PMID- 21072397
OWN - NLM
STAT- MEDLINE
DCOM- 20110324
LR  - 20131121
IS  - 1477-9234 (Electronic)
IS  - 1477-9226 (Linking)
VI  - 40
IP  - 1
DP  - 2011 Jan 7
TI  - Unsymmetrical diimine complexes of iron(II) and manganese(II): synthesis, 
      structure and photoluminescence of an isomer.
PG  - 146-55
LID - 10.1039/c0dt00883d [doi]
AB  - Two bis(unsymmetrical diimine) complexes of 
      (L(NO(2))(varphi1))(L(NO(2))(varphi2))M(II)Cl(2) family with M = Fe and Mn, are reported 
      (L(NO(2))(varphi) = (E)-3-nitro-N-(pyridine-2-ylmethylene)aniline; varphi = dihedral angle 
      between the diimine unit including pyridine ring and the phenyl ring planes). 
      Pure tcc-(L(NO2)(33.6))(L(NO2)(79.3))Fe(II)Cl(2).0.5H(2)O (1) and 
      tcc-(L(NO2)(32.0))(L(NO2)(79.4))Mn(II)Cl(2).0.5H(2)O (2) isomers have been 
      successfully isolated in high yields and characterized by elemental analyses, 
      variable temperature magnetic susceptibility measurements, IR, mass, UV-vis and 
      Mossbauer spectra including the single-crystal X-ray structure determinations 
      that identified strong intermolecular non-bonding interactions in lattice (tcc 
      refers to trans-cis-cis positions with respect to pyridine N-imine N-Cl donors). 
      Geometries optimizations of all possible tcc, ttt, ctc, ccc and cct isomers of 
      iron at the B3LYP/DFT level in gas-phase have shown that the tcc-isomer 
      incorporating two non-equivalent ligands as in 
      (L(NO(2))(42))(L(NO(2))(61))Fe(II)Cl(2), 1 (g), is stabilized by 6-20 kJ mol(-1) 
      compared to other isomers where two ligands are equivalent. The frozen methanol 
      glasses of 1 and 2 are luminescent at 77 K (1: lambda(ext) = 370, lambda(em) = 521 nm, chi(2) 
      = 1.3, tau(avg) = 0.57 ns; 2: lambda(ext) = 368, lambda(em) = 524 nm, chi(2) = 1.1, tau(avg) = 
      0.90 ns). The DFT calculations have identified four closely spaced localized pi(*) 
      orbitals comprising of two non-equivalent ligands as UPMOs. The features contrast 
      the tcc-isomer of (L(varphi))(2)Fe(II)Cl(2) (3), congener of 1 without -NO(2) 
      substitution and non-emissive (bpy)(2)Fe(II)Cl(2) (4) where two ligands are 
      equivalent. TD-DFT calculations have assigned intra-ligand (IL) and ligand to 
      ligand charge transfer (LLCT) dominated excited states as the origin of 
      luminescence of 1 and 2.
FAU - Roy, Amit Saha
AU  - Roy AS
AD  - Department of Chemistry, R. K. Mission Residential College, Narendrapur, 
      Kolkata-103, India.
FAU - Biswas, Manas Kumar
AU  - Biswas MK
FAU - Weyhermuller, Thomas
AU  - Weyhermuller T
FAU - Ghosh, Prasanta
AU  - Ghosh P
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20101111
PL  - England
TA  - Dalton Trans
JT  - Dalton transactions (Cambridge, England : 2003)
JID - 101176026
RN  - 0 (Ferrous Compounds)
RN  - 0 (Imines)
RN  - 42Z2K6ZL8P (Manganese)
SB  - IM
MH  - Crystallography, X-Ray
MH  - Ferrous Compounds/chemical synthesis/*chemistry
MH  - Imines/chemical synthesis/*chemistry
MH  - Luminescence
MH  - Manganese/*chemistry
MH  - Models, Molecular
MH  - Quantum Theory
MH  - Spectrophotometry, Ultraviolet
MH  - Spectroscopy, Fourier Transform Infrared
MH  - Spectroscopy, Mossbauer
MH  - Stereoisomerism
EDAT- 2010/11/13 06:00
MHDA- 2011/03/25 06:00
CRDT- 2010/11/13 06:00
PHST- 2010/11/13 06:00 [entrez]
PHST- 2010/11/13 06:00 [pubmed]
PHST- 2011/03/25 06:00 [medline]
AID - 10.1039/c0dt00883d [doi]
PST - ppublish
SO  - Dalton Trans. 2011 Jan 7;40(1):146-55. doi: 10.1039/c0dt00883d. Epub 2010 Nov 11.