New Set of Multicomponent Crystals as Efficient Heterogeneous Catalysts for the Synthesis of Cyclic Carbonates.

Three new multicomponent crystals 1a-1c of Zn(II), Mn(II), and Co(II), respectively, were synthesized by the reaction of 2,6-bis(hydroxymethyl)pyridine, the respective metal salts, and sodium benzoate in a 1:1:2 ratio. One component of these multicomponent crystals 1a-1c is the dicationic 2,6-bis(hydroxymethyl)pyridine metal complex and the other component is the dianionic tetrabenzoate complex of the same metal. The complexes were fully characterized by single-crystal X-ray structure determination. The X-ray structure of these compounds 1a-1c reveals the formation of 1D supramolecular chain parallel to the crystallographic b axis via H-bonding interactions between the dicationic and dianionic parts of the respective compound. The Mn(II) (1b) and Co(II) (1c) complexes show antiferromagnetic coupling between the two associated metal centers via the H-bonding interaction pathway. All the three compounds 1a-1c were tested as heterogeneous catalytic systems for the successful conversion of epoxides to cyclic carbonates in solvent-free condition under approximately 10 bar of pressure of CO2 and temperature ranging between 60 and 80 °C along with tetrabutyl ammonium bromide acting as a cocatalyst. All the three compounds 1a-1c were found to have turnover number more than 1000 for the respective epoxides except for the conversion of cyclohexene oxide to cyclohexene carbonate.

Mixed azide and 5-(pyrimidyl)tetrazole bridged Co(II)/Mn(II) polymers: synthesis, crystal structures, ferroelectric and magnetic behavior.

The reaction of pyrimidine-2-carbonitrile, NaN(3) in the presence of Co(NO(3))(2)·6H(2)O or MnCl(2)·4H(2)O leads to the formation of complexes [Co(pmtz)(µ(1,3)-N(3))(H(2)O)](n) (1) and [Mn(pmtz)(µ(1,3)-N(3))(H(2)O)](n) (2) respectively, under hydrothermal condition [pmtz = 5-(pyrimidyl)tetrazolate]. These two complexes have been fully characterized by single crystal X-ray diffraction. Complex 1 crystallizes in a non-centrosymmetric space group Aba2 in the orthorhombic system and is found to exhibit ferroelectric behavior, whereas complex 2 crystallizes in the P2(1)/c space group in the monoclinic system. Variable temperature magnetic characterizations in the temperature range of 2-300 K indicate that complex 1 is a canted antiferromagnet (weak ferromagnet) with T(c) = 15.9 K. Complex 1 represents a unique example of a multiferroic coordination polymer containing tetrazole as a co-ligand. Complex 2 is a one-dimensional chain of Mn(II) bridged by a well-known antiferromagnetic coupler end-to-end azido ligand. In contrast to the role played by the end-to-end azido pathway in most of the transition metal complexes, complex 2 showed unusual ferromagnetic behavior below 40 K because of spin canting.

A series of transition metal-azido extended complexes with various anionic and neutral co-ligands: synthesis, structure and their distinct magnetic behavior.

The crystal structures and magnetic properties of five new transition metal-azido complexes with two anionic [pyrazine-2-carboxylate (pyzc) and p-aminobenzoate (paba)] and two neutral [pyrazine (pyz) and pyridine (py)] coligands are reported. All five complexes were synthesized by solvothermal methods. The complex [Co2(pyzc)2(N3)2(H2O)2]n (1) is 1D and exhibit canted antiferromagnetism, while the 3D complex [MnNa(pyzc)(N3)2(H2O)2]n (2) has a complicated structure and is weakly ferromagnetic in nature. [Mn2(paba)2(N3)2(H2O)2]n (3), is a 2D sheet and the MnII ions are found to be antiferromagnetically coupled. The isostructural 2D complexes [Cu3(pyz)2(N3)6]n (4) and [Cu3(py)2(N3)6]n (5) resemble remarkably in their magnetic properties exhibiting moderately strong ferromagnetism. Density functional theory calculations (B3LYP functional) have been performed to provide a qualitative theoretical interpretation of the overall magnetic behavior shown by these complexes.

Co(II) and Cr(III) complexes of formate-formamide mixed ligands: synthesis, structures, single crystal-to-single crystal transformation and magnetic behaviour.

Solvothermal treatment of an equimolar mixture of Co(NO(3))(2).6H(2)O, HCONH(2) and NaN(3) in MeOH at 100 degrees C yielded a three-dimensional NaCl type network Co(HCOO)(2)(HCONH(2))(2).HCONH(2) (1a) containing formamides in the pores of the structure. Solvated pink 1a undergoes single crystal-to-single crystal (SCSC) transformation at 215 degrees C to form the desolvated dark brown product Co(HCOO)(2)(HCONH(2))(2) (1b) with the retention of the original framework. Reversible single crystal-to-single crystal transformation of 1b (brown) to 1a (pink) in the presence of excess formamide was also established at room temperature. The coordination environment around Co(II) in both 1a and 1b is octahedral with a CoN(2)O(4) coordination composition. A similar reaction replacing Co(II) by Cr(III) produced a heterometallic 3D extended network Na[Cr(HCOO)(4)(HCONH(2))(2)].2H(2)O (2a) at 100 degrees C. An increase in reaction temperature to 150 degrees C produced a simple mononuclear complex Cr(HCOO)(3)(HCONH(2))(3).3H(2)O (2b). Variable temperature magnetic studies revealed the presence of a canting phenomena in both 1a and 1b, and hysteresis loop in the field dependent magnetisation plot at 2 K whereas complex 2a is simply paramagnetic in nature.

Three-component assembly of a metal-inorganic 3D Co(II) polymer containing bridging hydrazine.

Three-component metal-inorganic assembly of a Co(ii) network representing the first example of a 3D coordination polymer containing a hydrazine bridging ligand, has been synthesized and characterized.

Assembling metals (Co II and Mn II) with pyridylcarboxylates in the presence of azide: synthesis, structural aspects and magnetic behavior of three coordination polymers.

The reaction between Co(NO3)2.6H2O and substituted pyridylcarboxylic acid [nicotinic acid (Hnic) or trans-3-pyridylacrylic acid (Htpa)] in the presence of NaN3 under hydrothermal conditions yielded [Co(1.5)(nic)2 (Hnic)(N3)]n (1) and [Co(1.5)(tpa)2 (N3)(H2O)]n (2), respectively. Single crystal structure analyses reveal that both complexes are 3D complicated coordination polymers. The basic repeating units in both of the complexes are Co(3) trinuclear clusters containing syn-syn bridging carboxylate and end-on azido linker. A similar reaction using MnCl2.4H2O in presence of equimolar amounts of Htpa and NaN3 yielded a 2D corrugated sheet [Mn(tpa)2]n (3) containing no azide. Complex 3 can also be synthesized under hydrothermal conditions using Natpa in the absence of NaN3. Surprisingly, the same reaction at room temperature yielded a known mononuclear complex [Mn(tpa)2(H2O)4]. Variable temperature magnetic studies down to 2 K revealed the dominant antiferromagnetic nature of the first two complexes with a ferrimagnetic type of behavior despite the facts that they are homometallic and homospin systems. The susceptibility data in both cases were analyzed by a Co3 trinuclear model as well as considering inter-trimer interactions. Complex 3 is weakly antiferromagnetic in nature with an exchange parameter of J = -2 cm(-1) through the syn-anti bridging carboxylate pathway.

Dual role of azide in the formation of a 3D coordination polymer containing bridging 5-pyrimidinecarboxylate.

A new 3D framework [Mn4(5-pmc)4(1,1-N3)4]n () composed of a rare MnII4 square as the repeating secondary building unit, representing the first coordination polymer of 5-pyrimidinecarboxylate (5-pmc) has been successfully synthesized and characterized by X-ray single crystal structure analysis.