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A pyridine–tricarboxylic acid, 4-(6-carboxy-pyridin-3-yl)-isophthalic acid (H3cpia), was used as a versatile building block to synthesize three novel coordination polymers under hydrothermal conditions and formulated as [Mn8(μ3-Hcpia)2 (μ6-cpia)4(Hbiim)2(H2O)6]n·6nH2O (1), [Cu3(μ4-cpia)2(bipy)2(H2O)2]n·4nH2O (2), and [Ni3(μ3-cpia)2(dpe)3(H2O)2]n·4nH2O (3). Three supporting ligands, 2,2′-biimidazole (H2biim), 2,2′-bipyridine (bipy), and 1,2-di(4-pyridyl)ethane (dpe), were used in the synthesis. The structures of the studied products 1–3 varied significantly, ranging from a 1D chain (2) to 2D sheets (1 and 3). Furthermore, these compounds were evaluated as heterogeneous catalysts for the Henry reaction, achieving high product yields under optimized conditions. In addition, we investigated various reaction parameters and substrate scopes, and assessed the feasibility of catalyst recycling. This thorough investigation’s results highlight the versatility of H3cpia as a tricarboxylate building block in the formation of functional coordination polymers.

A pyridine-tricarboxylic acid, 5-(3′,5′-dicarboxylphenyl)nicotinic acid (H3dpna), was employed as a adjustable block to assemble a series of coordination polymers under hydrothermal conditions. The seven new coordination polymers were formulated as [Co(μ3-Hdpna)(μ-dpey)]n·nH2O (1), [Zn4.5(μ6-dpna)3(phen)3]n (2), [Co1.5(μ6-dpna)(2,2′-bipy)]n (3), [Zn1.5(μ6-dpna)(2,2′-bipy)]n (4), [Co3(μ3-dpna)2(4,4′-bipy)2(H2O)8]n·2nH2O (5),[Co(bpb)2(H2O)4]n[Co2(μ3-dpna)2(H2O)4]n·3nH2O (6), and [Mn1.5(μ6-dpna)(μ-dpea)]n (7), wherein 1,2-di(4-pyridyl)ethylene (dpey), 1,10-phenanthroline (phen), 2,2′-bipyridine(2,2′-bipy),4,4′-bipyridine(4,4′-bipy),1,4-bis(pyrid-4-yl)benzene (bpb), and 1,2-di(4-pyridyl)ethane (dpea) were employed as auxiliary ligands. The structural variation of polymers 1–7 spans the range from a 2D sheet (1–4, 6, and 7) to a 3D metal–organic framework (MOF, 5). Polymers 1–7 were investigated as heterogeneous catalysts in the Knoevenagel condensation reaction, leading to high condensation product yields (up to 100%) under optimized conditions. Various reaction conditions, substrate scope, and catalyst recycling were also researched. This work broadens the application of H3dpna as a versatile tricarboxylate block for the fabrication of functional coordination polymers.

Three new products, [Cu2(μ3-dppa)(2,2′-bipy)2(H2O)]n·2nH2O (1), [Co4(μ4-dppa)2(phen)4(H2O)4]·2H2O (2), and [Co2(μ6-dppa)(μ-4,4′-bipy)(H2O)2]n·3nH2O (3) were synthesized using a hydrothermal method from Cu(II) and Co(II) metal(II) chlorides, 3-(3,4-dicarboxyphenoxy)phthalic acid (H4dppa), and different auxiliary ligands, namely 2,2′-bipyridine (2,2′-bipy),1,10-phenanthroline (phen), and 4,4′-bipyridine (4,4′-bipy). Products 1–3 were characterized by elemental analysis, FTIR, TGA, PXRD, SEM, and single-crystal X-ray crystallography. The structure of 1 features a 1D chain of the 2C1 topological type. Compound 2 shows a discrete tetrameric complex. Product 3 demonstrates a 3D metal–organic framework (MOF) with the new topology. Their structure and topology, thermal stability, and catalytic activity were studied. In particular, excellent catalytic activity was demonstrated for copper(II)-polymer 1 in the cyanosilylation reaction at 35 °C.

Three 2D coordination polymers, [Cu2(µ4-dpa)(bipy)2(H2O)]n∙6nH2O (1), [Mn2(µ6-dpa)(bipy)2]n (2), and [Zn2(µ4-dpa)(bipy)2(H2O)2]n·2nH2O (3), were prepared by a hydrothermal method using metal(II) chloride salts, 3-(2′,4′-dicarboxylphenoxy)phthalic acid (H4dpa) as a linker, as well as 2,2′-bipyridine (bipy) as a crystallization mediator. Compounds 1–3 were obtained as crystalline solids and fully characterized. The structures of 1–3 were established by single-crystal X-ray diffraction, revealing 2D metal-organic networks of sql, 3,6L66, and hcb topological types. Thermal stability and catalytic behavior of 1–3 were also studied. In particular, zinc(II) coordination polymer 3 functions as a highly active and recoverable heterogeneous catalyst in the mild cyanosilylation of benzaldehydes with trimethylsilyl cyanide to give cyanohydrin derivatives. The influence of various parameters was investigated, including a time of reaction, a loading of catalyst and its recycling, an effect of solvent type, and a substrate scope. As a result, up to 93% product yields were attained in a catalyst recoverable and reusable system when exploring 4-nitrobenzaldehyde as a model substrate. This study contributes to widening the types of multifunctional polycarboxylic acid linkers for the design of novel coordination polymers with notable applications in heterogeneous catalysis.

Two new cadmium(II)-based materials, featuring two-dimensional (2D) [Cd2(μ6-deta)(bpy)(H2O)]n (1) and three-dimensional (3D) [Cd2(μ5-deta)(bpy)2(H2O)]n (2) structures, were constructed by the hydrothermal method from 2,3′,4′,5-diphenyl ether tetracarboxylic acid (H4deta) as an unexplored linker in research on coordination polymers (CPs) and 2,2′-bipyridine (bpy) as a mediator of crystallization. Microcrystalline samples of 1 and 2 were analyzed by IR/PXRD/EA/TGA and X-ray diffraction using single crystals. Structures and topologies of CPs 1 and 2 were established, revealing a 4,6L45 topological layer in 1 and a 3,5T1 topological framework in 2. Structural differences for 1 and 2 are attributed to distinct molar ratios between Cd2+ and bpy during the hydrothermal synthesis. Luminescence and thermal behavior of the obtained materials were also investigated. The present work opens up the use of an unexplored 2,3′,4′,5-diphenyl ether tetracarboxylic acid as a versatile and flexible linker toward the generation of functional coordination polymer materials.

New iron(II) three-dimensional coordination polymer (3D CP), [Fe(µ3-Hcpna)2]n (1), was assembled under hydrothermal conditions from 5-(4’-carboxyphenoxy)nicotinic acid (H2cpna) as a trifunctional organic N,O-building block. This stable microcrystalline CP was characterized by standard methods for coordination compounds in the solid state (infrared spectroscopy, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffraction). Structure and topology of 1 were examined and permitted an identification of a 3,6-connected framework of the rtl topological type. In addition, compound 1 acts as effective catalyst precursor for oxidative functionalization of alkanes (propane and cyclic C5−C8 alkanes) under homogeneous catalysis conditions, namely for the oxidation of saturated hydrocarbons with H2O2/H+ system to produce ketones and alcohols, and for alkane carboxylation with CO/H2O/S2O82− system to obtain carboxylic acids. The influence of an acid promoter and substrate scope (propane and cyclic C5−C8 alkanes) were investigated.

Two new copper(II) coordination compounds, namely a 1D coordination polymer [Cu(µ-cpna)(phen)(H2O)]n (1) and a discrete tetracopper(II) derivative [Cu(phen)2(H2O)]2[Cu2(µ-Hdppa)2(Hdppa)2] (2), were hydrothermally synthesized from copper(II) chloride as a metal source, 5-(4-carboxyphenoxy)nicotinic acid (H2cpna) or 5-(3,4-dicarboxylphenyl)picolinic acid (H3dppa) as a principal building block, and 1,10-phenanthroline (phen) as a crystallization mediator. Compounds 1 and 2 were isolated as air-stable microcrystalline solids and fully characterized by elemental and thermogravimetric analyses, IR spectroscopy, powder and single-crystal X-ray diffraction. In the solid state, the structure of 1 discloses the linear interdigitated 1D coordination polymer chains with the 2C1 topology. The crystal structure of an ionic derivative 2 shows that the mono- and dicopper(II) units are extended into the intricate 1D hydrogen-bonded chains with the SP 1-periodic net (4,4)(0,2) topology. Thermal stability and catalytic properties of 1 and 2 were also investigated. In fact, both Cu derivatives act as efficient homogeneous catalysts (catalyst precursors) for the mild oxidation of cycloalkanes by hydrogen peroxide to give the corresponding alcohols and ketones; the substrate scope and the effects of type and amount of acid promoter as well as bond-, regio-, and stereo-selectivity features were investigated.

Two new three-dimensional (3D) coordination compounds, namely a lead(II) coordination polymer (CP) {[Pb3(µ5-cpta)(µ6-cpta)(phen)2]·2H2O}n (1) and a zinc(II) metal-organic framework (MOF) {[Zn2(µ4-cpta)(µ-OH)(µ-4,4′-bipy)]·6H2O}n (2), were hydrothermally assembled from 2-(5-carboxypyridin-2-yl)terephthalic acid (H3cpta) as an unexplored principal building block and aromatic N,N-donors as crystallization mediators. Both products were isolated as air-stable microcrystalline solids and were fully characterized by IR spectroscopy, elemental and thermogravimetric analysis, and powder and single-crystal X-ray diffraction. Structural and topological features of CP 1 and MOF 2 were analyzed in detail, allowing to identify a topologically unique 4,5,5,6-connected net in 1 or a very rare 4,4-connected net with the isx topology in 2. Thermal stability and solid-state luminescent behavior of 1 and 2 were also investigated. Apart from revealing a notable topological novelty, both compounds also represent the first structurally characterized Pb(II) and Zn(II) derivatives assembled from H3cpta, thus opening up the application of this unexplored pyridine-tricarboxylate block in the design of new metal-organic architectures.

Selected recent examples of coordination polymers (CPs) or metal-organic frameworks (MOFs) constructed from different multifunctional carboxylic acids with phenyl-pyridine or biphenyl cores have been discussed. Despite being still little explored in crystal engineering research, such types of semi-rigid, thermally stable, multifunctional and versatile carboxylic acid building blocks have become very promising toward the hydrothermal synthesis of metal-organic architectures possessing distinct structural features, topologies, and functional properties. Thus, the main aim of this mini-review has been to motivate further research toward the synthesis and application of coordination polymers assembled from polycarboxylic acids with phenyl-pyridine or biphenyl cores. The importance of different reaction parameters and hydrothermal conditions on the generation and structural types of CPs or MOFs has also been highlighted. The influence of the type of main di- or tricarboxylate ligand, nature of metal node, stoichiometry and molar ratio of reagents, temperature, and presence of auxiliary ligands or templates has been showcased. Selected examples of highly porous or luminescent CPs, compounds with unusual magnetic properties, and frameworks for selective sensing applications have been described.

Using 57 universities directly under the Ministry of Education of China from 2009 to 2017 as the research samples, the overall efficiency, technology research efficiency, result transformation efficiency and efficiency influencing factors of the transformation of scientific research results in universities were explored using the leader-follower model in two-stage network Data Envelopment Analysis (DEA) and Tobit regression model, respectively. It is found that: firstly, the overall low efficiency of the scientific research results is primarily caused by the low efficiency of the transformation stage, which is on a downward trend and has lower average efficiency than the technology research stage. The efficiency of the technology research stage is on an upward trend, while the efficiency of the transformation stage is on a downward trend. Secondly, the number of universities reaching DEA effective in results transformation stage is more than that of technology R&D stage; Thirdly, the overall efficiency and result transformation efficiency of “985” universities are better than those of non-“985” universities, but the efficiency of technology R&D is lower than that of non-“985” universities; Fourthly, regional economic strength, government’s financial investment, the quality of patents, the number of papers, and the other eight factors all have an impact on efficiency.

5-(6-Carboxypyridin-3-yl)isophthalic acid (H3L) was utilized as an almost unexplored multifunctional ligand to construct, under hydrothermal conditions, ten new coordination compounds, namely, [Cd(μ2-H2L)2]n (1), [Ni(HL)(H2biim)2] (2), [Mn(μ2-HL) (phen)(H2O)]2·2H2O (3), {[Mn3(μ4-L)2(H2O)6]·3H2O}n (4), {[Co3(μ5-L)2(H2O)6]·2H2O}n (5), {[Ni3(μ4-L)2(H2O)6]·2H2O}n (6), {[Zn3(μ5-L)2(H2O)4]·2H2O}n (7), {[Mn3(μ5-L)2(H2O)6]·4H2O}n (8), {[Co3(μ4-L)2(μ2-4,4′-bipy)(H2O)6]·2H2O}n (9), and {[Ni3(μ5-L)2(H2O)6]·2H2O}n (10), also using an optional auxiliary ligand selected from 2,2′-biimidazole (H2biim), 1,10-phenanthroline (phen), or 4,4′-bipyridine (4,4′-bipy). The obtained compounds 1-10 were analyzed by IR spectroscopy, thermogravimetric and elemental analysis, and single-crystal and powder X-ray diffraction. The structures of the products vary from 3D MOFs (metal-organic frameworks 5 and 7-10) to 2D CPs (coordination polymers 1, 4, and 6) as well as to a discrete 0D monomer 2 and a dimer 3. The latter two are extended by multiple hydrogen bonds into complex 3D supramolecular networks. This structural difference in 1-10 is directed by the kind of metal(II) center, the deprotonation degree of the principal H3L building block, and/or the kind of auxiliary ligand. Notably, an addition of 4,4′-bipy can tune the structures of MOFs 8-10 by the coordination or template effect. Topological classification of metal-organic and H-bonded underlying networks was performed, disclosing a variety of topological nets: sql (in 1), 3,10T3 (in 3), 3,4L83 (in 4 and 6), tcs (in 5, 8, and 10), 3,4,5T95 (in 7), and sra (in 9), as well as a topologically unique network in 2. The magnetic properties (for compounds 3-6, 8-10) and luminescent properties (for compounds 1, 7) were also investigated and discussed. In fact, compound 7 exhibits an intense violet emission in the solid state. Measurements of the magnetic susceptibility indicate interactions of an antiferromagnetic nature between the adjacent metal(II) centers in the compounds 3-6 and 8-10. The obtained products represent the first series of metal-organic compounds assembled from the H3L precursor, thus opening up its application as a new pyridine-tricarboxylate organic block for designing CPs or MOFs. [ABSTRACT FROM AUTHOR]