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The enantioselective transformation of ubiquitous C–H bonds into valuable C═O bonds offers an efficient synthetic approach to construct carbonyl functionalized molecules. However, the grand obstacl...

Creating ordered metal–organic frameworks (MOFs) membranes with a scalable fabrication for continuous and homogeneous nanoarchitecture represents a category of tunable and functionalizable heterogeneous catalysts. In this work, we demonstrate a facile synthetic strategy for controlling Cu-MOF (1) to fabricate highly oriented MOF membranes (1a) with good controllability in membranes thickness on the macroporous Ni foam as the supporting scaffold, which can promote the growth of the uniform and high-quality MOF-based membranes with the benefit of readily accessible active sites. Nanoscale crystals of 1b also can be acquired by using surfactants as templates without Ni foam as surface-supported. Furthermore, MOFs-based 1–1b have indicated to be efficient heterogeneous catalysts to promote cascade indole acylation–Nazarov cyclization for producing cyclopentenone[b]indoles skeletons. In particular, their unique membrane structure of 1a, containing ordered structure and molecular tunability, affords a well-defi...

We have obtained a suite of two-dimensional layered isostructural coordination polymers [M(pypa)2(H2O)2]n (M = Mn (1), Co (2), Ni (3), Cu (4), respectively), Hpypa = 1H-[3-(4-pyridy)pyrazole]propionic acid), and used them in catalyzing the homocoupling of aromatic halides. 3 and 4 exhibit preeminent catalytic performance on the homocoupling of aryl bromide or aryl iodide without byproducts, while 2 only promoted the homocoupling of aryl iodide. But 1 showed no catalytic activities for all tested aromatic halides. Subsequently, density functional theory was performed for the balanced geometry frameworks, net charges of atoms, and energy of frontier molecule orbits. By using this method we determined that the catalytic performance was influenced by central metal ions. For further improving the catalytic performance, polyvinylpyrrolidone or polyethylene glycol 20000 (PEG 20000) was used as surfactants to synthesize the microscales of 3’s (3a and 3b). 3a and 3b showed more preeminent catalytic activity than 3.

To seek the effect that condition of the complexes has on the manufacture of the biaryl compounds, seven Ni(II) complexes, namely, {[Ni(L)0.5(bpa)(H2O)]·2H2O}n (1), {[Ni2(L)(dpp)2(H2O)]·4H2O}n (2), {[Ni(L)0.5(pbmb)(H2O)]·H2O}n (3), {[Ni2(L)(bmp)2(H2O)]·7H2O}n (4), {[Ni(L)0.5(pbib)1.5]·2H2O}n (5), {[Ni2(L)(pbib)1.5]·3H2O}n (6), and [Ni(L)0.5(beb)2(H2O)]n (7) (bpa = 1,2-bis(4-pyridyl)ethane, dpp = 1,3-di(4-pyridyl)propane, pbmb = 1,1′-(1,3-propane)bis(2-methylbenzimidazole), bmp = 1,5-bis(2-methylbenzimidazol) pentane, pbib = 1,4-bis(imidazol-1-ylmethyl)benzene, beb = 1,4-bis(2-ethylbenzimidazol-1-ylmethyl)benzene), have been gained through hydro(solvo)thermal reactions of 5,5′-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid ligand (H4L) with Ni(II) metal ions under the regulation and control of six N-donor ligands. 3-fold interpenetrating complex 1 belongs to a (4,4)-connected 3D bbf net with a vertex symbol of (64·82)(66) topology. 3-fold interpenetrating complex 2 presents a (4,4,4)-connected 3D bbf net wit...

By the solvothermal reactions of a [1,1′:3′,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid (H4tpta) with transition metal ions, three novel polymeric complexes, namely {[Ni2(tpta)(H2O)3]·H2O}n (1), {[Co4(tpta)2(4,4′-bpy)(H2O)3]·3H2O}n (2), and {[Mn2(tpta)(H2O)2]·2H2O}n (3), have been isolated. The heterometallic clusters of these polymeric complexes are dimeric and tetrameric, respectively. 1 is composed of dimeric paddle wheel Ni(II) units to generate a 2D structure. In complexes 2 and 3, metal ions form tetrameric units that extend via all dimensions to give 3D structures with the Schlafli symbol of (43)(43)(46·618·84) and (46)(412·53·69·74), respectively. The results of variable temperature magnetization measurements (χmT-T and χm–1-T) show that complexes 1 and 2 display unusual ferromagnetic coupling via the M–O–C–O–M bridges, while complex 3 shows predominantly antiferromagnetic behavior. The M(H) curve of 1 does not saturate until the highest field of 80 kOe, indicating the significant magnetic anisot...

To systematically explore the impact of coordination complexes on the synthesis of 2-imidazoline and 1,4,5,6-tetrahydropyrimidine derivatives, five Co(II)/Mn(II)/Cu(II) architectures, formulated as {[Co(L)0.5(H2O)2]·CH3OH·H2O}n (1), {[Co(L)0.5(pbib)]·4H2O}n (2), [Mn(L)0.5(Hatz)0.5(H2O)]n (3), {[Cu(L)0.5(phen)2][Cu(L)0.5(phen)2]·0.5L·5H2O}n (4), and {[Cu(L)0.5(2,2′-bpy)(H2O)]·H2O}n (5) (H4L = 5,5′-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid, pbib = 1,4-bis(imidazol-1-ylmethyl)benzene, Hatz = 1H-1,2,4-triazol-3-amine, phen = 1,10-phenanthroline, 2,2′-bipy = 2,2′-bipyridine), have been designed and synthesized. 1 presents a (4,4)-connected 2D sql net with its point (Schlafli) symbol of (44·62)2, which is finally extended to a 3D supramolecular framework by π···π stacking interactions. 2 has a 3D (4,4)-connected new topology net with a point symbol of (86)2. 3 features a (4,4)-connected 3-fold interpenetrating 3D pts topology network with the Schlafli symbol (42·84)2. 4 possesses two binuclear molecules, and...

To systematically explore the effect of polynuclear complexes on photocatalytic degradation of the organic dyes, a series of coordination complexes containing CdII clusters, formulated as {[Cd3L2(H2O)5]·H2O}n (1), {[Cd3L2(hbmb)(H2O)2]·2.5H2O}n (2), {[Cd3L2(btbb)(H2O)2]·2EtOH·1.5H2O}n (3), and {[Cd6L4(bipy)2(H2O)6]·3H2O}n (4) (H3L = 3,4-bi(4-carboxyphenyl)-benzoic acid, hbmb = 1,1′-(1,6-hexane)bis(2-methylbenzimidazole), btbb = 1,4-bis(2-(4-thiazolyl)benzimidazole-1-ylmethyl)benzene, 4,4′-bipy = 4,4′-bipyridine), have been designed and synthesized. Complex 1 based on trinuclear CdII clusters exhibits a new (3,3,6)-connected 3D framework. 2 belongs to a (3,3,8,8)-connected tfz-d topology net with pillar-layered frameworks assembled by two kinds of trinuclear CdII clusters. 3 is a 3D pillar-layered framework, which features a (3,8)-connected tfz-d net based upon one kind of trinuclear CdII cluster. 4 presents a new 3D (3,6,10)-connected framework with dinuclear and tetranuclear clusters. The photocatalytic p...