PMID- 28509544
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20180216
LR  - 20180216
IS  - 1520-510X (Electronic)
IS  - 0020-1669 (Linking)
VI  - 56
IP  - 11
DP  - 2017 Jun 5
TI  - Search for Electron Delocalization from [Fe(CN)(6)](3-) to the Dication of 
      Viologen in (DNP)(3)[Fe(CN)(6)](2).10H(2)O.
PG  - 6477-6488
LID - 10.1021/acs.inorgchem.7b00540 [doi]
AB  - K(3)Fe(CN)(6) reacts with the viologen 
      1,1'-bis(2,4-dinitrophenyl)-4,4'-bipyridinium dication, (DNP)(2+), to form a 
      supramolecular complex, (DNP)(3)[Fe(CN)(6)](2).10H(2)O (1). The crystal structure 
      of 1 reveals that there are two [Fe(CN)(6)](3-) anions within an organic 
      framework of three (DNP)(2+) cations with the shortest Fe(III)...Fe(III) 
      distances of ca. 9.8 A, distances that minimize extensive long-range magnetic 
      exchange coupling interactions between the [Fe(CN)(6)](3-) anions, and, thus, 1 
      is paramagnetic above ca. 17 K and exhibits weak ferromagnetic coupling between 
      17 and 3 K and antiferromagnetic coupling between 3 and 1.8 K. The long 
      Fe(III)...Fe(III) distances permit slow spin-spin and slow spin-lattice 
      paramagnetic relaxation, relative to the iron-57 Larmor precession frequency, as 
      is evidenced by the Mossbauer spectra measured between 3 and 60 K; between 85 and 
      295 K, rapid paramagnetic relaxation is observed. Both the slow spin-spin and 
      slow spin-lattice relaxation are mediated by the organic, pi-conjugated viologen 
      cations. The Fe-C distances, the Mossbauer isomer shifts, the temperature 
      dependence of the magnetic susceptibility, and the 3 K magnetization results all 
      indicate the presence of low-spin Fe(III) ions in the [Fe(CN)(6)](3-) anions in 
      1. There is no unequivocal indication of the presence of any formal electron 
      delocalization or transfer from the [Fe(CN)(6)](3-) anion to the (DNP)(2+) 
      cations in the results obtained from X-ray crystallography, magnetic 
      measurements, and Mossbauer spectra. Because of enhancement of the spin-orbit 
      coupling by the heavy-atom or -ion effect, the Fe(III) ions in the 
      [Fe(CN)(6)](3-) anions interact with the (DNP)(2+) cations, causing them to 
      fluoresce with increasing intensity upon cooling from 90 to 25 K when excited at 
      300 nm. The resulting luminescence of the viologen (DNP)(2+) cation induced by 
      the [Fe(CN)(6)](3-) anions indicates the presence of significant mixing of the 
      molecular orbitals derived from the [Fe(CN)(6)](3-) anions and the molecular 
      orbitals associated with the (DNP)(2+) cations to yield bonding supramolecular 
      orbitals in 1, a mixing that is also observed between 50 and 3 K in the 
      temperature dependence of the isomer shift of 1.
FAU - Abouelwafa, Ahmed S
AU  - Abouelwafa AS
AD  - Departement de Chimie Physique, Universite de Geneve , 30 Quai Ernest Ansermet, 
      CH-1211 Geneve, Switzerland.
AD  - Institut fur Anorganische Chemie, Karlsruhe Institute of Technology , 
      Engesserstrasse 15, D-76131 Karlsruhe, Germany.
FAU - Hauser, Andreas
AU  - Hauser A
AD  - Departement de Chimie Physique, Universite de Geneve , 30 Quai Ernest Ansermet, 
      CH-1211 Geneve, Switzerland.
FAU - Mereacre, Valeriu
AU  - Mereacre V
AD  - Institut fur Anorganische Chemie, Karlsruhe Institute of Technology , 
      Engesserstrasse 15, D-76131 Karlsruhe, Germany.
FAU - Lan, Yanhua
AU  - Lan Y
AD  - Institut fur Anorganische Chemie, Karlsruhe Institute of Technology , 
      Engesserstrasse 15, D-76131 Karlsruhe, Germany.
FAU - Long, Gary J
AU  - Long GJ
AUID- ORCID: 0000-0002-6573-5927
AD  - Department of Chemistry, Missouri University of Science and Technology, 
      University of Missouri , Rolla, Missouri 65409-0010, United States.
FAU - Grandjean, Fernande
AU  - Grandjean F
AD  - Department of Chemistry, Missouri University of Science and Technology, 
      University of Missouri , Rolla, Missouri 65409-0010, United States.
AD  - Faculty of Sciences, University of Liege , B-4000 Sart-Tilman, Belgium.
FAU - Buth, Gernot
AU  - Buth G
FAU - Anson, Christopher E
AU  - Anson CE
AD  - Institut fur Anorganische Chemie, Karlsruhe Institute of Technology , 
      Engesserstrasse 15, D-76131 Karlsruhe, Germany.
FAU - Powell, Annie K
AU  - Powell AK
AUID- ORCID: 0000-0003-3944-7427
AD  - Institut fur Anorganische Chemie, Karlsruhe Institute of Technology , 
      Engesserstrasse 15, D-76131 Karlsruhe, Germany.
LA  - eng
PT  - Journal Article
DEP - 20170516
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
EDAT- 2017/05/17 06:00
MHDA- 2017/05/17 06:01
CRDT- 2017/05/17 06:00
PHST- 2017/05/17 06:00 [pubmed]
PHST- 2017/05/17 06:01 [medline]
PHST- 2017/05/17 06:00 [entrez]
AID - 10.1021/acs.inorgchem.7b00540 [doi]
PST - ppublish
SO  - Inorg Chem. 2017 Jun 5;56(11):6477-6488. doi: 10.1021/acs.inorgchem.7b00540. Epub 
      2017 May 16.