Hierarchical Spin‐Crossover Cooperativity in Hybrid 1D Chains of Fe^II‐1,2,4‐Triazole Trimers Linked by [Au(CN)₂]⁻ Bridges

Abstract

Foremost, practical applications of spin‐crossover (SCO) materials require control of the nature of the spin‐state coupling. In existing SCO materials, there is a single, well‐defined dimensionality relevant to the switching behavior. A new material, consisting of 1,2,4‐triazole‐based trimers coordinated into 1D chains by [Au(CN)2]− and spaced by anions and exchangeable guests, underwent SCO defined by elastic coupling across multiple dimensional hierarchies. Detailed structural, vibrational, and theoretical studies conclusively confirmed that intra‐trimer coupling was an order of magnitude greater than the intramolecular coupling, which was an order of magnitude greater than intermolecular coupling. As such, a clear hierarchy on the nature of elastic coupling in SCO materials was ascertained for the first time, which is a necessary step for the technological development of molecular switching materials.

Highly Efficient and Selective Recognition of Dicyanoaurate(I) by a Bambusuril Macrocycle in Water

“…The anions are bound at an angle ( � 50°) with only half the anion perturbing into the anion-binding cavity, exhibiting a single CÀ H•••M interaction. Both anions are found in a bent conformation with angles less than 170°, not usually observed for Au [17][18][19] and even more rare in case of Ag. [20][21][22] The cyanide ligand found within the anion-binding cavity is coordinated to the metal at an angle of 166°, in contrast with most of the literature values of 175°-180°o bserved for these fairly linear anions.…”

Synthesis methods, structure and applications of metal di-, tetra- and dihalodicyanoaurates

“…Описанные с цианоауратами металлов бидентантные мостиковые N-доноры нелинейного характера включают в себя пиримидин [87], 1,2-бис(4-пиридил)этан (bipe) [156] и (E)-1-фенил-N-(1,2,4-триазол-4-ил)метанимин (bztrz) [157]. Синтез комплексов с ними приведен ниже.…”

“…типов октаэдрически окруженных ядер занных шестью μ 2 -молекулами bztrz места у Fe(1) занято мостиковым и терминальным анионами [ bztrz-лигандом. Остаточный положительный заряд компенсируется свободными дицианоаурат ионами, участвующими с [Au(CN 3,210 Å. Гостевые молекулы воды и метанола располагаются в небольших карманах между с седними полимерными цепочками [157].…”

“…--мостиками в Au I •••Au I -контактах длиной в интервале 3,102 Гостевые молекулы воды и метанола располагаются в небольших карманах между с седними полимерными цепочками[157].Bulletin of the South Ural State University. Ser.…”

Guest water-induced structural transformation and spin-crossover variation of a two-dimensional Hofmann-type compound

“…[1][2][3][4][5][6][7][8][9][10][11] This interconversion is usually observed in transition metal ion compounds with 3d 4 -3d 7 electronic configurations. [12][13][14][15][16][17][18][19][20][21] As a consequence of the spin transition, the magnetic susceptibility, optical properties, crystal lattice, and other chemical and physical properties of the material can be significantly shifted. Therefore, such materials hold great promise for diverse applications in fields like data storage, displays, and sensors.…”