Exploring porosity in a flexible 3D organic-inorganic {ZnII3(4DPNDI)[W(CN)]} coordination network.

A 2D cyanido-bridged architecture Zn-[W(CN)] is smoothly pillared by ,'-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide (4DPNDI) into 3D hybrid porous coordination polymer (PCP) {ZnII3(DMA)[W(CN)](4DPNDI)·8DMA}. It shows significant uptake of HO, MeOH or CHCl vapours with easy regeneration to the native form, and breathing-type CO adsorption contrasting non-porosity towards N, providing a new example of a highly flexible porous material.

Influence of O-H⋅⋅⋅Pt interactions on photoluminescent response in the (EtN){[Pt(bph)(CN)][phenylene-1,4-diresorcinol]} framework.

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 (EtN)[Pt(bph)(CN)]⋅rez3⋅/HO (Pt2rez3) (bph=biphenyl-2,2'-diyl; rez3=3,3",5,5"-tetrahydroxy-1,1':4',1"-terphenyl, phenylene-1,4-diresorcinol coformer, a linear quaternary hydrogen bond donor) co-crystal salt based on the recently appointed promising [Pt(bph)(CN)] luminophore. Within the extended hydrogen-bonded subnetwork [Pt(bph)(CN)] complexes and rez3 coformer molecules form two types of contacts: the O-H⋅⋅⋅N ones in the equatorial plane of the complex and non-typical O-H⋅⋅⋅Pt ones along its axial direction.

Nonlinear and Emissive {[M(CN)]···Polyresorcinol} (M = Fe, Co, Cr) Cocrystals Exhibiting an Ultralow Frequency Raman Response.

Optically active functional noncentrosymmetric architectures might be achieved through the combination of molecules with inscribed optical responses and species of dedicated tectonic character. Herein, we present the new series of noncentrosymmetric cocrystal salt solvates (PPh)[M(CN)](L)·solv (M = Cr(III), Fe(III), Co(III); L = polyresorcinol coformers, multiple hydrogen bond donors: 3,3',5,5'-tetrahydroxy-1,19-biphenyl, DiR, = 2, or 5'-(3,5-dihydroxyphenyl)-3,3″,5,5″-tetrahydroxy-1,19:3',1″-terphenyl, TriRB, = 1) denoted as and , respectively. The hydrogen-bonded subnetworks {[M(CN)];L} of , , or topology are formed through structural matching between building blocks within supramolecular -bis(chelate)-like {[M(CN)];(L)(L)} or tris(chelate)-like {[M(CN)];(L)} fragments.

Site Selectivity for the Spin States and Spin Crossover in Undecanuclear Heterometallic Cyanido-Bridged Clusters.

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 realizing new undecanuclear topology: Fe[Fe(bzbpen)][W(CN)][W(CN)]·18MeOH (), Na[Co(bzbpen)][W(CN)][W(CN)]·28MeOH (), Na[Ni(bzbpen)][W(CN)][W(CN)]·27MeOH (), and Co[Co(/-pabh)][W(CN)][W(CN)]·26MeOH [ and ; bzbpen = ,-dibenzyl-,-bis(pyridin-2-ylmethyl)ethane-1,2-diamine; /-pabh = (/)--(1-naphthyl)-1-(pyridin-2-yl)methanimine], of size up to 11 nm, ca. 2.

New Dinuclear Macrocyclic Copper(II) Complexes as Potentially Fluorescent and Magnetic Materials.

Two dinuclear copper(II) complexes with macrocyclic Schiff bases and were prepared by the template reaction of ()-(+)-1,1'-binaphthalene-2,2'-diamine and 2-hydroxy-5-methyl-1,3-benzenedicarboxaldehyde , or 4--butyl-2,6-diformylphenol with copper(II) chloride dihydrate. The compounds were characterized by spectroscopic methods. X-ray crystal structure determination and DFT calculations confirmed their geometry in solution and in the solid phase.

Supramolecular -"Bis(Chelation)" of [M(CN)] (M = Cr, Fe, Co) by Phloroglucinol (HPG).

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 ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic -metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh)[M(CN)](HPG)·2MeCN (M = Cr, ; Fe, ; Co ; HPG = phloroglucinol, 1,3,5-trihydroxobenzene).

Exploring the structure-property schemes in anion-π systems of d-block metalates.

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 inorganic anions or organic residues have been widely reviewed in recent years, those involving anionic d metal comlexes as the main components have been treated with a rather secondary interest. However, actively exploring the new systems of the latter type we have recognized systematic advances in the field.

Binding of anionic Pt(ii) complexes in a dedicated organic matrix: towards new binary crystalline composites.

The square-planar [PtX] 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). The formation and properties of {[PtCl]; HAT(CN)} aggregates in MeCN solution were evaluated based on their UV-Vis spectra to reveal the approximate binding constant K = 7.9(2) × 10 dm mol, molar absorption coefficient ε = 1.

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.

Tuning of High Spin Ground State and Slow Magnetic Relaxation within Trimetallic Cyanide-Bridged {Ni Co [W (CN) ] } and {Mn Co [W (CN) ] } Clusters.

Two series of trimetallic {Ni Co [W (CN) ] } (NiCoW) and {Mn Co [W (CN) ] } (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 the solid state follow the stoichiometric concentration in the mother MeOH solutions fairly well. The structural studies revealed a definite strong tendency of smaller 3d ions to locate in the central [M(μ-NC) ] moiety of the skeleton: Ni over the Co and Co over Mn .

Modulation of the Fe spin crossover effect in the pentadecanuclear {Fe[M(CN)]} (M = Re, W) clusters by facial coordination of tridentate polyamine ligands.

Spin crossover (SCO) materials, revealing the externally tunable transition between two different spin states, arouse great scientific interest due to their perspective application in information storage, display devices and sensing. Of special importance are the molecular systems offering the possibility of multimodal switching within many spin centers. This is achievable in polynuclear clusters consisting of several SCO-active complexes, however, such molecules are very rare.

Anion-π recognition between [M(CN)] complexes and HAT(CN): structural matching and electronic charge density modification.

Hexacyanidometalates (M = Fe, Co) and multisite anion receptor HAT(CN) (1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile) recognize each other in acetonitrile solution and self-assemble into the novel molecular networks (PPh)[M(CN)][HAT(CN)] (M = Fe, 1; Co, 2) and (AsPh)[M(CN)][HAT(CN)]·2MeCN·HO (M = Fe, 3; Co, 4). 1-4 contain the stacked columns {[M(CN)];[HAT(CN)]} separated by the organic cations. All of the M-C[triple bond, length as m-dash]N vectors point collectively towards the centroids of pyrazine rings on neighboring HAT(CN) molecules, with Ncentroid distances that are under 3 Å.