© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Phys. Status Solidi C 8, No. 9, 2735–2738 (2011) / DOI 10.1002/pssc.201084052
The influence of Cd
2+
and Mg
2+
on the electrical and thermal properties
of manganese mercury thiocyanate crystals
and its Lewis base adducts-future materials
for photonics device fabrication
Santhosh Kumar R.
1
, S. Chandralingam
2
, Sijosh George
3
, Sreekanth G.
3
,
Michael Augustine
3
, and Ginson P. Joseph
3*
1
Department of Physics, St. George’s College Aruvithura, Kottayam-686622, Kerala, India
2
Department of Physics, Jawaharlal Nehru Technological University, Hyderabad-500085, India
3
Department of Physics, St. Thomas College Pala, Kottayam-686574, Kerala, India
Received 3 October 2010, accepted 4 February 2011
Published online 24 May 2011
Keywords organobimetallic, dielectric, TGA-DTA
*
Corresponding author: e-mail ginsonpj@gmail.com, Phone: + 91-9447064652
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1 Introduction
Growth of organo-metallic single crystals has been a
subject of perennial concern to realize the use of these ma-
terials for device applications. An important aspect of util-
izing organo-metallic structure for nonlinear optical appli-
cations is their unique charge transfer transitions, either
from metal to ligand or ligand to metal [1]. Thiocyanate
(SCN
-
) is a highly versatile ambidentate ligand with two
terminal modes and thirteen multidentate bridging modes
of coordination. The concept developed by Pearson [2] on
the hard and soft acids and bases rationalizes that the soft
cations show a pronounced affinity for coordination with
softer ligands, whereas, the hard cations prefer coordina-
tion with harder ligands. In these complexes, mercury is
usually tetrahedrally S-coordinated, while the ion of the
metal may be surrounded by four or six ligands. For in-
stance, the –SCN- ligands in MnHg(SCN)
4
bridge the tet-
rahedrally coordinated N-bonded Mn atoms and the tetra-
hedrally coordinated S-bonded Hg atoms into a 3-D net-
work with space group 14 [3].
.
MnHg(SCN)
4
exhibits high
hyperpolarizability due to the extended π-conjugation of
the Mn-NCS-Hg bridges and their parallel alignments in
the 3-D crystal structure. This 3-D network provides a lar-
ger domain for polarizability, which in turn induces a large
macroscopic nonlinearity. As second order nonlinear opti-
cal (SONLO) materials, bimetallic thiocyanates such as
ZnCd(SCN)
4
, ZnHg(SCN)
4
, CdHg(SCN)
4,
CoHg(SCN)
4,
MnHg(SCN)
4
(C
2
H
6
O
8
)
2
CdHg(SCN)
4
(C
2
H
6
O
8
)
2
and
MnHg(SCN)
4
(abbreviated as ZCTC, ZMTC, CMTC,
MMTD,CMTD and MMTC, respectively), exhibit rela-
tively high SHG efficiecy than urea, KDP, at short wave-
lengths [4].
The metal thiocyanates and their Lewis-base adducts
are one of the interesting themes of structural chemistry [5].
This encouraging switch over is mainly attributed to the
improvement of NLO property by the addition of DMSO
ligand. The introduction of DMSO aids better electronic
oscillations in SCN ligand, leading to an enhancement in
NLO efficiency. The present study explains the influence
of metal on manganese mercury thiocyanate (MMTC) and
manganese mercury thiocyanate bisdimethylsulfoxide
(MMTD), a Lewis base adducts of MMTC. The second
Single crystasls of pure and doped MMTC and MMTD crys-
tals were grown by slow evaporation technique. The TGA
traces of doped crystals show a marginal increase in the ther-
mal stability of the samples. The influence of metal substitu-
tion on the dielectric properties of the MMTC and MMTD
crystals has been investigated and reported.