Thomas M. Marschner

Bio: Thomas M. Marschner is an academic researcher. The author has contributed to research in topics: Copper & Isostructural. The author has an hindex of 3, co-authored 5 publications receiving 86 citations.

Stable copper(i) complexes and methods related thereto

Abstract: There is disclosed stable copper(I) complexes and methods relating thereto. The stable copper(I) complexes comprise a copper(I) ion complexed by a multi-dentate ligand which favors the +1 oxidation state for copper. Methods of this invention include the use of the stable copper(I) complexes as wound healing agents, anti-oxidative agents, anti-inflammatory agents, lipid modulating agents, signal transduction modulating agents, hair growth agents, and anti-viral agents. Exemplary stable copper(I) complexes include neocuproine copper(I) and bathocuproine disulfonic acid copper(I).

Stable copper(i) complexes as active therapeutic substances

Abstract: There is disclosed stable Copper(I) complexes and methods relating thereto. The stable Copper(I) complexes comprise a Copper(I) ion complexed by a multi-dentate ligand which favors the +1 oxidation state for copper. Uses of this invention include the use of the stable Copper(I) complexes as wound healing agents, anti-oxidative agents, anti-inflammatory agents, lipid modulating agents, signal transduction modulating agents, hair growth agents, and anti-viral agents. Uses of this invention also include inhibition of viral infection, as well as inhibiting transmission of sexually transmitted diseases. Exemplary stable Copper(I) complexes include neocuproine Copper(I) and bathocuproine disulfonic acid Copper(I).

Complexes cuivreux stables utilises comme substances a activite therapeutique

Abstract: Complexes cuivreux stables et procedes associes. Ces complexes cuivreux stables comprennent un ion cuivreux amene a former un complexe avec un ligand multidente qui favorise l'etat d'oxydation +1 du cuivre. Les applications de cette invention comprennent l'utilisation des complexes cuivreux stables comme agents de cicatrisation, agents antioxydants, agents anti-inflammatoires, agents de modulation lipidique, agents de modulation de transduction de signaux, agents de croissance capillaire et agents antiviraux. Ces utilisations comprennent egalement l'inhibition des infections virales, ainsi que de la transmission de maladies sexuellement transmissibles. Les complexes cuivreux stables cites a titre d'exemple sont le compose cuivreux/neocuproine et le compose cuivreux/acide bisulfonique bathocuproine.

Complexes stables de cuivre(i) et leur utilisation comme substances therapeutiques actives

Abstract: L'invention concerne des composes stables de cuivre(I) et des procedes affins. Les composes stables de cuivre(I) comprennent un ion de cuivre(I) associe a un ligand polydente qui favorise l'etat d'oxydation +1 du cuivre. Les procedes decrits comprennent l'utilisation des composes stables de cuivre(I) comme agents de guerison de blessures, agents antioxydants, agents anti-inflammatoires, modulateurs de lipides, modulateurs de la transduction de signaux, comme agents stimulant la pousse des cheveux et comme agents antiviraux. Des exemples de composes stables de cuivre(I) comprennent la neocupreine de cuivre(I) et l'acide disulfonique de bathocuproine de cuivre(I).

3D energetic metal-organic frameworks: synthesis and properties of high energy materials.

Abstract: Metal–organic frameworks (MOFs) have attracted great attention because of their intriguing molecular topologies and potential applications in chemical separation, gas storage, drug delivery, catalysis and chemical sensor technology. Particularly, MOFs could also be potential energetic materials because of their high densities and high heats of detonation. For example, Hope-Weeks and co-workers recently reported two hydrazine-perchlorate 1D MOFs [(Ni(NH2NH2)5(ClO4)2)n (NHP), and (Co(NH2NH2)5(ClO4)2)n (CHP)] with linear polymeric structures, which were regarded as possibly the most powerful metal-based energetic materials known to date, with heats of detonation comparable with that of hexanitrohexaazaisowutzitane (CL-20; about 1.5 kcalg ). Unfortunately, these coordination polymers were highly sensitive to impact deriving from their low rigidity characteristic of such linear polymeric structures, which makes practical use infeasible. In order to decrease the sensitivities, the same authors also used a hydrazine derivative (hydrazine-carboxylate) as the ligand to construct MOFs with 2D sheet structures [((Co2(N2H4)4(N2H3CO2)2)(ClO4)2·H2O)n (CHHP) and ((Zn2(N2H4)3(N2H3CO2)2)(ClO4)2·H2O)n (ZnHHP)], which showed a considerable reduction to the sensitivity, however, concomitantly their heats of detonation decreased (Figure 1). Despite these advances, current coordination frameworks are only limited to be a 1D or 2D structure. Compared with 1D linear and 2D layered structures, three-dimensional (3D) frameworks possess more complicated connection modes, which could further enhance structural reinforcement, hence improve the stabilities and energetic properties. A lot of 3D MOFs have been synthesized with interesting magnetic, catalytic, and luminescent properties, some of them incorporate a variety of energetic moities such as nitrate anions (NO3 ), perchlorate anions (ClO4 ) into the 3D frameworks. However, their potential applications as energetic materials have not been disclosed or discussed; relevant data about energetic properties are also missing in the literature. Additionally, both reported 1D and 2D energetic MOFs based on the perchlorate anions, have been scrutinized by the US Environmental Protection Agency (EPA) because they promote thyroid dysfunction and are teratogenic. Continuing our interest in finding new highly energetic, eco-friendly energetic materials, we explore the preparation of halogen-free energetic 3D MOFs, for which two polymers [Cu(atrz)3(NO3)2]n (1) and [Ag(atrz)1.5(NO3)]n (2) were designed by replacing the hydrazine ligand with 4,4’-azo1,2,4-triazole (atrz). Here, we chose to use atrz as a ligand for the following reasons: 1) as a nitrogen-rich heterocyclic backbone, atrz possesses a high nitrogen content (N%= Figure 1. Energetic MOFs with different topologies.

Synthesis, linear, and quadratic-nonlinear optical properties of octupolar D3 and D2d bipyridyl metal complexes

Abstract: A series of D 3 (Fe I I , Ru I I , Zn I I , Hg I I ) and D 2 d (Cu I , Ag I , Zn I I ) octupolar metal complexes featuring different functionalized bipyridyl ligands has been synthesized, and their thermal, linear (absorption and emission), and nonlinear optical (NLO) properties were determined. Their quadratic NLO susceptibilities were determined by harmonic light scattering at 1.91 μm, and the molecular hyperpolarizability (β 0 ) values are in the range of 200-657×10 - 3 0 esu for octahedral complexes and 70-157 x 10 - 3 0 esu for tetrahedral complexes. The octahedral zinc(n) complex 1e, which contains a 4,4'-oligophenylenevinylene-functionalized 2,2'-bipyridine, exhibits the highest quadratic hyperpolarizability ever reported for an octupolar derivative (λ m a x = 482 nm, β 1 . 9 1 (1e)=870 × 10 - 3 0 esu, β 0 (1e) =657 ×10 - 3 0 esu). Herein, we demonstrate that the optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and π linkers), and the nature of the metallic centers. For example, the length of the n-conjugated backbone, the Lewis acidity of the metal ion, and the increase of ligand-to-metal ratio result in a substantial enhancement of β. The contribution of the metal-to-ligand (MLCT) transition to the molecular hyperpolarizability is also discussed with respect to octahedral d 6 complexes (M=Fe, Ru).

Zinc(II) as a Versatile Template for the Design of Dipolar and Octupolar NLO-phores

Abstract: Thermally stable dipolar and octupolar (D2d, D3) NLO-phores are readily accessible by combining one, two, or three 4,4'-bis(dialkylaminostyryl)-[2,2']-bipyridyl ligands with zinc(II) salts. The off-resonant beta0 values point out the superiority of octupoles versus dipoles in terms of nonlinearity/transparency tradeoff. The octahedral tris(bipyridyl)zinc(II) complex exhibits a very large beta0 value (241 x 10-30 esu), which is the largest ever reported for octupolar molecules.

Self-assembly of coordination polymers from AgX (X = SbF(6)(-), PF(6)(-), and CF(3)SO(3)(-)) and oxadiazole-containing ligands.

Abstract: The coordination chemistry of the oxadiazole-containing rigid bidentate ligands 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L1), 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (L2), and 2,5-bis(3-aminophenyl)-1,3,4-oxadiazole (L3) with inorganic Ag(I) salts has been investigated. Four new coordination polymers (1, 2, 3, and 5) and one new bimetallic macrocyclic supramolecular complex (4) were synthesized from solution reactions of L1−L3 with inorganic Ag(I) salts, respectively. Compounds {[Ag(L1)]SbF6}n (1) (1, monoclinic, P21/c, a = 6.6846(4) A, b = 27.1113(15) A, c = 8.6802(5) A, β = 94.1080(10)°, Z = 4) and {[Ag(L1)]PF6}n (2) (2, monoclinic, P21/c, a = 6.6753(3) A, b = 27.2824(14) A, c = 8.2932(4) A, β = 94.6030(10)°, Z = 4) were obtained from the reactions of L1 with AgSbF6 and AgPF6 in a CH2Cl2/CH3OH mixed solvent system, respectively. Compounds 1 and 2 are isostructural and feature a novel two-dimensional zeolite-like net with two different individual rings. {[Ag(L2)]SbF6}n (3) (3, monoclinic, P21/c, a = 5.5677(3) A,...

Synthesis and characterization of new coordination polymers generated from oxadiazole-containing organic ligands and inorganic silver(I) salts.

Abstract: The coordination chemistry of the oxadiazole-containing rigid bidentate ligands 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L2) and 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole (L3) with inorganic Ag(I) salts has been investigated. Four new coordination polymers were prepared by solution reactions and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. [[Ag(L2)]SO3CF3]n (1)(triclinic, P1; a = 10.1231(7) A, b = 13.9340-(10) A, c = 13.9284(10) A, alpha = 116.7300(10) degrees, beta = 94.6890(10) degrees, gamma = 108.7540(10) degrees, Z = 4) was obtained by the combination of L2 with AgOTf in a CH2Cl2/CH3OH mixed-solvent system and features a unique one-dimensional elliptical macrocycle-containing chain motif. The approximate dimensions of the rings are ca. 22 x 11 A. [[Ag-(L2)](ClO4)(CH3OH)0.5(H2O)0.5]n (2) (triclinic, P1; a = 8.4894(5) A, b = 13.9092(8) A, c = 14.1596(8) A, alpha = 71.1410(10) degrees, beta = 77.3350(10) degrees, gamma = 81.5370(10) degrees, Z = 4) was generated from the reaction of L2 with AgClO4 in a H2O/CH3OH mixed-solvent system and consists of one-dimensional chains that are linked to each other by weak noncovalent pi-pi interactions into two-dimensional sheets. Uncoordinated ClO4-counterions and guest solvent molecules are located between the layers. [[Ag(L2)]NO3]n (3) was obtained by the combination of L2 with Ag(NO3)2 in a MeOH/H2O mixed-solvent system (triclinic, P1; a = 8.3155(6) A, b = 8.8521(6) A, c = 9.8070(7) A, alpha = 74.8420(10) degrees, beta = 77.2800(10) degrees, gamma = 68.6760(10) degrees, Z = 2). In the solid state, it exhibits an interesting pair of chains associated with C-H...O hydrogen bonds. [[Ag(L3)]SO3CF3]n (4) is generated from L3 and AgSO3CF3 in a CH2Cl2/MeOH mixed-solvent system and crystallizes in the unusual space group Pnnm, with a = 7.9341(4) A, b = 11.5500(5) A, c = 18.1157(8) A, and Z = 4. It adopts a novel three-dimensional structural motif in the solid state with big rhombic channels (ca. 15 x 10 A).