Changes in magnetic order through two consecutive dehydration steps of metal-phosphonate diamond chains.

Hydrothermal reactions of the multitopic ligand 1-hydroxy-1-(piperidin-4-yl)methylidenebisphosphonic acid (hpdpH) with cobalt or nickel sulfates afforded two new isostructural metal phosphonates, M (hpdpH)(HO)·4HO [M = Co (Co-10HO), Ni (Ni-10HO)]. Their structures consist of parallel diamond chains of three MO octahedra bridged by the POC tetrahedra. Six of the seven oxygen atoms of the ligand are involved in coordination; for two ligands that amounts to 12 bonds for 3 MO and the remaining six are occupied by terminal water molecules.

Polymorphic layered copper phosphonates: exfoliation and proton conductivity studies.

Three polymorphic copper carboxylate-phosphonates are reported, namely, α-Cu(4-cnappH)(H2O) (α-Cu-1), α-Cu(4-cnappH)(H2O)·0.5H2O (α-Cu-2) and β-Cu(4-cnappH)(H2O) (β-Cu), where 4-cnappH3 is (4-carboxynaphthalen-1-yl)phosphonic acid. All show layer structures but with different layer topologies.

Homochiral iron(ii)-based metal-organic nanotubes: metamagnetism and selective nitric oxide adsorption in a confined channel.

Homochiral iron(ii)-based nanotubular metal phosphonates (R)- and (S)-[Fe(pemp)(H2O)2] [pemp2- = (R)- or (S)-(1-phenylethylamino)methylphosphonate] are reported showing metamagnetism at low temperature. The dehydrated product features coordinatively unsaturated and redox-active metal ion sites that enable it to strongly bind nitric oxide at room temperature.

Formation Mechanism and Reversible Expansion and Shrinkage of Magnesium-Based Homochiral Metal-Organic Nanotubes.

Two pairs of homochiral magnesium phosphonates, namely (R)-, (S)-[Mg(pemp)(H O) ] (1) and (R)-, (S)-Mg (pemp) (H O) ]⋅3 H O (2) are reported (pemp =(R)- or (S)-(1-phenylethylamino) methylphosphonate). Compounds 1 show one-dimensional tubular structures. The tube wall is purely inorganic, containing six-membered rings made up of corner-sharing {MgO N} octahedra and {PO C} tetrahedra.

Enantiopure phosphonic acids as chiral inducers: homochiral crystallization of cobalt coordination polymers showing field-induced slow magnetization relaxation.

This Communication reports, for the first time, that enantiopure phosphonic acids can serve as chirality-inducing agents towards homochiral coordination polymers. Hence homochiral chain compounds (M)- or (P)-Co(SO4)(1,3-bbix)(H2O)3 (1M or 1P) are obtained successfully using an achiral precursor of 1,3-bis((1H-benzo[d]imidazol-1-yl)methyl)benzene (1,3-bbix) in the presence of a catalytic amount of (S)- or (R)-3-phenyl-2-((phosphonomethyl)amino)propanoic acid [(S)- or (R)-2-ppapH3]. Furthermore, compound 1M provides the first example of homochiral cobalt compounds showing field-induced single ion magnet behavior.

Chirality- and pH-Controlled Supramolecular Isomerism in Cobalt Phosphonates and Its Impact on the Magnetic Behavior.

Two pairs of enantiomeric compounds with formulas (S)- or (R)-Co3 (ppap)2 (4,4'-bpy)2 (H2 O)2 ⋅4 H2 O [(S)-1 or (R)-1], (S)- or (R)-Co3 (ppap)2 (4,4'-bpy)2 (H2 O)2 ⋅3 H2 O [(S)- or (R)-2), and related racemic compound Co3 (ppap)2 (4,4'-bpy)2 (H2 O)2 ⋅4 H2 O (rac-3; 4,4'-bpy=4,4'-bipyridine, H3 ppap=3-phenyl-2-[(phosphonomethyl)amino]propanoic acid) are reported. Compounds 1 and rac-3 show identical three-dimensional framework structures, whereas compounds 2 have two-dimensional layer structures. Compounds 1 and 2 are catenation isomers, formation of which is controlled solely by the pH of the reaction mixtures, whereas the formation of isomeric compounds 1 and rac-3 is controlled purely by the chirality of the phosphonate ligand.

Racemic cobalt phosphonates incorporating flexible bis(imidazole) co-ligands.

By incorporating flexible bis(imidazol-1-ylmethyl)benzene (bix) co-ligands, four new racemic cobalt phosphonates with formulae Co3(3-ppap)2(1,4-bix)2(H2O)4·4H2O (1), Co3(3-ppap)2(1,3-bix)2(H2O)4·5H2O (2), Co3(3-ppap)2(1,2-bix)2(H2O)4·4H2O (3) and Co3(ppa)2(1,2-bix)2·4H2O (4) are isolated, where 3-ppapH3 represents 3-phenyl-3-((phosphonomethyl)amino)propanoic acid and ppaH3 is 2-phenyl-2-(phosphonomethylamino)acetic acid. Compounds 1-3 crystallize in the monoclinic space group P21/c and show two-dimensional structures in which the Co3(3-ppap)2 chains are bridged by 1,4-bix, 1,3-bix and 1,2-bix ligands in trans-modes, respectively. Within the chain, a racemic dimer of Co2(3-ppap)2(2-) is found, where the Co atoms are doubly bridged by O-P-O units from the (S)- and (R)-3-ppap(3-) ligands.

Homochiral metal phosphonate nanotubes.

A new type of homochiral metal-organic nanotubular structures based on metal phosphonates are reported, namely, (R)- or (S)-[M(pemp)(H2O)2][M = Co(II) (1), Ni(II) (2)] [pemp(2-) = (R)- or (S)-(1-phenylethylamino)methylphosphonate]. In these compounds, the tube-walls are purely inorganic, composed of metal ions and O-P-O bridges. The cavity of the nanotube is hydrophilic with one coordination water pointing towards the center, while the outer periphery of the nanotube is hydrophobic, decorated by the phenylethyl groups of pemp(2-).

pH-controlled polymorphism in a layered dysprosium phosphonate and its impact on the magnetization relaxation.

Two polymorphic layered dysprosium phosphonates α-Dy(2-qpH)(SO4)(H2O)2 (α-Dy) and β-Dy(2-qpH)(SO4)(H2O)2 (β-Dy) (2-qpH2 = 2-quinolinephosphonic acid) which crystallize in monoclinic P2₁/c and triclinic P1̄ space groups, respectively, are reported. Both exhibit field-induced slow relaxation of magnetization at low temperature. The energy barrier for β-Dy is nearly three times that for α-Dy, attributed to the structural differences in the two phases.

(C-meso-N-meso-5,12-Dimethyl-7,14-diphenyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene)nickel(II) bis-[O,O'-bis-(4-methyl-phen-yl) dithio-phosphate].

The title complex, [Ni(C(24)H(32)N(4))](C(14)H(14)O(2)PS(2))(2), comprises a centrosymmetric [Ni(meso-diphen-yl[14]dien)](2+) dication (meso-diphen-yl[14]dien is C-meso-N-meso-5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene) and two O,O'-bis-(4-methyl-phen-yl) dithio-phosphate anions. The Ni(II) ion lies on an inversion center and is chelated by a tetra-amine macrocycle ligand in a slightly distorted NiN(4) square-planar geometry. Two S atoms from symmetry-related anions are located in pseudo-axial positions with respect to the Ni(II) ion, with Ni⋯S distances of 3.

(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)copper(II) bis-[O,O'-(o-phenyl-ene)dithio-phosphate].

In the title compound, [Cu(C(16)H(36)N(4))](C(6)H(4)O(2)PS(2))(2), the Cu(II) cation lies on an inversion center and is chelated by the macrocyclic tetra-amine ligand in a slightly distorted CuN(4) square-planar geometry. The axial positions are occupied by two O,O'-(o-phenyl-ene)dithio-phosphate anions with long Cu⋯S distances of 3.0940 (7) Å.

(C-meso-N-meso-5,12-Dimethyl-7,14-diphenyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene)copper(II) bis-[O,O'-bis-(4-methyl-phen-yl)dithio-phosphate].

In the title compound, [Cu(C(24)H(32)N(4))](C(14)H(14)O(2)PS(2))(2), the Cu(II) atom lies on an inversion center and is chelated by the macrocyclic ligand in a distorted CuN(4) square-planar geometry. Two O,O'-bis-(4-methyl-phen-yl)dithio-phosphate anions occupy the axial positions with long Cu⋯S distances of 3.0090 (8) Å.

(meso-5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra-azacyclo-tetra-deca-4,11-diene)copper(II) bis-[O,O'-bis-(4-methyl-phen-yl) dithio-phosphate].

The title compound, [Cu(C(16)H(32)N(4))](C(14)H(14)O(2)PS(2))(2) or [Cu(trans[14]dien)][S(2)P(OC(6)H(4)Me-4)(2)](2), where trans[14]dien is meso-5,7,7,12,14,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-deca-4,11-diene, was obtained by the reaction of [Cu(trans[14]dien)](ClO(4))(2) and [(C(2)H(5))(2)NH](2) [S(2)P(OC(6)H(4)Me-4)(2)](2). The Cu(II) atom lies on a centre of inversion and possesses a relatively undistorted square-planar coordination arrangement with four N atoms of the macrocyclic tetra-mine trans[14]dien [Cu-N = 1.9716 (19) and 2.

(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)nickel(II) bis-[O,O'-bis-(4-methyl-phen-yl) thio-phosphate].

In the centrosymmetric title complex, [Ni(C(16)H(36)N(4))](C(14)H(14)O(3)PS)(2), the Ni(II) ion is coordinated by four N atoms and two O atoms within a slightly distorted NiN(4)O(2) octa-hedral geometry. The asymmetric unit consits of one Ni(II) ion that is located on a center of inversion, half of the macrocylic ligand and one anion occupying general positions. Intra-molecular N-H⋯O and N-H⋯S hydrogen bonding is found between the macrocyclic ligand and the monothio-phosphate anion.

(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene)nickel(II) bis-[O,O'-bis-(4-tert-butyl-phen-yl) dithio-phosphate].

The title salt, [Ni(C(16)H(32)N(4))](C(20)H(26)O(2)PS(2))(2), comprises a centrosymmetric [Ni(Me(6)[14]dieneN(4))](2+) dication (Me(6)[14]dieneN(4) is 5,7,7,12,14,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene) and two O,O'-bis-(4-tert-butyl-phen-yl) dithio-phosphate anions. The Ni(II) ion lies on an inversion centre and displays a slightly distorted NiN(4) square-planar chelation arrangement with four N atoms from the Me(6)[14]dieneN(4) macrocycle. Two S atoms from symmetry-related anions are located in pseudo-axial positions with respect to the Ni(II) ion, with Ni⋯S distances of 3.

(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetra-azacyclo-tetra-deca-ne)copper(II) bis-(O,S-dibenzyl dithio-phosphate).

In the crystal structure of the title compound, [Cu(C(16)H(36)N(4))](C(14)H(14)O(2)PS(2))(2), the Cu(II) atom is located on an inversion center and is chelated by four N atoms of the macrocyclic meso-5,5,7,12,12,14- hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-decane ligand in a square-planar geometry, with Cu-N distances of 2.013 (3) and 2.014 (3) Å.

Bis(O,O'-diphenethyl dithio-phosphato-κS,S')bis-(4-methyl-pyridine-κN)nickel(II).

The title complex, [Ni(C(16)H(18)O(2)PS(2))(2)(C(6)H(7)N)(2)], exhibits a roughly octa-hedral coordination geometry. The Ni(II) atom lies on an inversion centre and is coordinated by four S atoms of O,O'-diphenethyl dithio-phosphate mol-ecules and two N atoms of 4-methyl-pyridine mol-ecules. Important geometric data include Ni-N = 2.

(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetra-azacyclo-tetra-deca-ne)nickel(II) bis-(O,O'-dibenzyl dithio-phosphate).

In the title salt-type 1:2 adduct, [Ni(C(16)H(36)N(4))](C(14)H(14)O(2)PS(2))(2) or [Ni(tet-a)][S(2)P(OCH(2)Ph)(2)](2), where tet-a is meso-5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-decane, the [Ni(tet-a)](2+) complex cation exhibits a relatively undistorted square-planar geometry about the Ni atom, which lies on an inversion centre and is coordinated by four macrocyclic N atoms. The two O,O'-bis-(2-phenyl-meth-yl) dithio-phosphate anions act as counter-ions to balance the charge and they inter-act with the complex through N-H⋯S hydrogen bonds. Important geometric data include Ni-N distances of 1.