The
presence of sharp bands observed in the region 475-425 cm1 confirms the
formation of uCr-Nbands [18]. In
electronic spectra chromium have shown two bands at 576-584 u1(E:28.38-38.49)
and 410-430 u2(E:43.00-43.82) nm,
respectively. These bands may be assigned to the transition 4T2g(F)¬4A2gand4T1g(P)¬4A2grespectively.
These transitions indicate the six-coordination of the central chromium ion.
All these [CrLn1-10X2]X complexes have shown
magnetic moment values of 3.80-4.00 BM at room temperature which correspond to
three unpaired electrons expected for high spin Cr(III) complexes.19
The binding energies (eV) of prepared ligands
;
CrX3 (where X = Cl-
or NO-3 or
CH3COO-) and [Cr X2]X
complexes for Cr2p1/2, 3/2and N1s photoelectron peaks are listed in
table I and shown in Fig 4-5).It was seen that the binding energies of Cr2p1/2,
3/2in starting material (Cr2p1/2= BE = ~285.8
286.2 and Cr2p3/2 = BE ~ 576.4 577.0 eV) CrCl3 or Cr(NO3)2
or Cr(CH3COO)2 were higher than in [CrX2]
X complexes (Cr2p1/2= BE = ~284.4 284.8 and Cr2p3/2
= BE ~ 575.4 575.6 eV) suggesting the electron density in chromium metal is
more in prepared molecular complexes [CrX2]X
than in CrX3 due to coordination [20, 21] (Fig 4). The N1s
photoelectron spectra of all these [CrX2]
X have shown only one single symmetrical photoelectron peak towards higher
binding energy side (~BE=402.8-403.8 eV) than N1s photoelectron peak of each
ligand (~BE=400.8 eV), suggesting all four nitrogen atoms of each ligand is
coordinated with chromium metal ion [22]. (Fig.-5) (Table 1). The Cr 3S1/2
photoelectron peak in all these [CrX2]
X complexes have shown asymmetric peak i.e. have shown multiple splitting
effect, suggesting all these complexes are paramagnetic.
CONCLUSION:
On
the basis of above physicochemical data of these [CrX2]X
complexes, i.e. elemental analysis, molar conductance, IR, electronic spectra, magnetic
moment and XPS data may suggest the structure of these as shown in Figs 1-3 and
an octahedral geometry may be established. Cr2p photoelectron spectra of all
[CrCl2]Cl
complexes have shown two peaks one of outer sphere chlorine atom on ~BE=200.2
eV and one of inner sphere chlorine atom on ~ BE = 202.4 eV with intensity 1 :
2 ratio respectively [97-98]. Similarly N1s photoelectron spectra of all [Cr
NO3]
NO3 have shown two peaks one of outer spherenitrogen peak of nitrate
ion on ~ BE = 405.0 eV and other for inner sphere nitrogen peak of nitrate ion
on ~ BE = 406.8 eV in 1: 2 intensity ratio respectively (Table 1).
ACKNOWLEDGMENTS:
The
author (D.K. Sahu) is very thankful to Head of Department of Chemistry, University
of Allahabad, Prayagraj, U.P. India for providing necessary facility to
successfully completed of this work.
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(Where X = Cl-
or NO-3 or CH3COO- and =
macrocyclic Schiff base ligands derived from condensation of trimesic acid or p-phthalic acid or
squaric acid with different aliphatic diamines) have been synthesised and
characterised by elemental analysis; molar conductance; electronic spectra; IR;
magnetic moment and XPS i.e. X-ray Photoelectron spectra data. An octahedral
geometry was established for them.
