Making soluble Dy single-molecule magnets red emissive through their functionalization by ruthenium-cyanido luminophores.

We present an efficient strategy for obtaining red-emissive molecular nanomagnets by exploring a heterometallic approach. We report the {[Dy(4-pyridone)][Ru(CN)(phen)]}·(CFSO)·2MeOH (phen = 1,10-phenanthroline) compound composed of exchange-coupled {DyIII2} single-molecule magnets functionalized by Ru(II)-cyanido units. The latter makes the resulting {DyIII2RuII2} cations a unique example of a soluble lanthanide SMM exhibiting red charge-transfer photoluminescence in the solution and solid state, well enhanced when compared with the cyanido precursor.

Chiral cadmium-amine complexes for stimulating non-linear optical activity and photoluminescence in solids based on aurophilic stacks.

The design of high-performance optical materials can be realized using coordination polymers (CPs) often supported by non-covalent interactions, such as metallophilicity. The challenge is to control two or more optical effects, , non-linear optics (NLO) and photoluminescence (PL). We present a new strategy for the combination of the NLO effect of second-harmonic generation (SHG) and the visible PL achieved by linking dicyanidoaurate(i) ions, which form luminescent metallophilic stacks, with cadmium(ii) complexes bearing chiral amine ligands, used to break the crystal's symmetry.

Optical Phenomena in Molecule-Based Magnetic Materials.

Since the last century, we have witnessed the development of molecular magnetism which deals with magnetic materials based on molecular species, i.e., organic radicals and metal complexes.

SHG-active luminescent thermometers based on chiral cyclometalated dicyanidoiridate(iii) complexes.

Multifunctional optical materials can be realized by combining stimuli-responsive photoluminescence (PL), , optical thermometry, with non-linear optical (NLO) effects, such as second-harmonic generation (SHG). We report a novel approach towards SHG-active luminescent thermometers achieved by constructing unique iridium(iii) complexes, -[Ir(CN)(,-pinppy)] (,-pinppy = (,)-2-phenyl-4,5-pinenopyridine), bearing both a chiral 2-phenylpyridine derivative and cyanido ligands, the latter enabling the formation of a series of molecular materials: (TBA)[Ir(CN)(,-pinppy)]·2MeCN (1) (TBA = tetrabutylammonium) and (Bu-DABCO)[Ir(CN)(,-pinppy)](i)·MeCN (2) (Bu-DABCO = 1-(-butyl)-1,4-diazabicyclo-[2.2.

Synchronous Switching of Dielectric Constant and Photoluminescence in Cyanidonitridorhenate-Based Crystals.

Switching of multiple physical properties by external stimuli in dynamic materials enables applications in, e.g., smart sensors, biomedical tools, as well as data-storage devices.

Neutral dicyanidoferrate(II) metalloligands for the rational design of dysprosium(III) single-molecule magnets.

Diamagnetic -dicyanidoferrate(II) complexes bearing blocking aromatic diimines, -[Fe(CN)(L)] (L = 2,2'-bipyridine, 1,10'-phenanthroline) serve as metalloligands to Dy centres leading to a rigid cyanido-bridged chain of vertex-sharing {DyFe} squares which constrains the equatorial plane of embedded 4f metal ions. This results in a novel convenient route to rationally designed single-molecule magnets as the magnetic anisotropy of Dy centres can be efficiently generated by inserting aromatic -oxide ligands on labile axial positions.

Solvent- and Temperature-Driven Photoluminescence Modulation in Porous Hofmann-Type Sr-Re Metal-Organic Frameworks.

A unique family of three-dimensional (3D) luminescent Sr-Re metal-organic frameworks (MOFs), {[Sr(MeOH)][Re(CN)(N)(bpen)]·MeOH} [; N = nitrido ligand, bpen = 1,2-bis(4-pyridyl)ethane, and MeOH = methanol], {[Sr(MeOH)][Re(CN)(N)(bpee)]·2MeOH} [; bpee = 1,2-bis(4-pyridyl)ethylene], and {[Sr(bpy)(MeOH)][Re(CN)(N)(bpy)]} (; bpy = 4,4'-bipyridine), is reported. They are obtained by the molecular self-assembly of Sr ions with tetracyanidonitridorhenate(V) metalloligands, [Re(CN)(N)], and pyridine-based organic spacers (L = bpen, bpee, bpy). Such a combination of molecular precursors results in bimetallic Sr-Re cyanido-bridged layers further bonded by organic ligands into pillared Hofmann-type coordination skeletons.

Tuning of the phase transition between site selective SCO and intermetallic ET in trimetallic magnetic cyanido-bridged clusters.

A series of crystalline phases composed of trimetallic 3d-5d-5d' {Fe[Re(CN)][W(CN)](MeOH)}·yMeOH (x = 1 (1), 2 (2), 3 (3), 4 (4) and 5 (5); y = 10-15) clusters were obtained by altering the octacyanidometalate composition. The temperature dependent studies involving SC XRD, SQUID magnetic measurements, IR spectroscopy and Fe Mössbauer spectroscopy revealed reversible phase transition with the retention of single crystal character in each congener. The transition was assisted by reversible spin-crossover (SCO) Fe↔Fe transition at the central Fe1(ii) site for FeReW (1), FeReW (2), FeReW (3) and FeReW (4).

Structural Disorder in High-Spin {CoW} ()-[Pyridine N-Oxides] () Architectures.

The combinations of Co(II), octacyanidotungstate(V), and monodentate pyridine -oxide (pyNO) or 4-phenylpyridine -oxide (4-phpyNO) led to crystallization of novel crystalline phases {Co[Co(pyNO)(MeOH)][W(CN)]} () and {Co[Co(4-phpyNO)(MeOH)][W(CN)]}·7MeOH·(4-phpyNO) (). In both architectures, metal-cyanide clusters are coordinated by -oxide ligands in a simple monodentate manner to give the spherical objects of over 1 nm core diameter and about 2.2 nm () and 3 nm () of the total diameter, terminated with the aromatic rings.

Bulky ligands shape the separation between the large spin carriers to condition field-induced slow magnetic relaxation.

Crystal engineering of magnetic relaxation in supramolecular networks based on almost isotropic cyanido-bridged {Mn9[W(CN)8]6L8(solv)8} clusters decorated by bulky 4,4'-di-tert-butyl-2,2'-bipyridine (But2bpy) and 4,7-diphenyl-1,10-phenanthroline (Ph2phen) ligands is presented. The three new compounds {MnII9[WV(CN)8]6(But2bpy)8(MeOH)8}·Pri2O·13MeOH (1), {MnII9[WV(CN)8]6(But2bpy)8(MeOH)6(H2O)2}·4Pri2O·2H2O (1a), and {MnII9[WV(CN)8]6(Ph2phen)8(MeOH)8}·29MeOH·6H2O (2) were characterized structurally and magnetically. Compound 1 exhibits unequivocal domination of repulsive intercluster contacts operating between the side But groups leading to intercluster distances exceeding 10 Å in all three dimensions.