Two tricyanometallate precursors, (Bu4N)[(Tp4Bo)Fe(CN)3].H2O.2MeCN (1) and (Bu4N)[(pzTp)Fe(CN)3] (2) [Bu4N+ = tetrabutylammonium cation; Tp4Bo = tris(indazolyl)hydroborate; pzTp = tetrakis(pyrazolyl)borate], with a low-spin FeIII center have been synthesized and characterized. The reactions of 1 or 2 with [Cu(Me3tacn)(H2O)2](ClO4)2 (Me3tacn = N,N',N' '-trimethyl-1,4,7-triazacyclononane) afford two pentanuclear cyano-bridged clusters, [(Tp4Bo)2(Me3tacn)3Cu3Fe2(CN)6](ClO4)4.5H2O (3) and [(pzTp)2(Me3tacn)3Cu3Fe2(CN)6](ClO4)4.4H2O (4), respectively. Assembly reactions between 2 and [Ni(phen)(CH3OH)4](ClO4)2 (phen = 1,10-phenanthroline) or Zn(OAc)2.2H2O afford a molecular box [(pzTp)4(phen)4Ni4Fe4(CH3OH)4(CN)12](ClO4)4.4H2O (5) and a rectangular cluster [(pzTp)2Zn2Fe2(OAc)2(H2O)2(CN)6] (6). Their molecular structures were determined by single-crystal X-ray diffraction. In complexes 1 and 2, the central FeIII ions are coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp4Bo- or pzTp-. Both complexes 3 and 4 show a trigonal-bipyramidal geometry, in which [(L)Fe(CN)3]- units occupy the apical positions and are linked through cyanide to [Cu(Me3tacn)]2+ units situated in the equatorial plane. Complex 5 possesses a cubic arrangement of eight metal irons linked through edge-spanning cyanide bridges, while complex 6 shows Zn2Fe2(CN)4 rectangular structure, in which FeIII and ZnII ions are alternately bridged by the cyanide groups. Intramolecular ferromagnetic couplings are observed for complexes 3-5, and they have S = 5/2, 5/2, and 6 ground states and appreciable magnetic anisotropies with negative D values equal to -0.49, -2.39, and -0.39 cm-1, respectively.
Using the tricyano precursor, (Bu4N)[(Tp)Fe(CN)3] (Tp = Tris(pyrazolyl) hydroborate) (1), four new tetranuclear clusters, [(Tp)Fe(CN)3Cu(Tp)]2.2H2O (2), [(Tp)Fe(CN)3Cu(bpca)]2.4H2O (3) (bpca = bis(2-pyridylcarbonyl)amidate anion), [(Tp)Fe(CN)3Ni(tren)]2(ClO4)2.2H2O (4) (tren = tris(2-amino)ethylamine), and [(Tp)Fe(CN)3Ni(bipy)2]2[(Tp)Fe(CN)3]2.6H2O (5) (bipy = 2,2'-bipyridine), have been synthesized and structurally characterized. The four clusters possess similar square structures, where FeIII and MII (M = CuII or NiII) ions alternate at the rectangle corners. There exist intermolecular - stacking interactions through pyrazolyl groups of Tp- ligands in complexes 2 and 4, which lead to 1D chain structures. Complex 5 shows a 3D network structure through the coexistence of - stacking effects and hydrogen-bonding interactions. Magnetic studies show intramolecular ferromagnetic interactions in all four clusters. The exchange parameters are +11.91 and +1.38 cm(-1) for clusters 2 and 3, respectively, while uniaxial molecular anisotropy can be detected in complex 3 due to the distorted core in its molecular structure. Complex 4 has a ground state of S = 3 and shows SMM behavior with an effective energy barrier of U = 18.9 cm(-1). Unusual spin-glass-like dynamic relaxations are observed for complex 5.
Abstract-Inductive transfer learning and semi-supervised learning are two different branches of machine learning. The former tries to reuse knowledge in labeled out-of-domain instances while the later attempts to exploit the usefulness of unlabeled in-domain instances. In this paper, we bridge the two branches by pointing out that many semi-supervised learning methods can be extended for inductive transfer learning, if the step of labeling an unlabeled instance is replaced by re-weighting a diff-distribution instance. Based on this recognition, we develop a new transfer learning method, namely COITL, by extending the co-training method in semi-supervised learning. Experimental results reveal that COITL can achieve significantly higher generalization and robustness, compared with two stateof-the-art methods in inductive transfer learning.
An effective Pd-catalyzed hydrocarboxylation of aryl olefins with AcO and formic acid is described. A variety of 2- and 3-arylpropanoic acids can be regioselectively formed by the judicious choice of ligand without the use of toxic CO gas.
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