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Metal-Organic Frameworks with d–f Cyanide Bridges: Structural Diversity, Bonding Regime, and Magnetism

  • Marilena Ferbinteanu
  • Fanica Cimpoesu
  • Stefania TanaseEmail author
Chapter
Part of the Structure and Bonding book series (STRUCTURE, volume 163)

Abstract

We present a selection of metal-organic frameworks based on d–f and f–f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the interdisciplinary approach developed. Significant experimental and computational strategies of other researchers are also reviewed. The bonding regime of lanthanide units in MOFs is similar to those encountered in mono- or polynuclear f-type coordination compounds. However, the steric demands of constructing a three-dimensional network determine specific ligand composition and topologies at the local f nodes. Due to weak interaction propensity of the inner shell f orbitals, the electronic structure treatments of lanthanide units require certain conceptual and technical subtleties. With proper handling, multiconfiguration wave function approaches as well as density functional theory (DFT) treatments can be analyzed in terms of meaningful ligand field (LF) modeling. The interplay of LF and spin–orbit (SO) effects in determining the magnetic anisotropy is illustrated, after reviewing the experimental magnetic behavior of several d–f cyanide-bridged systems.

Keywords

Computational chemistry Cyanide bridges Lanthanide ions Ligand field theory Magnetic anisotropy Prussian blue analogues 

Abbreviations

ADF

Amsterdam density functional

AO

Atomic orbital

AOC

Average of configurations

bpy

2,2′-Bipyridyl

bpym

2,2′-Bipyrimidine

CASSCF

Complete active space self-consistent field

DFT

Density functional theory

DMF

Dimethylformamide

EDA

Energy decomposition analysis

H2mpca

5-Methyl-2-pyrazine dicarboxylic acid

HF

Hartree–Fock

hfac

1,1,1,5,5,5-Hexafluoro-pentane-2,4-dionate

HINA

Isonicotinic acid

LF

Ligand field theory

LFDFT

Ligand field density functional theory

MO

Molecular orbital

MOF

Metal-organic framework

PBAs

Prussian blue analogues

PT2

Second-order perturbation

pz

Pyrazine

pzam

Pyrazine-2-carboxamide

ROHF

Restricted open-shell Hartree–Fock

SO

Spin–orbit

terpy

2,2:6′2″-Terpyridine

Notes

Acknowledgments

ST thanks the Netherlands Organisation for Scientific Research (NWO) for a Veni grant. FC and MF acknowledge support from the Romania-Italy cooperation grant of Romanian Academy and PCE 14/2013 UEFISCDI research grant. We thank Dr. Alessandro Stroppa for useful discussions.

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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Marilena Ferbinteanu
    • 1
  • Fanica Cimpoesu
    • 2
  • Stefania Tanase
    • 3
    Email author
  1. 1.Faculty of Chemistry, Inorganic Chemistry DepartmentUniversity of BucharestBucharestRomania
  2. 2.Institute of Physical ChemistryBucharestRomania
  3. 3.Van’t Hoff Institute for Molecular SciencesUniversity of AmsterdamAmsterdamThe Netherlands

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