Intrinsic Fluorescence–Spin Crossover Interplay in the 3D FeII Hofmann-Type MOF {FeII(2,6-di(pyridin-4-yl)naphthalene)[MI(CN)2]2}·x(PhNO2) (MI = Ag, Au)
4 affiliations
- 1Instituto de Ciencia Molecular, Departamento de Química Inorgánica, Universidad de Valencia, Catedrático José Beltrán 2, Paterna, Valencia46980, Spain.
- 2Departamento de Física Aplicada, Universitat Politècnica de València, Camino de Vera s/n, Valencia46022, Spain.
- 3LCC-CNRS, Université de Toulouse, CNRS, Toulouse31077, France.
- 4Departamento de Química Física, Universitat de València, Dr Moliner 50, Burjassot46100, Spain.
Abstract
We report the synthesis, characterization, and photophysical properties of two isoreticular 3D Hofmann-type Metal-Organic Frameworks (MOFs), {Fe II (2,6-di(pyridin-4-yl), incorporating a naphthalene-based fluorescent ligand as bridging pillars. Single-crystal X-ray diffraction analysis of 1Au reveals a doubly interpenetrated primitive cubic (pcu) framework constructed from {Fe II 4 [M I (CN) 2 ] 4 } n grids pillared by the organic linker, with nitrobenzene molecules occupying the accessible voids and engaged in multiple host-guest interactions. Magnetic and calorimetric studies show a thermally induced and complete spin crossover (SCO) in both compounds, with similar transition temperatures but distinct cooperativity, including a multistep behavior pronounced in the Ag derivative. Variable-temperature fluorescence measurements of 1Ag and 1Au display an emission band centered at ca. 585 nm, whose intensity decreases upon cooling in correlation with the LS state population. This behavior is attributed to a reabsorption process consistent with an inner filter effect, highlighting the role of the spin-state-dependent optical properties of the framework. Structural analysis suggests that differences in the metal-cyanide linkage influence host-guest interactions and lattice response, thereby modulating the SCO profile. These results provide insights into the interplay between intrinsic fluorescence and SCO in porous frameworks and contribute to the rational design of multifunctional SCO-based materials.
Related
- Competing Ring-Opening and Hofmann Elimination Pathways in Aqueous TEMPO Catholytes: A First-Principles Study
- Fast and Slow Motions Drive Elusive Polymorphic Transitions in a Naphthalene-Diimide Crystal
- Unsymmetrical naphthalene diimides as electrochromic materials: tailoring structure for controlled optical and redox properties.
- Regioisomer-dependent room-temperature phosphorescence and low-k dielectric properties of naphthalene-bridged organoboranes.
- Naphthalene-Fused Meta-Dual-Boron Compounds Enable an 80 nm Redshift with Concurrently Narrowed Full Widths at Half Maximum
BibTeX
@article{orellanasilla2026intrinsic,
title = {{Intrinsic Fluorescence–Spin Crossover Interplay in the 3D FeII Hofmann-Type MOF FeII(2,6-di(pyridin-4-yl)naphthalene)[MI(CN)2]2·x(PhNO2) (MI = Ag, Au)}},
author = {Alejandro Orellana-Silla and M Carmen Muñoz and Gábor Molnár and Carlos Bartual-Murgui and José Antonio Real},
journal = {Inorganic Chemistry},
year = {2026},
month = sep,
doi = {10.1021/acs.inorgchem.6c02744},
url = {https://hal.science/hal-05745712v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Intrinsic Fluorescence–Spin Crossover Interplay in the 3D FeII Hofmann-Type MOF {FeII(2,6-di(pyridin-4-yl)naphthalene)[MI(CN)2]2}·x(PhNO2) (MI = Ag, Au)
AU - Alejandro Orellana-Silla
AU - M Carmen Muñoz
AU - Gábor Molnár
AU - Carlos Bartual-Murgui
AU - José Antonio Real
PY - 2026
DA - 2026/09/01
JO - Inorganic Chemistry
DO - 10.1021/acs.inorgchem.6c02744
UR - https://hal.science/hal-05745712v1
AB - We report the synthesis, characterization, and photophysical properties of two isoreticular 3D Hofmann-type Metal-Organic Frameworks (MOFs), {Fe II (2,6-di(pyridin-4-yl), incorporating a naphthalene-based fluorescent ligand as bridging pillars. Single-crystal X-ray diffraction analysis of 1Au reveals a doubly interpenetrated primitive cubic (pcu) framework constructed from {Fe II 4 [M I (CN) 2 ] 4 } n grids pillared by the organic linker, with nitrobenzene molecules occupying the accessible voids and engaged in multiple host-guest interactions. Magnetic and calorimetric studies show a thermally induced and complete spin crossover (SCO) in both compounds, with similar transition temperatures but distinct cooperativity, including a multistep behavior pronounced in the Ag derivative. Variable-temperature fluorescence measurements of 1Ag and 1Au display an emission band centered at ca. 585 nm, whose intensity decreases upon cooling in correlation with the LS state population. This behavior is attributed to a reabsorption process consistent with an inner filter effect, highlighting the role of the spin-state-dependent optical properties of the framework. Structural analysis suggests that differences in the metal-cyanide linkage influence host-guest interactions and lattice response, thereby modulating the SCO profile. These results provide insights into the interplay between intrinsic fluorescence and SCO in porous frameworks and contribute to the rational design of multifunctional SCO-based materials.
SN - 0020-1669
SN - 1520-510X
ER -