Reaction of transition metal formate M(HCOO)(2).2H2O (M = Mn, Co, Ni) with 4,4'-bpy (4,4-bipyridine) has led to four new compounds with the formula M(HCOO)2(4,4'-bpy).nH2O (M = Mn, Co (1.Mn, 2.Co), n = 0; M = Co, Ni (3.Co, 4.Ni), n = 5). Compounds 1.Mn and 2.Co are isomorphous and crystallized in the tetragonal crystal system with the chiral space group P4(1)2(1)2. They are of three-dimensional diamondoid structure connected by anti-anti formate with 4,4'-bpy in the cavities of the framework reinforcing the intermetallic connections; the diamond-like net was observed also in their azide analogue (Mn(N3)2(4,4'-bpy)). Compounds 3.Co and 4.Ni are isomorphous also but crystallized in the monoclinic crystal system with the space group Cc. Both structures are uninterpenetrated 3D "CdSO4" type with big channels, constructed by anti-anti formate and 4,4'-bpy. This type of net was not observed in their azide analogue. Residing in the channels, water molecules form a new type of 1D tape constructed by vertex-sharing cyclic pentamers. Magnetic measurements were performed on all of these four compounds. 1.Mn and 2.Co are weak ferromagnets with the critical temperature Tc = 5.3 and 7.4 K, respectively. 3.Co is an antiferromagnet with Neel temperature TN = 3.0 K, and 4.Ni is a weak ferromagnet below 20 K. Hysteresis loop can be observed for 2.Co and 4.Ni at 1.8 K. As an analogue of azide, formate can be used to construct molecular architectures, which structurally and magnetically have great similarities to and also differences from those of azide. This offers a promising method for the design of new molecular architectures with formate. 相似文献
Self-assemblies of amphiphilic molecules are proposed to play a ubiquitous role at the early stages of evolution in the formation of primitive biopolymers. [1] As regard to the significance of N-phosphoryl amino acids as a model for the co-evolution of protein and nucleic acids at the prebiotic stage, [2] amphiphilic N-phosphoryl amino acids with two hydrophobic tails were synthesized. [3] 相似文献
In this study, we developed an efficient Ir-catalyzed cascade umpolung allylation/2-aza-Cope rearrangement of tertiary α-trifluoromethyl α-amino acid derivatives for the preparation of a variety of quaternary α-trifluoromethyl α-amino acids in high yields with excellent enantioselectivities. The umpolung reactivity empowered by the activation of the key isatin-ketoimine moiety obviates the intractable enantioselectivity control in Pd-catalyzed asymmetric linear α-allylation. In combination with quasi parallel kinetic resolution or kinetic resolution, the generality of this method is further demonstrated by the first preparation of enantioenriched quaternary trifluoromethyl β-, γ-, δ- and ε-amino acid derivatives.In this study, we developed an efficient Ir-catalyzed cascade umpolung allylation/2-aza-Cope rearrangement for the preparation of a variety of quaternary trifluoromethyl α-ε-amino acids in high yields with excellent enantioselectivities.相似文献
The synthesis, structures, and magnetic properties of four cyano-bridged M(II)Ru(III)2 compounds prepared from the paramagnetic Ru(III) building blocks, trans-[Ru(salen)(CN)2]- 1 [H2salen = N,N'-ethylenebis(salicylideneimine)] and trans-[Ru(acac)2(CN)2]- (Hacac = acetylacetone), are described. Compound 2, {Mn(CH3OH)4[Ru(salen)(CN)2]2}.6CH3OH.2H2O, is a trinuclear complex that exhibits antiferromagnetic coupling between Mn(II) and Ru(III) centers. Compound 3, {Mn(H2O)2[Ru(salen)(CN)2]2.H2O}n, has a 2-D sheetlike structure that exhibits antiferromagnetic coupling between Mn and Ru, leading to ferrimagnetic-like behavior. Compound 4, {Ni(cyclam)[Ru(acac)2(CN)2]2}.2CH3OH.2H2O (cyclam = 1,4,8,11-tetraazacyclotetradecane), is a trinuclear complex that exhibits ferromagnetic coupling. Compound 5, {Co[Ru(acac)2(CN)2]2}n, has a 3-D diamond-like interpenetrating network that exhibits ferromagnetic ordering below 4.6 K. The density functional theory (DFT) method was used to calculate the molecular magnetic orbitals and the magnetic exchange interaction between Ru(III) and M(II) (Mn(II), Ni(II)) ions. 相似文献
Detecting the underlying performance of hydrated electrons and hydroxyl radicals in the cationic water cluster can greatly help to understand the inter reaction mechanism in the liquid water and aqueous solutions. Based on our previous (H2O)10+ research, we have paid attention to more problems of larger cationic clusters in this work, including the existence of hemibonded type, long-range correction functions, and hydrogen-bonded site analyses. The lower-energy structures of the cationic water cluster (H2O)12+ have been comprehensively explored, and more experienced functions are introduced to check the ground state and vibration spectrum. Unlike the configuration regularity of neutral (H2O)12 clusters and small cationic water clusters, those new-found structures for (H2O)12+ are inclined to adopt three dimension (3D) cage-like structures and the H2O-OH2 structure appears in the higher energy isomer. The calculation reveals that the lowest stable isomer is the 3D cage structure W14 predicted at MP2 level, which has not been reported yet. In the thermal simulation, structure transition from the cage-like to the ring-like occurs at T?>?≈256 K, and the two dimension (2D) ring-like structure occupies a dominant position at high temperature range. The infrared spectra explain that the difference of the spectra between the 2D net structures and 3D cage-structures is mainly caused by the weight fluctuation of single acceptor-single donor (AD), double acceptor-single donor (AAD), and single acceptor-double donor (ADD) sites in these isomers. This further gives a similarity relation between (H2O)12+ and H+(H2O)12 clusters in the shape of the network and spectral characteristics. By molecular orbitals and topological analysis, we find that the lone pair orbital on hydroxyl radical dominates the reactivity and stability of cationic system. The present research may be helpful for exploring the evolution law of the larger cationic water clusters in the future.