A complete review of all known octacyanide-based clusters with an extensive discussion their structures, magnetic properties and multifunctionality.

"Converting" light energy to magnetization is the attribute of molecule-based compounds called photomagnets and inaccessible for conventional magnetic solids. The design synthesis such compounds, however, a formidable challenge, only few examples are known, all with rather low ordering temperatures well below boiling point liquid nitrogen. Herein, cyanide-bridged coordination polymer, {[MnII(imidazole)]2[WIV(CN)8]} n, exhibiting highest light-induced temperature ever observed hysteresis loop...

Abstract Bistable and stimuli‐responsive molecule‐based materials are promising candidates for the development of molecular switches sensors future technologies. The CN‐bridged {NH 4 [Ni(cyclam)][Fe(CN) 6 ]⋅5 H 2 O} n chain exists in two valence states: Ni II ‐Fe III ( 1 HT ) LT shows unique multiresponsivity under ambient conditions to various stimuli, including temperature, pressure, light, humidity, which generate measurable response form significant changes magnetic susceptibility color....

Abstract Luminescent metal‐organic frameworks (MOFs) are widely exploited as sensors due to their versatility and sensitivity external stimuli. Although there numerous luminescent MOF‐based thermometers or humidity sensors, only a few examples allow efficient detection of both these parameters. We present family MOF‐materials based on Sr 2+ Ba ions, 4,4′‐bipyridine‐ N , ’‐dioxide (4,4′‐bpdo) linkers, [M III (CN) 6 ] 3− species, described by the formulas {[Sr II 2.5 (NO 3 )][Sr (H 2 O)]}[M ]∙...

Two 3D bimetallic cyanido-bridged coordination polymers, [CuII(H4tetac)]2[MIV(CN)8]·4H2O (M = MoIV (1) and WIV (2)), based on copper(II) complex of tetracarboxylic-derivative cyclam, H4tetac (=1,4,8,11-tetrazacyclotetradecane-6,6,13,13-tetracarboxylic acid), have been synthesized characterized in terms structure, proton conductivity, the photomagnetic effect. The isostructural compounds crystallize polar Fdd2 space group present a diamond-like topology. carboxylic groups structure yield...

Functional materials incorporating cyanido-bridged Dy^IIICo^III molecules combine visible photoluminescence and slow magnetic relaxation, both switchable by the level of humidity within reversible room temperature dehydration process.

While metal-organic frameworks (MOFs) are at the forefront of cutting-edge porous materials, extraordinary sorption properties can also be observed in Prussian Blue Analogs (PBAs) and related materials comprising extremely short bridging ligands. Herein, we present a bimetallic nonporous cyanide-bridged coordination polymer (CP) {[Mn(imH)]2[Mo(CN)8]} n (1Mn; imH = imidazole) that efficiently reversibly capture release water molecules over tens cycles without any fatigue despite being based...

An alternating bimetallic {(H3O)[Ni(III)(cyclam)][Fe(II)(CN)6]·5H2O}n chain undergoes reversible dehydration at 40 °C accompanied by electron transfer which leads to Ni(II)-Fe(III) in about 50% of metal centres. The hydrated dark blue form is a paramagnet while the dehydrated yellowish-green shows ferromagnetic coupling between neighbouring Ni(II) and Fe(III).

Hexacyanidometallates of transition metal ions govern the topology and photoluminescence bimetallic d–f hybrid coordination networks incorporating uranyl cations.

The synthesized chiral (R)- and (S)-2-(1-hydroxyethyl)pyridine ligands (R/S-mpm) were introduced to self-assembled CoII-[WV(CN)8] 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 1-S; M Ni, 2-R 2-S). They consist 15 metal centers, 9 CoII or NiII ions, 6 [WV(CN)8]3– embedded in 6-capped body-centered cube topology. Bidentate mpm coordinated eight external sites induce their...

A new form of 2D honeycomb-like network is characterised by flat layers and undergoes single-crystal-to-single-crystal transformation to corrugated hexadecahydrate.

An inorganic three-dimensional [NiII(H2O)2]2[WIV(CN)8]·4H2O (1) framework undergoes a single-crystal-to-single-crystal transformation upon thermal dehydration, producing fully anhydrous phase NiII2[WIV(CN)8] (1d). The dehydration process induces changes in optical, magnetic, and expansion properties. While 1 reveals typical positive of the crystal lattice, greenish-yellow color, paramagnetic behavior, 1d is first ever reported octacyanido-based solid revealing negative expansion, also...

The development of new technologies requires research on novel functional materials. In recent years, controlling the optical properties magnetic materials has been investigated in fields such as chemistry, physics, and science. This brief review surveys property tuning molecular with an emphasis cyanido‐bridged coordination polymers. this article, particular interest is devoted to exhibiting drastic colour changes, photoinduced magnetisation, tuneable photoemission properties. Additionally,...

Reaction between [Ni(cyclam)](2+) and [W(CN)(8)](4-) leads to the formation of a 3D diamond-like network [Ni(cyclam)](2)[W(CN)(8)]·3.5H(2)O (1). The structure is characterised by intersecting channels 3-4 Å in diameter, filled with crystallisation water, most which released upon drying air, causing crystals collapse. Analogous compound [Ni(cyclam)](2)[Nb(CN)(8)]·3.5H(2)O (2), based on paramagnetic Nb(IV), could only be obtained as powder, due decomposition [Nb(CN)(8)](4-) complex under slow...

The coexistence of dehydration-driven charge transfer, magnetic interactions, and high proton conductivity was found in two bimetallic alternating CN-bridged chains {(H3O)[NiIII(cyclam)][MII(CN)6]·5H2O} n (M = Ru (1), Os (2); cyclam 1,4,8,11-tetraazacyclotetradecane). Dehydration these materials causes structural transformation triggers transfer between the metal centers: NiIII-NC-MII → NiII-NC-MIII. CT process, whose extent is tuned by change anionic building block, significant increase...

Abstract Discrete molecular species that can perform certain functions in response to multiple external stimuli constitute a special class of multifunctional materials called smart molecules. Herein, cyanido‐bridged coordination clusters {[Fe II (2‐pyrpy) 2 ] 4 [M IV (CN) 8 } ⋅ MeOH 6 H O (M=Mo ( 1 solv ), M=W ) and 2‐pyrpy=2‐(1‐pyrazolyl)pyridine are presented, which show persistent solvent driven single‐crystal‐to‐single‐crystal transformations upon sorption/desorption water methanol Three...

Changes in structure and magnetic properties accompanying guest removal, inclusion, or exchange two CN-bridged 2D networks of honeycomb topology: {[Ni(cyclam)]3[Fe(CN)6]2}n (1) {[Ni(cyclam)]3[Cr(CN)6]2}n (2) (cyclam = 1,4,8,11-tetraazacyclotetradecane) were studied by PXRD measurements. For each compound four pseudopolymorphic forms differing characteristics identified: fully hydrated form stable water, partly the air at ambient conditions, anhydrous form, MeOH-modified form. All can be...

Functional crystalline materials based on bimetallic cyanido-bridged {[DyIII(4-Mephen)(dmf)4][MV(CN)8]}·0.5H2O (M = Re, 1; Mo, 2; W, 3; 4-Mephen 4-methyl-1,10-phenanthroline) helices have been prepared. 1 is the first heterometallic coordination polymer incorporating an unexplored [ReV(CN)8]3– ion. Implementation of ReV-based diamagnetic analogue broadly investigated paramagnetic [MoV(CN)8]3– and [WV(CN)8]3– ions into d–f framework results in yellow photoluminescence originating from 4F9/2 →...

The 2D coordination network (NH4)2[NiII(cyclam)]3[NbIV(CN)8]2·21H2O (1·21H2O) was obtained on a cation-assisted synthetic pathway. reaction between [Ni(cyclam)]2+ and [Nb(CN)8]4- in the presence of excess NH4Cl resulted formation negatively charged layers with simultaneous incorporation NH4+ cations into microporous channels structure. 1·21H2O can be partly dehydrated single-crystal-to-single-crystal structural transformation to give (NH4)2[NiII(cyclam)]3[NbIV(CN)8]2·14H2O (1·14H2O)....

Molecular magnetism draws from the fundamental ideas of structural chemistry and combines them with experimental physics resulting in one highest profile current topics, namely molecular materials that exhibit multifunctionality. Recent advances design new generations multifunctional magnets retain functions building blocks non-trivial magnetic properties at higher temperatures provide promising evidence they may be useful for future construction nanoscale devices. This article is not a...

Structures and solvatomagnetic properties of two 1D CN‐bridged assemblies based on the complex [Mn(cyclam)] 3+ (cyclam = 1,4,8,11‐tetraazacyclotetradecane) were characterised. The isostructural {[Mn(cyclam)][Cr(CN) 6 ] · 6H 2 O} n ( 1· O) {[Mn(cyclam)][Fe(CN) 2· chains crystallise in space group C 2/ m . When dried air at a slightly elevated temperature hexahydrates undergo irreversible partial dehydration to stable dihydrates 2H O O. structure model proposed from powder XRD data shows lower...

Materials combining photoluminescence (PL) with sorption properties, such as those based on supramolecular assemblies or coordination polymers, are considered good candidates for the construction of optical sensors external stimuli....

A unique family of three-dimensional (3D) luminescent SrII–ReV metal–organic frameworks (MOFs), {[SrII(MeOH)5][ReV(CN)4(N)(bpen)0.5]·MeOH}n [1·MeOH; N3– = nitrido ligand, bpen 1,2-bis(4-pyridyl)ethane, and MeOH methanol], {[SrII(MeOH)4][ReV(CN)4(N)(bpee)0.5]·2MeOH}n [2·MeOH; bpee 1,2-bis(4-pyridyl)ethylene], {[SrII(bpy)0.5(MeOH)2][ReV(CN)4(N)(bpy)0.5]}n (3·MeOH; bpy 4,4′-bipyridine), is reported. They are obtained by the molecular self-assembly Sr2+ ions with tetracyanidonitridorhenate(V)...

Two 1D CN-bridged coordination polymers based on the cyclam (cyclam = 1,4,8,11-tetraazacyclotetradecane) complex of nickel in an unusual oxidation state III have been characterised terms structure and solvatomagnetic properties. The {[Ni(cyclam)][Cr(CN)6]·6H2O}n (1) {[Ni(cyclam)][Fe(CN)6]·6H2O}n (2) chains are isostructural crystallise space group C2/m. They undergo reversible partial dehydration at 40 °C to {[Ni(cyclam)][Cr(CN)6]·3H2O}n (1d) {[Ni(cyclam)][Fe(CN)6]·3H2O}n (2d), accompanied...