Sandip Mukherjee

Versatility of azide in serendipitous assembly of Copper(II) Magnetic Polyclusters

Engineering at the molecular level is one of the most exciting new developments for the generation of functional materials. However, the concept of designing polynuclear extended structures from bottom up is still not mature. Although progress has been made with secondary building units (SBUs) in metal organic frameworks (MOFs), the control seems to be just an illusion when it comes to bridging ligands such as the azide ion. When we say that the azido ligand is versatile in its bridging capabilities, what we mean is that it would be difficult to predict or control its bridging properties. However, this kind of serendipity is not always bad news. For example, scientists have shown that the azido ligand can mediate magnetic exchanges between paramagnetic metals in a predictable fashion (usually depending upon the bonding geometries). Therefore, it is a well-respected ligand in polynuclear assemblies. Serendipitous assemblies offer new magnetic structures that we may not otherwise even think about synthesizing. The azido ligand forms a variety of complexes with copper(II) using different blocking amines or pyridine based ligands. Its structural nature changes upon changing the substitution on amine, as well as the amount of blocking ligand. In principle, if we take any of these complexes and provide more coordination sites to the bridging azido ligands by removing a fraction of the blocking ligands, we can get new complexes with intricate structural networks and therefore different magnetic properties with the same components as used for the parent complex. In this Account, we mainly discuss the development of a number of new topological and magnetic exchange systems synthesized using this concept. Not all of these new complexes can be grouped according to their basic building structures or even by the ratio of the metal to blocking ligand. Therefore, we divided the discussion by the nuclearity of the basic building structures. Some of the complexes with the same nuclearities have very similar or even almost identical basic structures. However, the way these building units are joined together (by the azido bridges) to form the overall extended structures differ almost in every case. The complexes having the Cu6 core are particularly interesting from a structural point of view. Although they have almost identical basic structures, some of them are extended in three dimensions, but two of them are extended in two dimensions by two different bridging networks. In the complexes having linear Cu4 basic units, we find that using similar ligands does not always give the same bridging networks even within the basic building structures. These complexes have also enriched the field of molecular magnetism. One of the complexes with a Cu3 building unit has provided us with the opportunity to study the competing behavior of two different kinds of magnetic exchange mechanism (ferromagnetic and antiferromagnetic) acting simultaneously between two metal ions. Through density functional theory calculations, we showed how they work independently and their additive nature to produce the overall effect. The exciting methodology for the generation of copper(II) polyclusters presented in this Account will provide the opportunity to explore analogous serendipitous assembly of diverse structures with interesting magnetic behavior using other transition metal ions having more than one unpaired electrons.

Synthesis, Structures, and Magnetic Behavior of a Series of Copper(II) Azide Polymers of Cu4 Building Clusters and Isolation of a New Hemiaminal Ether as the Metal Complex

Four new neutral copper azido polymers, [Cu(4)(N(3))(8)(L(1))(2)](n) (1), [Cu(4)(N(3))(8)(L(2))(2)](n) (2), [Cu(4)(N(3))(8)(L(3))(2)](n) (3), and [Cu(9)(N(3))(18)(L(4))(4)](n) (4) [L(1-4) are formed in situ by reacting pyridine-2-carboxaldehyde with 2-[2-(methylamino)ethyl]pyridine (mapy, L(1)), N,N-dimethylethylenediamine (N,N-dmen, L(2)), N,N-diethylethylenediamine (N,N-deen, L(3)), and N,N,2,2-tetramethylpropanediamine (N,N,2,2-tmpn, L(4))], have been synthesized by using 0.5 mol equiv of the chelating tridentate ligands with Cu(NO(3))(2)·3H(2)O and an excess of NaN(3). Single-crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu(II)(4) building blocks. The overall structure of 3 is two-dimensional, while the other three complexes are one-dimensional in nature. Complex 1 represents a unique example containing hemiaminal ether arrested by copper(II). Complexes 1 and 2 have a rare bridging azido pathway: both end-on and end-to-end bridging azides between a pair of Cu(II) centers. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all four complexes. Density functional theory calculations (B3LYP functional) have been performed on complexes 1-3 to provide a qualitative theoretical interpretation of their overall ferromagnetic behavior.

A Rare Phenoxido/Acetato/Azido Bridged Trinuclear and an Unprecedented Phenoxido/Azido Bridged One-Dimensional Polynuclear Nickel(II) Complexes: Synthesis, Crystal Structure, and Magnetic Properties with Theoretical Investigations on the Exchange Mechanism

The reaction of a tridentate Schiff base ligand HL (2-[(3-dimethylaminopropylimino)-methyl]-phenol) with Ni(II) acetate or perchlorate salts in the presence of azide as coligand has led to two new Ni(II) complexes of formulas [Ni(3)L(2)(OAc)(2)(μ(1,1)-N(3))(2)(H(2)O)(2)]·2H(2)O (1) and [Ni(2)L(2)(μ(1,1)-N(3))(μ(1,3)-N(3))](n)(2). Single crystal X-ray structures show that complex 1 is a linear trinuclear Ni(II) compound containing a μ(2)-phenoxido, an end-on (EO) azido and a syn-syn acetato bridge between the terminal and the central Ni(II) ions. Complex 2 can be viewed as a one-dimensional (1D) chain in which the triply bridged (di-μ(2)-phenoxido and EO azido) dimeric Ni(2) units are linked to each other in a zigzag pattern by a single end-to-end (EE) azido bridge. Variable-temperature magnetic susceptibility studies indicate the presence of moderate ferromagnetic exchange coupling in complex 1 with J value of 16.51(6) cm(-1). The magnetic behavior of 2 can be fitted in an alternating ferro- and antiferromagnetic model [J(FM) = +34.2(2.8) cm(-1) and J(AF) = -21.6(1.1) cm(-1)] corresponding to the triple bridged dinuclear core and EE azido bridge respectively. Density functional theory (DFT) calculations were performed to corroborate the magnetic results of 1 and 2. The contributions of the different bridges toward magnetic interactions in both compounds have also been calculated.

Molecular Marriage through Partner Preferences in Covalent Cage Formation and Cage-to-Cage Transformation

Unprecedented self-sorting of three-dimensional purely organic cages driven by dynamic covalent bonds is described. Four different cages were first synthesized by condensation of two triamines and two dialdehydes separately. When a mixture of all the components was allowed to react, only two cages were formed, which suggests a high-fidelity self-recognition. The issue of the preference of one triamine for a particular dialdehyde was further probed by transforming a non-preferred combination to either of the two preferred combinations by reacting it with the appropriate triamine or dialdehyde.

Self‐Assembled Pd6 Open Cage with Triimidazole Walls and the Use of Its Confined Nanospace for Catalytic Knoevenagel‐ and Diels–Alder Reactions in Aqueous Medium

The two-component self-assembly of a 90° Pd(II) acceptor and a triimidazole donor led to the formation of a water-soluble semi-cylindrical cage with a hydrophobic cavity, which was separately crystallized with hydrophilic- and hydrophobic guests. The parent cage was found to catalyze the Knoevenagel condensation reaction of a series of aromatic mono-aldehydes with active methylene compounds, such as Meldrums acid or 1,3-dimethylbarbituric acid. The confined hydrophobic nanospace within this cage was also used in the catalytic Diels-Alder reactions of 9-hydroxymethylanthracene with N-phenylmaleimide or N-cyclohexylmaleimide.

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.

Two novel heterometallic chains featuring Mn(II) and Na(I) ions in trigonal-prismatic geometries alternately linked to octahedral Mn(IV) ions: synthesis, structures, and magnetic behavior.

Two new one-dimensional heterometallic complexes, [Mn(3)Na(L)(4)(CH(3)CO(2))(MeOH)(2)](ClO(4))(2)·3H(2)O (1), [Mn(3)Na(L)(4)(CH(3)CH(2)CO(2))(MeOH)(2)](ClO(4))(2)·2MeOH·H(2)O (2) [LH(2) = 2-methyl-2-(2-pyridyl)propane-1,3-diol], have been synthesized and characterized by X-ray crystallography. Both complexes feature Mn(II) and Na(I) ions in trigonal-prismatic geometries that are linked to octahedral Mn(IV) ions by alkoxy bridges. Variable-temperature direct- and alternating-current magnetic susceptibility data indicated a spin ground state of S = 11/2 for both complexes. Density functional theory calculations performed on 1 supported this conclusion.

Sr2+ and Cd2+ coordination polymers: the effect of the different coordinating behaviour of a newly designed tricarboxylic acid

This article presents the investigation of the coordination behavior of a newly synthesized tricarboxylate ligand, obtained by joining imidazole dicarboxylic acid and 4-carboxybenzyl moieties [cbimdaH3, 1-(4-carboxybenzyl)-1H-imidazole-4,5-dicarboxylic acid]. Two novel coordination polymers were obtained through solvothermal reactions under similar conditions namely [Sr(cbimdaH)(H2O)]n (1) and [Cd2(cbimdaH)2(H2O)6]n·(DMF)3n(H2O)3n (2), with the ligand behaving as a dianionic tricarboxylate linker. The single crystal X-ray structures show that while 1 forms a 3D coordination polymer, 2 forms a 1D polymer which is further assembled in three dimensions through supramolecular interactions (H-bonding). Complex 1 consists of Sr2+ ions in a distorted dodecahedral coordination geometry, while 2 consists of Cd2+ ions in distorted pentagonal bipyramidal geometries. A topology study reveals that 1 has a new topology based on the 5,6-coordinated 3D net architecture. The luminescence properties of the complexes in the solid state and their thermal stabilities were studied.

Role of Dicarboxylate Linkers in MnIII‐Salicylaldoximate Based Extended Structures: Synthesis, Structures, and Magnetic Behavior

Four new oxo-centered Mn(III)-salicylaldoximate triangle-based extended complexes [Mn(III)6O2(salox)6(EtOH)4(phda)]n·(saloxH2)n·(2H2O)n (1), [Mn(III)6O2(salox)6(MeOH)5(5-I-isoph)]n·(3MeOH)n (2), [Mn(III)6O2(salox)6(MeOH)4(H2O) (5-N3-isoph)]n·(4MeOH)n (3) and [Mn(III)3NaO(salox)3(MeOH)4(5-NO2-isoph)]n·(MeOH)n (H2O)n (4) [salox=salicylaldoximate, phda=1,3-phenylenediacetate, isoph=isophthalate] have been synthesized under similar reaction conditions. Single crystal X-ray structures show that in 1, only one type of Mn6 cluster is arranged in 1D, whereas in 2 and 3 there are two types of clusters, differing in the way the triangle units are joined and assembled. In complex 4, however, the basic building structure is heteronuclear and based on Mn3 units extended in 2D. Susceptibility measurements (dc and ac) over a wide range of temperatures and fields show that the complexes 1, 2, and 3 behave as single molecule magnets (SMMs) with S=4 ground state, while 4 is dominantly antiferromagnetic with a ground spin state S=2. Density functional theory calculations have been performed on model complexes to provide a qualitative theoretical interpretation for their overall magnetic behavior.