Cluster-Expanded Prussian Blue Analogues

Abstract

A method for expanding the pores in crystalline frameworks is demonstrated with the substitution of face-capped octahedral [Re 6 Q 8 (CN) 6 ] 4-(Q ) Se, Te) clusters into the Prussian blue structure. The clusters react in aqueous solution with Ga 3+ and Fe 3+ , respectively, to precipitate Ga 4 [Re 6 Se 8 (CN) 6 ] 3 ‚xH 2 O and Fe 4 [Re 6 -Te 8 (CN) 6 ] 3 ‚xH 2 O. Rietveld analysis of X-ray powder diffraction data for the former compound confirms the expanded crystal structure, which features large water-filled cavities more than twice the volume of those in Prussian blue. The new materials can be dehydrated without loss of integrity, and maintain crystallinity at temperatures up to 250 or 300°C. Further, the increase in void volume is shown to significantly enhance their capacities as molecular sieves and enable absorption of larger alcohol molecules such as ethanol and n-propanol. A soluble form of the black iron-containing phase exhibits a cluster-to-metal charge-transfer band at 736 nm, slightly lower energy than the metal-to-metal charge-transfer band responsible for the color of Prussian blue.

Structure of a new molecular rhenium cluster complex: trans-{[Ni(NH3)5]2×[Re6Se8(CN)4(OH)2]}·6H2O

“…The lengths of Re-Re (2.6147-2.640 Å), Re-Se (2.5159-2.5395 Å), Re-C (2.090-2.106 Å), and C-N (1.145-1.149 Å) bonds are comparable to the data for other complexes containing the [Re 6 Se 8 (CN) 6 ] 4cluster core [10][11][12][13][14][15][16][17][18][19][20], but are somewhat longer (∼0.02 Å) than Re-Re, Re-Se, Re-O (2.080 Å) bonds in the complexes with the [Re 6 Se 8 (OH) 6 ] 4cluster core [5,21]. Molecular complexes and crystallization water molecules are joined by an extended system of hydrogen bonds.…”

Supramolecular Frameworks Built up from Red‐Phosphor­escent trans‐Re6 Cluster Building Blocks: One Pot Synthesis, Crystal Structures, and DFT Investigations

“…Indeed, many molecular assemblies and nanomaterials built up from M 6 clusters carriers of original chemical and physical properties [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] or as structuring moieties have been reported these last years. [26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43] M 6 clusters in medium oxidation state are stabilized by inorganic face-capping and terminal inorganic or organic ligands to form [{M 6 Q ], interstitial L ligands and water molecules. 1 and 2 present 2D and 3D cluster frameworks, respectively.…”

“…Many 3D frameworks with topology related to Prussian blue or Super-Prussian blue series as well as layered structures have been reported in the literature. [26][27][28][29][30][31][32][33][34][35][36][37][48][49][50][51][52] Some of them could be relevant materials for the elaboration of chemical sensors. [28] A second strategy is the use of bidentate linkers.…”

Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5− as building blocks

“…square antiprism geometry is distorted, In Ce 3+ coordination cation, the Ce-O bonds are in the range of 0.2400(2)-0.2600(15) nm. The average bond lengths for Ce-O (DMF) and Ce-O d are 0.2420 nm and 0.2500 nm, and the Ce-O w bond length is 0.2600 (15) nm, which indicates that the charge density at O (DMF) is larger than that of O w and O d .In the coordination geometry of the Ce 3+ cation, when the three terminal oxygen atoms (O3, O6 and O8) are distributed in equilateral triangle motif, steric hindrances are the smallest between anion-anion, cation-cation and anion-cation interactions, but that is not really the case.The O(3)-Ce(1)-O(6), O(8)-Ce(1)-O(3) and O(8)-Ce(1)-O(6) bond angles are 74.7(5)°, 148.3(5)° and 135.9(5)°, respectively, probably because that steric hindrance of DMF molecules coordinated with Ce 3+ coordination cation is bigger.…”

“…Combination applications of routine synthetic methods and various new synthetic methods will continually impregnate new vital force and energy for POMs chemistry [7][8][9][10][11] . In the fields of designing and assembling molecule-based materials with structures constructed by the so-called anion-cation salts or host-guest solids, POMs act as inorganic building blocks with novel structures and benign performances due to their surface bridging or terminal oxygen atoms possessing the strong coordination and bonding capability [12][13][14][15][16][17][18] . Many isolated and 1D crystal structures with saturated Keggin anions as building blocks have been reported [19][20][21][22][23][24][25][26][27][28] , however, 2D and high dimensional structures are relatively rare [29][30][31] .…”