Charge‐Transfer Phase Transition of a Cyanide‐Bridged Fe^II/Fe^III Coordination Polymer

Abstract

Heterometallic Prussian blue analogues are known to exhibit thermally induced charge transfer, resulting in switching of optical and magnetic properties. However, charge-transfer phase transitions have not been reported for the simplest FeFe cyanide-bridged systems. A mixed-valence Fe(II) /Fe(III) cyanide-bridged coordination polymer, {[Fe(Tp)(CN)3 ]2 Fe(bpe)⋅5 H2 O}n , which demonstrates a thermally induced charge-transfer phase transition, is described. As a result of the charge transfer during this phase transition, the high-spin state of the whole system does not change to a low-spin state. This result is in contrast to FeCo cyanide-bridged systems that exhibit charge-transfer-induced spin transitions.

Redox‐Assisted Self‐Assembly of a Water‐Soluble Cyanido‐Bridged Mixed Valence {CoIII/FeII}2 Square

“…[1][2][3][4] Somes eminal works exist that have proved to be the startingp oint for the better understanding of the intervalence charget ransfer and the coupling established between the metal centers involved. [3,[5][6][7][8][9][10][11][12] Considerable research hasb een devoted to these compounds for al ong time, but recentlye mphasis has shifted from simple dinuclears ystems [4,[13][14][15][16][17][18][19][20][21][22] or non-discrete complex materials [13,[23][24][25][26][27] to discrete homo-or heterosupramolecular species. [16,[28][29][30][31][32][33][34][35][36][37] The establishmento fs tructure-property relationships for the latter,a sw ell as their theoretical treatment, are facilitated by the fact that the structure is finite and the metal-coordination environments are well defined.…”

A cyanide-bridged FeIII–MnII heterobimetallic one-dimensional coordination polymer: synthesis, crystal structure, experimental and theoretical magnetism investigation

“…Among the fields associated with functional CPs, magnetism is of interest. Molecule-based magnetic materials (Sato et al, 1996;Shatruk et al, 2009;Aguilà et al, 2016;Cornia et al, 2011), including high-T c magnets (Sato et al, 1996), single-molecule magnets (SMMs) (Visinescu et al, 2016;Qian et al, 2013), single-chain magnets (SCMs) Ferbinteanu et al, 2005), spin-crossover (SCO) materials (Lan, Valverde-Muñ oz et al, 2019; Zhang et al, 2017) and chiral magnetic materials (Zhang, Ferko et al, 2014;Zhang, Kang et al, 2016;Zhang et al, 2015;Ru et al, 2014), continue to attract interest due to the magnetic coupling properties between the paramagnetic metal centres, the magneto-structural correlation and the exotic magnetic phenomena. Therefore, a large number of CPs with unique magnetic properties and novel topologies have been designed and synthesized, many of which exhibit interesting magnetic properties.…”

Role of the Outer Metal of Double Metal Cyanides on the Catalytic Efficiency in Styrene Oxidation

“…The reported catalytic activity in this family of compounds shows a certain dependence on the involved metal (M) [15], an effect that deserves to be studied since it could be used as a way of tuning the catalytic properties of these materials. The outer cations of this type of compound maintain mixed valences [16,17], which can act as mediators in the transfer of electrons [18]. Likewise, all M metals are sited at the pore surface, with the possibility of direct interaction with the reactants molecules in the reaction medium.…”