Atanu Dey

Slow Magnetic Relaxation in Co(III)–Co(II) Mixed-Valence Dinuclear Complexes with a CoIIO5X (X = Cl, Br, NO3) Distorted-Octahedral Coordination Sphere

The reaction of the multisite coordination ligand (LH4) with CoX2·nH2O in the presence of tetrabutylammonium hydroxide affords a series of homometallic dinuclear mixed-valence complexes, [Co(III)Co(II)(LH2)2(X)(H2O)](H2O)m (1, X = Cl and m = 4; 2, X = Br and m = 4; 3, X = NO3 and m = 3). All of the complexes have been structurally characterized by X-ray crystallography. Both cobalt ions in these dinuclear complexes are present in a distorted-octahedral geometry. Detailed magnetic studies on 1-3 have been carried out. M vs H data at different temperatures can be fitted with S = 3/2, the best fit leading to D(3/2) = -7.4 cm(-1), |E/D| < 1 × 10(-3), and g = 2.32 for 1 and D(3/2) = -9.7 cm(-1), |E/D| <1 × 10(-4), and g = 2.52 for 2. In contrast to 1 and 2, M vs H data at different temperatures suggest that compound 3 has comparatively little magnetic anisotropy. In accordance with the large negative D values observed for compounds 1 and 2, they are single-molecule magnets (SMMs) and exhibit slow relaxation of magnetization at low temperatures under an applied magnetic field of 1000 Oe with the following energy barriers: 7.9 cm(-1) (τo = 6.1 × 10(-6) s) for 1 and 14.5 cm(-1) (τo = 1.0 × 10(-6) s) for 2. Complex 3 does not show any SMM behavior, as expected from its small magnetic anisotropy. The τo values observed for 1 and 2 are much larger than expected for a SMM, strongly suggesting that the quantum pathway of relaxation at very low temperatures is not fully suppressed by the effects of the applied field.

Syntheses, structures, and magnetic properties of a family of heterometallic heptanuclear [Cu5Ln2] (Ln = Y(III), Lu(III), Dy(III), Ho(III), Er(III), and Yb(III)) complexes: observation of SMM behavior for the Dy(III) and Ho(III) analogues.

Sequential reaction of the multisite coordination ligand (LH3) with Cu(OAc)2·H2O, followed by the addition of a rare-earth(III) nitrate salt in the presence of triethylamine, afforded a series of heterometallic heptanuclear complexes containing a [Cu5Ln2] core {Ln = Y(1), Lu(2), Dy(3), Ho(4), Er(5), and Yb(6)}. Single-crystal X-ray crystallography reveals that all the complexes are dicationic species that crystallize with two nitrate anions to compensate the charge. The heptanuclear aggregates in 1-6 are centrosymmetrical complexes, with a hexagonal-like arrangement of six peripheral metal ions (two rare-earth and four copper) around a central Cu(II) situated on a crystallographic inversion center. An all-oxygen environment is found to be present around the rare-earth metal ions, which adopt a distorted square-antiprismatic geometry. Three different Cu(II) sites are present in the heptanuclear complexes: two possess a distorted octahedral coordination sphere while the remaining one displays a distorted square-pyramidal geometry. Detailed static and dynamic magnetic properties of all the complexes have been studied and revealed the single-molecule magnet behavior of the Dy(III) and Ho(III) derivatives.

Molecular transition-metal phosphonates

Molecular transition-metal phosphonates are of relatively recent origin and can be assembled by several synthetic strategies. The nuclearity and the structure of the metal aggregates can be modulated by several factors including the stoichiometry of the reactants, nature of the metal precursor and the type of phosphonic acid used. This perspective summarizes some of the recent work carried out on copper(II)-, zinc(II)- and cadmium(II) phosphonates with particular emphasis on their synthesis and structure.

Hydroxide-Free Cubane-Shaped Tetranuclear [Ln4] Complexes

The reaction of the lanthanide(III) chloride salts [Gd(III), Tb(III), and Dy(III)] with a new chelating, flexible, and sterically unencumbered multisite coordinating compartmental Schiff-base ligand (E)-2-((6-(hydroxymethyl)pyridin-2-yl)methyleneamino)phenol (LH2) and pivalic acid (PivH) in the presence of triethylamine (Et3N) affords a series of tetranuclear Ln(III) coordination compounds, [Ln4(L)4(μ2-η(1)η(1)Piv)4]·xH2O·yCH3OH (1, Ln = Gd(III), x = 3, y = 6; 2, Ln = Tb(III), x = 6, y = 2; 3, Ln = Dy(III), x = 4, y = 6). X-ray diffraction studies reveal that the molecular structure contains a distorted cubane-like [Ln4(μ3-OR)4](+8) core, which is formed by the concerted coordination action of four dianionic L(2-) Schiff-base ligands. Each lanthanide ion is eight-coordinated (2N, 6O) to form a distorted-triangular dodecahedral geometry. Alternating current susceptibility measurements of complex 3 reveal frequency- and temperature-dependent two-step out-of-phase signals under zero direct current (dc) field, which is characteristic of single-molecule magnet behavior. Analysis of the dynamic magnetic data under an applied dc field of 1000 Oe to fully or partly suppress the quantum tunneling of magnetization relaxation process affords the anisotropic barriers and pre-exponential factors: Δ/kB = 73(2) K, τ0 = 4.4 × 10(-8) s; Δ/kB = 47.2(9) K, τ0 = 5.0 × 10(-7) s for the slow and fast relaxations, respectively.

Amending the Anisotropy Barrier and Luminescence Behavior of Heterometallic Trinuclear Linear [MIILnIIIMII] (LnIII=Gd, Tb, Dy; MII=Mg/Zn) Complexes by Change from Divalent Paramagnetic to Diamagnetic Metal Ions

The sequential reaction of a multisite coordinating compartmental ligand [2-(2-hydroxy-3-(hydroxymethyl)-5-methylbenzylideneamino)-2-methylpropane-1,3-diol] (LH4 ) with appropriate lanthanide salts followed by the addition of [Mg(NO3 )2 ]⋅6 H2 O or [Zn(NO3 )2 ]⋅6 H2 O in a 4:1:2 stoichiometric ratio in the presence of triethylamine affords a series of isostructural heterometallic trinuclear complexes containing [Mg2 Ln](3+) (Ln=Dy, Gd, and Tb) and [Zn2 Ln](3+) (Ln=Dy, Gd, and Tb) cores. The formation of these complexes is demonstrated by X-ray crystallography as well as ESI-MS spectra. All complexes are isostructural possessing a linear trimetallic core with a central lanthanide ion. The comprehensive studies discussed involve the synthesis, structure, magnetism, and photophysical properties on this family of trinuclear [Mg2 Ln](3+) and [Zn2 Ln](3+) heterometallic complexes. [Mg2 Dy](3+) and [Zn2 Dy](3+) show slow relaxation of the magnetization below 12 K under zero applied direct current (dc) field, but without reaching a neat maximum, which is due to the overlapping with a faster quantum tunneling relaxation mediated through dipole-dipole and hyperfine interactions. Under a small applied dc field of 1000 Oe, the quantum tunneling is almost suppressed and temperature and frequency dependent peaks are observed, thus confirming the single-molecule magnet behavior of complexes [Mg2 Dy](3+) and [Zn2 Dy](3+) .

Cyclo- and Carbophosphazene-Supported Ligands for the Assembly of Heterometallic (Cu2+/Ca2+, Cu2+/Dy3+, Cu2+/Tb3+) Complexes: Synthesis, Structure, and Magnetism

The carbophosphazene and cyclophosphazene hydrazides, [{NC(N(CH(3))(2))}(2){NP{N(CH(3))NH(2)}(2)}] (1) and [N(3)P(3)(O(2)C(12)H(8))(2){N(CH(3))NH(2)}(2)] were condensed with o-vanillin to afford the multisite coordination ligands [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-OH)(m-OCH(3))}(2)}] (2) and [{N(2)P(2)(O(2)C(12)H(8))(2)}{NP{N(CH(3))N═CH-C (6)H(3)-(o-OH)(m-OCH(3))}(2)}] (3), respectively. These ligands were used for the preparation of heterometallic complexes [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuCa(NO(3))(2)}] (4), [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{Cu(2)Ca(2)(NO(3))(4)}]·4H(2)O (5), [{NC(N(CH(3))(2))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuDy(NO(3))(4)}]·CH(3)COCH(3) (6), [{NP(O(2)C(12)H(8))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuDy(NO(3))(3)}] (7), and [{NP(O(2)C(12)H(8))}(2){NP{N(CH(3))N═CH-C(6)H(3)-(o-O)(m-OCH(3))}(2)}{CuTb(NO(3))(3)}] (8). The molecular structures of these compounds reveals that the ligands 2 and 3 possess dual coordination pockets which are used to specifically bind the transition metal ion and the alkaline earth/lanthanide metal ion; the Cu(2+)/Ca(2+), Cu(2+)/Tb(3+), and Cu(2+)/Dy(3+) pairs in these compounds are brought together by phenoxide and methoxy oxygen atoms. While 4, 6, 7, and 8 are dinuclear complexes, 5 is a tetranuclear complex. Detailed magnetic properties on 6-8 reveal that these compounds show weak couplings between the magnetic centers and magnetic anisotropy. However, the ac susceptibility experiments did not reveal any out of phase signal suggesting that in these compounds slow relaxation of magnetization is absent above 1.8 K.

Decanuclear Ln10 Wheels and Vertex‐Shared Spirocyclic Ln5 Cores: Synthesis, Structure, SMM Behavior, and MCE Properties

The reaction of a Schiff base ligand (LH3) with lanthanide salts, pivalic acid and triethylamine in 1:1:1:3 and 4:5:8:20 stoichiometric ratios results in the formation of decanuclear Ln10 (Ln = Dy (1), Tb (2), and Gd (3)) and pentanuclear Ln5 complexes (Ln = Gd (4), Tb (5), and Dy (6)), respectively. The formation of Ln10 and Ln5 complexes are fully governed by the stoichiometry of the reagents used. Detailed magnetic studies on these complexes (1-6) have been carried out. Complex 1 shows a SMM behavior with an effective energy barrier for the reversal of the magnetization (Ueff) = 16.12(8) K and relaxation time (τo) = 3.3×10(-5) s under 4000 Oe direct current (dc) field. Complex 6 shows the frequency dependent maxima in the out-of-phase signal under zero dc field, without achieving maxima above 2 K. Complexes 3 and 4 show a large magnetocaloric effect with the following characteristic values: -ΔSm = 26.6 J kg(-1) K(-1) at T = 2.2 K for 3 and -ΔSm = 27.1 J kg(-1) K(-1) at T = 2.4 K for 4, both for an applied field change of 7 T.

Carbophosphazene-supported ligand systems containing pyrazole/guanidine coordinating groups.

Carbophosphazene-based coordination ligands [{NC(NMe(2))}(2){NP(3,5-Me(2)Pz)(2)}] (1), [{NC(NEt)(2)}{NC(3,5-Me(2)Pz)}{NP(3,5-Me(2)Pz)(2)}] (2), [NC(3,5-Me(2)Pz)](2)[NP(3,5-Me(2)Pz)(2)] (3), [{NCCl}(2){NP(NC(NMe(2))(2))(2)}] (4), and [{NC(p-OC(5)H(4)N)}(2){NP(NC(NMe(2))(2))(2)}] (5) were synthesized and structurally characterized. In these compounds, the six-membered C(2)N(3)P ring is perfectly planar. The reaction of 1 with CuCl(2) afforded [{NC(NMe(2))}(2){NHP(O)(3,5-Me(2)Pz)}·{Cu(3,5-Me(2)PzH)(2)(Cl)}][Cl] (6). The ligand binds to Cu(II) utilizing the geminal [P(O)(3,5-Me(2)Pz)] coordinating unit. Similarly, the reaction of 2 with PdCl(2) afforded, after a metal-assisted P-N hydrolysis, [{NC(NEt)(2)}{NC(3,5-Me(2)Pz)}{NP(O)(3,5-Me(2)Pz)}·{Pd(3,5-Me(2)PzH)(Cl)}] (7). In the latter, the [P(O)(3,5-Me(2)Pz)] unit does not coordinate; in this instance, the Pd(II) is bound by a ring nitrogen atom and a carbon-tethered pyrazolyl nitrogen atom. The reaction of 3 with PdCl(2) also results in P-N bond hydrolysis affording [{NC(3,5-Me(2)Pz)(2)}{NP(O)(3,5-Me(2)Pz)}{Pd(Cl)}] (8). In contrast to 7, however, in 8, the Pd(II) elicits a nongeminal η(3) coordination from the ligand involving two carbon-tethered pyrazolyl groups and a ring nitrogen atom. Metalated products could not be isolated in the reaction of 3 with K(2)PtCl(4). Instead, a P-O-P bridged carbodiphosphazane dimer, [{NC(3,5-Me(2)Pz)NHC(3,5-Me(2)Pz)}{NP(O)}](2) (9), was isolated as the major product. Finally, the reaction of 5 with PdCl(2) resulted in [{NC(OC(5)H(4)N)}(2){NP(NC(NMe(2))(2))(2)}·{PdCl(2)}] (10). In the latter, the exocyclic P-N bonds are quite robust and are involved in binding to the metal ion. Compounds 6-10 have been characterized by a variety of techniques including X-ray crystallography. In all of the compounds, the bond parameters of the inorganic heterocyclic rings are affected by metalation.

Syntheses and structures of a family of heterometallic pentanuclear [MnIII3LnNa] (Ln = Dy, Tb, Gd and Nd) complexes: H-bonding reduces the nuclearity from nine to five

The reaction of a multisite coordination ligand (LH3) with LnCl3·6H2O, followed by the addition of Mn(OAc)2·4H2O, sodium azide and pivalic acid in the presence of triethylamine in a 2 : 1 : 1 : 4 : 4 : 6 (LH3 : LnCl3 : Mn(OAc)2 : NaN3 : pivalic acid : Et3N) stoichiometric ratio afforded a series of heterometallic pentanuclear neutral complexes containing a [MnIII3LnNa] core {Ln = Dy (1), Tb (2), Gd (3) and Nd (4)}. The oxidation states of the MnIII ions were confirmed by BVS calculation. All the complexes were characterized by X-ray crystallography. The pentametallic aggregates form a trigonal-bipyramidal geometry in which the three MnIII ions are in the equatorial plane whereas the sodium and lanthanide ions are in the apical positions. Three different types of MnIII ions are present in the complexes and all are in a distorted octahedral geometry. An all-oxygen environment is found to be present around the lanthanides as well as the sodium ions. The lanthanide ion is eight-coordinated and in distorted dodecahedral geometry, while the sodium ion is six-coordinate in a distorted trigonal prismatic geometry in 1–4. The pentanuclear core [MnIII3LnNa] is a subset of one-half of the nonanuclear ensemble, [MnIII6LnNa2]+, reported in literature. We propose that the reduction in the nuclearity of the heterometallic metal ensemble occurs as a result of the influence of hydrogen bonding interactions present in the system.

Heterometallic Heptanuclear [Cu5Ln2] (Ln = Tb, Dy, and Ho) Single-Molecule Magnets Organized in One-Dimensional Coordination Polymeric Network

The reaction of a multisite coordination ligand, LH3, with Cu(II) salts and Ln(NO3)3·nH2O in a 1:2:1 stoichiometric ratio in the presence of triethylamine was found to afford a series of one-dimensional heterometallic [{Cu5Ln2(L)2(μ3-OH)4(ClO4)(NO3)3(OH2)5}(ClO4)2(H2O)x]∞ [Ln = Tb(1), Dy(2) and Ho(3), x = 4.25, 5.5, and 5 for 1-3, respectively] coordination polymers. Complexes 1-3 have been characterized by single crystal X-ray crystallography. The detailed study of the magnetic properties has also been performed and compared with the parent [Cu5Ln2] molecular analogues. The ac susceptibility measurements for complexes 1-3 confirm their SMM behavior with the following characteristics: Δeff/kB = 23.4 K, τ0 = 1.1 × 10-6 s and Δeff/kB = 27.9 K, τ0 = 6.6 × 10-7 s under 0 and 1200 Oe dc fields, respectively for 1; Δeff/kB = 8.3 K, τ0 = 3.1 × 10-6 s for 2 under 0 dc field. For 3, the fast QTM below 4 K prevents the estimation of the SMM energy barrier. Remarkably, the magnetic and SMM properties of the previously reported molecular [Cu5Ln2] analogues are preserved after their assembly in these coordination networks.