
Robert PodgajnyJagiellonian University | UJ · Faculty of Chemistry
Robert Podgajny
Professor
Wanted: early stage collaborators (BSc, MSc, PhD students) in the field of Coordination and Supramolecular Chemistry
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Publications (134)
A 2D cyanido-bridged architecture Zn II -[W V (CN) 8 ] 3– is smoothly pillared by N , N' -di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide (DPNDI) into 3D hybrid porous coordination polymer (PCP) {Zn II 3 (DMA) 6 [W V (CN) 8 ] 2 (DPNDI)·8DMA}. It shows significant uptake of H 2 O, MeOH or CHCl 3 vapours with...
Tunable photoluminescence (PL) is one of the hot topics in current materials science, and research performed on the molecular phases is at the forefront of this field. We present the new (Et4N)2[PtII(bph)(CN)2]⋅rez3⋅¹/3H2O (Pt2rez3) (bph=biphenyl‐2,2’‐diyl; rez3=3,3”,5,5”‐tetrahydroxy‐1,1’:4’,1”‐terphenyl, phenylene‐1,4‐diresorcinol coformer, a lin...
Design of metallosupramolecular materials encompassing more than one kind of supramolecular interaction can become deceptive, but it is necessary to better understand the concept of the controlled formation of supramolecular systems. Herein, we show the structural diversity of the bis-compartmental phenoxo-benzimidazole ligand H3L¹ upon self-assemb...
The triphenylmethane (trityl) group has been recognized as a supramolecular synthon in crystal engineering, molecular machine rotors and stereochemical chirality inductors in materials science. Herein we demonstrate for the first time how it can be utilized in the domain of molecular magnetic materials through shaping of single molecule magnet (SMM...
Polynuclear molecular clusters offer an opportunity to design new hierarchical switchable materials with collective properties, based on variation of the chemical composition, size, shapes, and overall building blocks organization. In this study, we rationally designed and constructed an unprecedented series of cyanido-bridged nanoclusters realizin...
Two dinuclear copper(II) complexes with macrocyclic Schiff bases K1 and K2 were prepared by the template reaction of (R)-(+)-1,1′-binaphthalene-2,2′-diamine and 2-hydroxy-5-methyl-1,3-benzenedicarboxaldehyde K1, or 4-tert-butyl-2,6-diformylphenol K2 with copper(II) chloride dihydrate. The compounds were characterized by spectroscopic methods. X-ray...
The new heterometallic compounds, [{Cu(pn)2}2Ni(NCS)6]n·2nH2O (1), [{CuII(trien)}2Ni(NCS)6CuI(NCS)]n (2) and [Cu(tren)(NCS)]4[Ni(NCS)6] (3) (pn = 1,2-diaminopropane, trien = triethylenetetramine and tren = tris(2-aminoethylo)amine), were obtained and characterized by X-ray analysis, IR spectra, XAS and magnetic measurements. Compounds 1, 2 and 3 sh...
Anisotropy of conventional magnetocaloric effect (MCE) and rotating magnetocaloric effect (RMCE) have been investigated in quasi-two-dimensional coordination polymer (AdeH){CuII[WV(CN)8]}·2H2O with high magnetic anisotropy and topological phase transition. Magnetic entropy changes (ΔSmag) were calculated from magnetic measurements of single crystal...
We present the new cyanido-bridged rhombus {[FeII(TPMA)]2[WV(CN)8]2}2– (Fe2W2) (TPMA = tris(2-pyridylmethyl)amine) cluster as a potential Secondary Building Block (SBB) for construction of polynuclear molecular materials. Fe2W2 is formed easily in self-assembly process between [FeII(TPMA)]Cl2 and TBA3[W(CN)8] in H2O/MeOH media, and was co-crystalli...
Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular orde...
For the first time, an abundant series of 12 colorful binary and ternary millimeter-sized core-shell composite crystals, representative of hierarchical crystalline species, were designed and prepared from functional magnetic polynuclear clusters phases using the epitaxial growth method. The synthesis is based on isomorphous (space group C2/c) cryst...
Moulick A, Milosavljevic V, Vlachova J, et al. Int J Nanomedicine. 2018;12:1277–1291.
The authors have advised due to an error that occurred inadvertently at the time of figure assembly, the QD+C image in Figure 1E on page 1282 is incorrect.
The correct Figure 1 is as follows.
Figure 1 Optical property analysis and dynamic light scattering (DLS) o...
Mutual positioning and non-covalent interactions in anion-aromatic motifs are crucial for functional performance of biological systems. In this context, regular, comprehensive Protein Data Bank (PDB) screening that involves various scientific points of view and individual critical analysis is of utmost importance. Analysis of anions in spheres with...
We report a new structure of {[Co(bpy)2(ox)][{Cu2(bpy)2(ox)}Fe(ox)3]}n·8.5nH2O NCU-1 presenting a rare ladder topology among oxalate-based coordination polymers with anionic chains composed of alternately arranged [Cu2(bpy)2(ox)]2+ and [Fe(ox)3]3- moieties. Along the a axis, they are separated by Co(III) units to give porous material with voids of...
Anion-π based compounds, materials, and processes have gained significant interest due to the diversity of their aesthetic non-covalent synthons, and thanks to their significance in biological systems, catalytic processes, anion binding and sensing, or the supramolecular organization of hierarchical architectures. While systems based on typical ino...
An original example of modular crystal engineering involving molecular magnetic {CuII[WV(CN)8]}- bilayers and adeninium cations (AdeH+) toward the new layered molecular magnet (AdeH){CuII[WV(CN)8]}·2H2O (1) is presented. 1 crystallizes within the monoclinic C2 space group (a = 41.3174(12), b = 7.0727(3), c = 7.3180(2) Å, β = 93.119(3)°, and V = 213...
The square-planar [PtX4]²⁻ complexes (X = Cl, Br) were successfully incorporated into preprogrammed hybrid organic–inorganic systems, exploiting their expected strong anion–π interactions with π-acidic hexaazaphenylenehexacarbonitrile, HAT(CN)6. The formation and properties of {[PtCl4]²⁻; HAT(CN)6} aggregates in MeCN solution were evaluated based o...
The series of crystalline phases composed of trimetallic 3d-5d-5d’ {Fe9[Re(CN)8]6-x[W(CN)8]x(MeOH)24}ꞏyMeOH (x = 1 (1), 2 (2), 3 (3), 4 (4) and 5 (5); y = 10-15) clusters were obtained by altering the octacyanidometalates composition. The temperature dependent studies involving SC XRD, SQUID magnetic measurements, IR spectroscopy and 57Fe Mössbauer...
Polynuclear coordination clusters (PCCs) provide considerable design capabilities towards various functions based on structural non-rigidity and spin state transitions, optical performance, catalytic properties and porosity. The elaboration of new synthetic pathways is fundamental towards advanced switchable and sensing materials, however, the reco...
Diverse functional potential of heterometallic systems based on octacyanidometallates places them at the forefront of research into modern molecule-based materials.
Combined Single-Crystal XRD, solution ¹³C and ¹⁹⁵Pt NMR, solid-state ¹⁹⁵Pt NMR and UV-vis measurements, together with comprehensive (TD)DFT calculations, are used to describe the supramolecular interactions and sequential concerted structural transformation occurring in a {PPh4⁺;[Pt(CN)4]2–;TCP;CH2Cl2} supramolecular system (TCP – tetracyanopyrazin...
The combinations of Co(II), octacyanidotungstate(V), and monodentate pyridine N-oxide (pyNO) or 4-phenylpyridine N-oxide (4-phpyNO) led to crystallization of novel crystalline phases {CoII[CoII8(pyNO)12(MeOH)12][WV(CN)8]6} (1) and {CoII[CoII8(4-phpyNO)7(MeOH)17][WV(CN)8]6}·7MeOH·(4-phpyNO)3 (2). In both architectures, metal–cyanide clusters are coo...
In this paper, three new heterometallic compounds were described and compared with the molecular formula [Cu(pn)2Zn(NCS)4] (1), [Cu(N,N-Me2-en)2Zn(NCS)4] (2), [Cu(N-Me-en)2Zn(NCS)4]∙½H2O (3) where pn = 1,2−diaminopropane, N,N-Me2-en = N,N‒dimethylethylenediamine and N-Me-en = N-methylethylenediamine, respectively. The compounds mentioned above were...
Crystal engineering of magnetic relaxation in the supramolecular networks based on nearly isotropic cyanido-bridged {Mn 9 [W(CN) 8 ] 6 L 8 (solv) 8 } clusters decorated by bulky 4,4’-di-tert-butyl-2,2’-bipyridine (But 2 bpy) and 4,7-diphenyl-1,10-phenanthroline (Ph 2 phen) ligands is presented. The three new...
Heterotrimetallic twenty-metal-centred {[MIIxCuII13–x(Me3tacn)12(H2O)][WIV(CN)8]2[WV(CN)8]5}·[WV(CN)8]·n(solvent) (M = Co, x = 1, 1; M = Ni, x = 1.5, 2; M = Mn, x = 1.5, 3; M = Fe, x = 1.5, 4; solvent = MeOH, H2O) and fifteen-metal-centred {CoII[CuII(Me3tacn)]8[WV(CN)8]6}·18MeOH (5) metal–cyanide clusters have been synthesized and characterized. Th...
Three new complexes forming a dynamic system and given by the following formulae: [Cu2(bpy)4Fe(ox)3]NO3•H2O 1, [Fe(bpy)3]2[Fe(ox)3]NO3•10H2O 2 and [Cu(bpy)3]2[Fe(ox)3]NO3•10H2O 3 (bpy – 2,2’-bipyridine, ox – oxalate), were synthesized from a methanol-water mixture or water, and characterized structurally, spectroscopically and magnetically. Compoun...
Homoleptic 5d metal ions polycyanido-complexes with high coordination numbers (C.N.), 8 for [W(CN)8]3-, 7 for [Re(CN)7]3-, and 6 for [Pt(CN)6]2-, are found to form supramolecular anion-π chains with the multisite anion receptor HAT(CN)6 (hexaazatriphenylenehexacarbonitrile). The chains adopt a zig-zag topology in the case of (XPh4)3[W(CN)8]·HAT(CN)...
The battle to conquer the magnificent molecular fortress located at the breath‐taking view of primeval desert mountain terrain is depicted in the graphic. Some positions are still to be taken, and they witness the dreadful duel scenes between the soldiers of the opposite armies that claim their rights. As their forces and skills are well balanced,...
Despite the importance of cell membranes for maintenance of integrity of cellular structures, there is still a lack of methods that allow simple real-time visualization of their damage. Herein, we describe gadolinium-Schiff base-doped quantum dots (QDs)-based probes (GdQDs) for a fast facile spatial labeling of membrane injuries. We found that GdQD...
Invited for the cover of this issue is the group of Robert Podgajny at Jagiellonian University. The image depicts the concept of the anion–π interactions between multisite anion receptors and cyanido‐complexes, in respect to the possible control of the formation of future polynuclear complexes. Read the full text of the article at 10.1002/chem.2018...
Multisite anion receptors AT(CN)6 and [M(CN)4]²⁻ stack under the regime of anion–π interactions to create the platform for a sponge‐like behavior and anion → receptor charge transfer. More information can be found in the Full Paper by R. Podgajny et al. (DOI: 10.1002/chem.201802933).
Two series of trimetallic {NiIIxCoII9‐x[WV(CN)8]6} (NiCoW) and {MnIIxCoII9‐x[WV(CN)8]6} (MnCoW) (x = 1‐8) crystalline solid solutions were constructed and systematically studied by SEM EDX, single crystal X‐ray diffraction (SC XRD) and magnetic measurements. The atomic Ni:Co:W and Mn:Co:W ratios in solid state follow fairly the stoichiometric conce...
We present the synthesis, crystal structures, spectroscopic characterization and comprehensive quantum‐chemical calculations for the novel series of anion‐π hybrid salts (XPh4)2[M(CN)4][HAT(CN)6]·3MeCN [X = P, M = NiII (1), PdII (3), PtII (5); X = As, M = NiII (2), PdII (4), PtII (6); HAT(CN)6 = 1,4,5,8,9,11‐hexaazatriphenylenehexacarbonitrile]. Th...
The combination of [WV(CN)8]3- anions with 3d metal cations MII in MeOH leads to the formation of pentadecanuclear spherical cyanido-bridged clusters {M[M(solv)3]8[M’(CN)8]6}, M9M’6. By decorating their surface with organic ligands or/and by installation of different ions in their coordination skeleton, one could tune high spin in the ground state,...
Conventional (MCE) and rotating (RMCE) magnetocaloric effects have been explored in the two-dimensional (2D) coordination polymer {(tetren)H5)0.8Cu(II)4[W(V)(CN)8]4·7.2H2O}n (WCu-t; tetren = tetraethylenepentamine). The unusual magnetostructural properties were exploited, including the bilayered Prussian Blue like coordination skeleton and the XY e...
In this study we have involved experimental and quantum Monte Carlo methods to investigate both the static and dynamic magnetic properties, which confirmed that the compound does not undergo a phase transition to a long range ordered state down to 2.0 K. However, magnetic measurements point to non negligible intercluster interactions in the low tem...
Cyanide-bridged {Mn(II)9[W(V)(CN)8]6} clusters with the ground state spin SSG = 39/2 were connected by a 4,4'-dipyridyl disulfide (4,4'-dpds) linker into 2-D double-connected coordination layers of the I(0)O(2) type, {Mn(II)9(4,4'-dpds)4(MeOH)16[W(V)(CN)8]6}·12MeOH (1). The intercluster contacts are controlled by the bridging Mn(II)-(4,4'-dpds)-Mn(...
Spin crossover (SCO) materials, revealing the externally tunable transition between two different spin states, arouse a great scientific interest due to the perspective application in information storage, display devices and sensing. Of a special importance are the molecular systems offering the possibility of multimodal switching within many spin...
Hexacyanidometalates (M = Fe(III), Co(III)) and multisite anion receptor HAT(CN)6 (1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile) recognize each other in acetonitrile solution and self-assemble into the novel molecular networks (PPh4)3[M(CN)6][HAT(CN)6] (M = Fe, 1; Co, 2) and (AsPh4)3[M(CN)6][HAT(CN)6]·2MeCN·H2O (M = Fe, 3; Co, 4). 1-4 contain t...
The rotating magnetocaloric effect (RMCE) is a new issue in the field of magnetic refrigeration. We have explored this subject on the two-dimensional (2D) enantiopure {[MnII(R-mpm)2]2[NbIV(CN)8]}·4H2O (where mpm = α-methyl-2-pyridinemethanol) coordination ferrimagnet. In this study, the magnetic and magnetocaloric properties of single crystals were...
CdTe/ZnSe core/shell quantum dot (QD), one of the strongest and most highly luminescent nanoparticles, was directly synthesized in an aqueous medium to study its individual interactions with important nucleobases (adenine, guanine, cytosine, and thymine) in detail. The results obtained from the optical analyses indicated that the interactions of th...
FTIR spectrum of CdTe/ZnSe QDs.
Abbreviations: FTIR, fourier transform infrared spectroscopy; QD, quantum dot.
In principle, any molecular magnet or coordination polymer, based on paramagnetic centers, can be a molecular magnetic sponge if it shows reversible solvent-induced structural and magnetic changes. This chapter talks about the original molecular magnetic sponges developed by Olivier Kahn and coworkers. It focuses on cyanide-bridged systems, where t...
Pentadecanuclear {CoII9[WV(CN)8]6} clusters were combined with bidentate 2,2′-bipyridine N,N′-dioxide (2,2′-bpdo) ligands resulting in two distinct molecules, {Co9W6(2,2′-bpdo)7} (cluster A) and {Co9W6(2,2′-bpdo)6} (cluster B), capped by seven and six 2,2′-bpdo ligands, respectively. They crystallize within a single {Co9W6(2,2′-bpdo)7}·{Co9W6(2,2′-...
The precisely controlled stoichiometric mixtures of Co(2+) and Fe(2+) metal ions were combined with the [W(V)(CN)8](3-) metalloligand in the methanolic solution which gave the series of trimetallic cyanido-bridged {Fe9-xCox[W(CN)8]6(MeOH)24}∙12MeOH (x = 0, 1, …, 8, 9; compounds 0, 1, …, 8, 9) clusters. All the compounds 0-9 are isostructural, and c...
The cyanido-bridged {CoII9[WV(CN)8]6} Single-Molecule Magnets grow spontaenously from the methanolic solution of Co2+ and [WV(CN)8]3- ions. Here, these molecules were combined with 2,2’-bipyridine N-oxide (2,2’-bpmo) ligand resulting in three novel crystalline phases: {CoII[CoII(2,2’-bpmo)(MeOH)]6[CoII(2,2’-bpmo)(MeCN)]2[WV(CN)8]6}∙8H2O∙2MeCN∙2MeOH...
A series of isostructural C3-symmetrical triple stranded dinuclear lanthanide [Ln2L3](NO3)3 molecules have been synthesized using subcomponent self-assembly of Ln(NO3)3 with 2-(methylhydrazino)benzimidazole and 4-tert-butyl-2,6-diformylphenol, where Ln = Tb(1), Dy(2), Ho(3), Er(4), Tm(5), Yb(6). The temperature dependent and field dependent magneti...
The synthesized chiral (R)- and (S)-2-(1-hydroxyethyl)pyridine ligands (R/S-mpm) were introduced to self-assembled CoII-[WV(CN)8] and NiII-[WV(CN)8] magnetic systems giving a remarkable series of four enantiopure cyanido-bridged clusters, {MII[MII(R/S-mpm)(MeOH)]8[WV(CN)8]6}·14MeOH (M = Co, 1-R and 1-S; M = Ni, 2-R and 2-S). They consist of 15 meta...
The unique enantiopure {[Λ-Co(II)((R)-mpm)2]3[W(V)(CN)8]2}·9H2O [(R)-1] and {[Δ-Co(II)((S)-mpm)2]3[W(V)(CN)8]2}·9H2O [(S)-1], where mpm = α-methylpyridinemethanol, magnetic spongelike materials, crystallizing in the chiral P21 space group, are constructed of cyanido-bridged {Co3W2} trigonal bipyramids with three cis-[Co(II)(mpm)2(μ-NC)2] moieties i...
The self-assembly of iron(II) ions with rare octacyanidorhenate(V) metalloligands in a methanolic solution results in the formation of a nanometric pentadecanuclear {Fe(II) 9 [Re(V) (CN)8 ]6 (MeOH)24 }⋅10 MeOH (1) molecule with a six-capped body-centered cubic topology. The cluster demonstrates a thermally-induced spin-crossover phase transition at...
The self-assembly of iron(II) ions with rare octacyanidorhenate(V) metalloligands in a methanolic solution results in the formation of a nanometric pentadecanuclear {FeII9[ReV(CN)8]6(MeOH)24}⋅10 MeOH (1) molecule with a six-capped body-centered cubic topology. The cluster demonstrates a thermally-induced spin-crossover phase transition at T1/2=195...
Octacyanidometallates make an important branch of cyanide-based molecular magnets that not only follow the trends in modern magnetochemistry and materials science but also have stimulated these fields from the very beginning and still blaze a trail by introducing new concepts such as heterotrimetallic systems, new functionalities and cross-effects...
Pyrazine-N,N'-dioxide (pzdo) was used as a linker in the design and synthesis of hybrid octacyanometalate-based networks. Four new compounds Na-6[W-v(CN)(8)](2)(pzdo)(7)center dot 5H(2)O (1), K-3 [W-V(CN) (8)](p z d o)(2)center dot 4 H2O (2), {Mn-6(II)(pzdo)(4)(MeOH)(10)[W-V(CN)(8)](4)}center dot 4MeOH (3), and {Mn-2(II)(pzdo)(H2O)(4)[W-V(CN)(8)]}c...
A bimetallic pentadecanuclear cyanido-bridged {Fe9[W(CN)8]6 (MeOH)24}·xMeOH cluster of an Fe(II/III)-W(IV/V) mixed valence nature, reveals a reversible single-crystal-to-single-crystal transformation, concomitant with metal-to-metal charge transfer between Fe and W ions. The dominance of (HS)Fe(II)-NC-W(V) units at a high temperature, and (HS)Fe(II...
Unique two dimensional enantiopure cyanido-bridged {[Mn-II(R-mpm) (2)](2)[Nb-IV(CN)(8)]}center dot 4H(2)O and {[Mn-II(S-mpm)(2)](2)[Nb-IV(CN)(8)]}center dot 4H(2)O (1-S) (mpm = alpha-methyl-2-pyridine-methanol) ferrimagnets with T-C = 23.5 K were synthesized and characterized. They reveal natural optical activity (NOA) due to the chiral crystal str...
Cyanido-bridged high-spin {CoII[CoII(MeOH)3]8[WV(CN)8]6} (Co9W6) clusters revealing single-molecule magnet behavior were combined with 4,4′-bipyridine-N,N′-dioxide (4,4′-bpdo) linkers, giving unique H-bonded supramolecular {CoII9(MeOH)24[WV(CN)8]6}·4,4′-bpdo·MeOH·2H2O (1) chains and one-dimensional coordination {CoII[CoII(4,4′-bpdo)1.5(MeOH)]8[WV(C...
The novel layered {CoII
3(2,29-bpdo)4(H2O)4[WV(CN)8]2}?8H2O (1) network (2,29-bpdo = 2,29-bipyridine-
1,19-dioxide) is built of 2-D corrugated cyanide-bridged brick-wall skeletons parallel to the bc
crystallographic plane. The coordination of chelating 2,29-bpdo to Co(II) gives 7-membered coordination
rings. Magnetic and heat capacity measurements...
Which way to choose? The trimetallic cyanide-bridged Fe(6) Co(3) W(6) cluster serves as a molecular platform for two cooperating electron transfer channels, W(V) -CN-(HS) Co(II) ⇄W(IV) -CN-(LS) Co(III) and W(V) -CN-(HS) Fe(II) ⇄W(IV) -CN-(HS) Fe(III) . {Co(II) (3) Fe(II) (6) [W(V) (CN)(8) ](6) (MeOH)(24) }⋅x MeOH has a first-order unique spin trans...
Wo soll es hingehen? Der trimetallische Cyanid‐verbrückte Fe6Co3W6‐Cluster beherbergt zwei kooperierende Elektronentransferkanäle, WV–CN–HSCoII WIV–CN–LSCoIII und WV–CN–HSFeII WIV–CN–HSFeIII. {CoII3FeII6[WV(CN)8]6(MeOH)24}⋅x MeOH ist durch einen thermischen ladungstransferinduzierten Spinübergang erster Ordnung charakterisiert und zeigt Spinbistabi...
To identify the origin of the XY spin dimensionality in the bilayered system {Cu4(tetrenH5)[W(CN)8]4·7.2H2O}n (WCuT) we use a combination of single-crystal experiments (bulk magnetization, neutron flipping ratio, electron magnetic resonance, neutron diffraction) and theoretical modeling (exchange-charge model of the crystal field, dipolar energy, a...
To identify the origin of the XY spin dimensionality in the bilayered system {Cu4(tetrenH5)[W(CN)8]4·
7.2H2O}n (WCuT) we use a combination of single-crystal experiments (bulk magnetization, neutron flipping
ratio, electron magnetic resonance, neutron diffraction) and theoretical modeling (exchange-charge model of
the crystal field, dipolar energy,...
We present a unique interpretation of X-ray absorption spectroscopy (XAS) spectra at Cu:K, W:L(3), and Mo:K edges of structurally related magnetic Cu(II)-[M(V)(CN)(8)](3-) compounds. The approach results in description of the structure of novel three-dimensional (3-D) Cu(II)(3)(pyz)[M(V)(CN)(8)](2)·xH(2)O, M = W (1), Mo, (2) polymers. Assemblies 1...
Complete overview of octacyanidometallate polymetallic assemblies is presented from a novel viewpoint of the importance of incorporated ligands. The ligands are classified according to their structure and binding mode in metal–ligand–octacyanidometallate systems and their impact on topology and functionality is discussed. Monodentate ligands favour...
Using a polyamine cation tetrenH55+ (tetren = tetraethylenepentaamine), we tailored the dynamic layered material (tetrenH5)1.6{CoII(H2O)2[MIV(CN)8]}4·xH2O (1, M = W, x = 12; 2, M = Mo, x = 11.2). 1 and 2 consist of strongly corrugated two-dimensional (2D) cyano-bridged monolayers {CoII(H2O)2[MIV(CN)8]}n2n– of square grid topology stacked in an alte...
The rapidly developing field of molecular magnetism supplies a multitude of novel compounds of unprecedented properties and structure. Molecular magnets predominantly belong to the class of compounds involving well localized magnetic moments. This feature together with the fact that the nature and symmetry of magnetic interactions is encrypted in t...
Crystals of (H3O){[Cu(dien)]4[W(CN)8]} [W(CN)8]2·6.5H2O (dien: diethylenetriamine) are prepared by slow diffusion of aqueous solutions of [Cu(dien)(H2O)2]Cl2 and Cs3[W(CN)8] in an H-tube at room temperature (pH 5.5, 22% yield).
The reversible removal of guest molecules in Mn2Nb magnetic coordination framework materials, as described by D. Pinkowicz, B. Sieklucka et al. in their Communication on page 3973 ff., causes a spectacular two-step molecular rearrangement of their skeleton involving the topotactic formation of an additional molecular bridge and the translocation of...
The aim and the scope of this review is to show the results of ten years of research following the first reports on magnetic and photomagnetic assemblies constructed from [M(CN)8]n–. It is illustrated on the basis of our own work as well as a wide range of studies carried out in numerous laboratories around the world. The diversity and evolution of...
The self-assembly of [CuII(dien)(H2O)2]2+ and [WV(CN)8]3− in aqueous solution leads to the formation (H3O){[CuII(dien)]4[WV(CN)8]}[WV(CN)8]2·6.5H2O (1). The crystal structure of 1 consists of an unprecedented {[CuII(dien)]4[WV(CN)8]}5+∞ chain of (2,8) topology, nonbridging [W(CN)8]3− anions, and crystallization water molecules. The analysis of magn...
Stairway to heaven: An Mn 2Nb coordination framework shows huge switching of the magnetic ordering temperature in two well-defined steps, finally reaching 100 K in its anhydrous form. The switching, controlled by removal/uptake of guest molecules, is related to an intraskeletal molecular rearrangement involving reversible formation/breaking of mole...
The cover picture shows the fragment of the cyanido-bridged framework of a series of 3D isostructural {[M′II(pyrazole)4]2[NbIV(CN)8]·4H2O}n (M′ = Mn, Fe, Co, Ni) molecular magnets illuminating the landscape of the old-fashioned ABIT-VH6 electronic motherboard. The Microreview by B. Sieklucka et al. on p. 305 ff presents different types of functiona...
Incorporation of urea molecules into the magnetic system MnII-[NbIV(CN)8] results in formation of two magnetic polymorphs {[MnII(H2O)(urea)2]2[NbIV(CN)8]}n chiral α and centric β crystallizing in space groups P41 and P1̅, respectively. Both polymorphs exhibit extremely similar structures and are soft ferrimagnets with critical temperatures of 43 an...
Pentadecanuclear cyano-bridged high spin {MnII9WV6(CN)48(solv)24} clusters serve as bifunctional molecular building blocks in the construction of a {MnII9[WV(CN)8]6(dpe)5(MeOH)10}·14MeOH (dpe = trans-1,2-di(4-pyridyl)ethylene) organic−inorganic hybrid network of I1O2 topology. The intercluster connections are formed by Mn−NC−W and Mn−dpe−Mn linkage...
The fast developing field of molecule-based magnets involving organic and coordination chemistry provides the physicist with a multitude of novel compounds of unprecedented structure. The magnetic structure of Cu 4 tetrenWCN 8 4 1 was shown to consist of weakly coupled double layers. By contrast, in the structur-ally similar compound Cu 2+x Cu 4 WC...