy) and one CH3CN solvent molecule. The CuII center has a distorted square-pyramidal coordination with three N atoms of the 4′-ferrocenyl-2,2′:6′,2′′- terpyridine (fctpy) ligand and one 1,10-phenanthroline (phen) N atom in the basal plane and a second phen N atom in the apical position with an axial distance of 2.254 (4) Å. The disordered ClO4 − anion is weakly coordinated to the CuII ion with a Cu—O distance of 2.766 (11) Å. The two cyclopentadienyl rings of the ferrocenyl group are almost eclipsed with a deviation of 4.7 (1) °, and are involved in intermolecular π–π interactions with the outer pyridyl rings of the fctpy ligands [centroid–centroid distance = 3.759 (2) Å.].

Hydrothermal syntheses, crystal structures, and magnetic properties of three manganese(II) complexes based on 4′-substituted 2,2′:6′,2″-terpyridine ligands

Three manganese coordination compounds, [Mn(Meophtpy)2] · 2ClO4 (Meophtpy = 4′-(4-methoxylphenyl)-2,2′:6′,2″-terpyridine) (I), [Mn(Ftpy)2](ClO4)2 (Ftpy = 4′-(2-furyl)-2,2′:6′,2″-terpyridine) (II) and [Mn(m-ClPhtpy)2] · 2ClO4 (m-ClPhtpy = 4′-(3-chlorophenyl)-2,2′:6′,2″-terpyridine) (III), have been synthesized by hydrothermal methods and characterized by IR, elemental analysis, powder and single-crystal X-ray diffraction analyses (CIF files CCDC nos. 945032 (I), 945033 (II), 945034 (III)). In most cases, the face-to-face interactions between pyridyl rings or phenyl rings facilitate the construction of 3D network in the crystal for all three complexes. The magnetic properties of three complexes have been investigated.

Syntheses and crystal structures of [Fe(m-NO2phtpy)2](ClO4)2 and [Fe(m-Clphtpy)2](ClO4)2 (m-NO2phtpy = 4′-(3-nitrophenyl)-2,2′:6′,2″-terpyridine and m-Clphtpy = 4′-(3-chlorophenyl)-2,2′:6′,2″-terpyridine)

Two iron compounds [Fe(m-NO2phtpy)2](ClO4)21 and [Fe(m-Clphtpy)2](ClO4)22 are synthesized and their structures are determined by single crystal X-ray diffraction. Crystal data for 1 are: orthorhombic, space group Pcca, a = 25.471(4) Å, b = 10.8182(18) Å, c = 14.682(2) Å, Z = 4. Crystal data for 2 are: orthorhombic, space group Pnna, a = 14.521(2) Å, b = 23.980(4) Å, c = 23.142(4) Å, and Z = 8. The iron atoms are coordinated by six N atoms from two terpyridines in both compounds. These two compounds are all linked by hydrogen bonds with C as donor and O as acceptor into a 3D network for 1 and a 2D network for 2. If viewed along the c direction in 1 and the a direction in 2, both compounds show the ordered figure with terpyridine overlapped as a square and the phenyl rings overlapped as a rectangle or a square.

Poly[[tetra-aquatetrakis-[μ(3)-5-(pyridine-4-carboxamido)-isophthalato]cobalt(II)digadolinium(III)] tetra-hydrate].

In the centrosymmetric polymeric title compound, {[CoGd2(C14H8N2O5)4(H2O)4]·4H2O}n, the GdIII cation is coordinated by one water molecule and four pyridine-4-carboxamidoisophthalate (L) anions in a distorted square-antiprismatic arrangement, while the CoII cation, located on an inversion center, is coordinated by two pyridyl-N atoms, two carboxylate-O atoms and two water molecules in a distorted octahedral geometry. The asymmetric unit contains two anionic L ligands: one bridges two Gd cations and one Co cation through two carboxyl groups and one pyridine-N atom; the other bridges two Gd cations and one Co cation through two carboxyl groups and the uncoordinated pyridine-N atom is hydrogen-bonded to the adjacent coordinated water molecule. Extensive O—H⋯O and N—H⋯O hydrogen bonds are present in the crystal structure.

(4′-Ferrocenyl-2,2′:6′,2′′-terpyridine-κ3N1,N1′,N1′′)(1,10-phenanthroline-κ2N,N′)zinc(II) bis­(perchlorate) acetonitrile monosolvate

In the title complex, [FeZn(C5H5)(C20H14N3)(C12H8N2)](ClO4)2·CH3CN, the ZnII atom is five-coordinated by a tridentate chelating 4′-ferrocenyl-2,2′:6′,2′′-terpyridine (fctpy) ligand and a bidentate chelating 1,10-phenanthroline (phen) ligand in a distorted square-pyramidal environment with a phen N atom located at the apical position [Zn—N = 2.259 (4) Å]. The terpyridyl motif in each fctpy ligand is coplanar, but the cyclopentadienyl ring is twisted by 9.5 (2)° out of coplanarity with each central pyridine. The two cyclopentadienyl rings of the ferrocenyl group are almost eclipsed with a deviation of 4.5 (1)°. In addition, intermolecular π–π interactions [centroid–centroid distance 3.753 (2) Å] are present between the cyclopentadienyl and outer pyridyl rings of the fctpy ligands. One of the perchlorate anions is equally disordered over two positions.

Syntheses, crystal structures and biological activity of the dialkytin complexes based on 2-oxo-3-phenylpropionic acid salicyloylhydrazone

Abstract Three new dialkytin complexes, {[o-OH–C6H4(O)C=N–N=C(CH2Ph)COO](n-Bu2Sn)}n (1), {[o-OH–C6H4(O)C=N–N=C(CH2Ph)COO](MeOH)(p-MeC6H5CH2)2Sn}2 (2), and {[o-OH–C6H4(O)C=N–N=C(CH2Ph)COO](EtOH)(C6H5CH2)2Sn}2 (3), were synthesized by reactions of 2-oxo-3-phenylpropionic acid salicyloylhydrazone with the corresponding diorganotin(IV) complex, respectively. All the complexes were characterized by IR, 1H, 13C, 119Sn NMR spectra, elemental analysis, X-ray single crystal diffraction and TGA. For in vitro antitumor activities, complexes were evaluated by the MTT assay against three human cancer cell lines (NCI-H460, HepG2 and MCF7) and human cell line (HL7702). The results showed that 1 may be a better potential candidate for further chemical optimization and cancer therapy than 2 and 3. The interactions between the complexes and calf thymus DNA were studied; the interaction of 1 with calf thymus DNA was intercalation, 2 and 3 were intercalation and electrostatic binding.