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Bhola Nath Sarkar a, Kishalay Bhar a, Soumi Chattopadhyay a, Sumitra Das a, Partha Mitra b,
Barindra Kumar Ghosh a,*
a
Department of Chemistry, The University of Burdwan, Burdwan 713104, India
b
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India
a r t i c l e i n f o a b s t r a c t
Article history: Two heptacoordinated one-dimensional coordination polymers of the type [Cd(L)(dca)]n(X)n (1 and 2)
Received 4 August 2009
[L = N,N0 -(bis-(pyridin-2-yl)benzylidene)diethylenetriamine; dca = dicyanamide; X = ClO4 (1), PF 6 (2)]
Received in revised form 22 September have been prepared and characterized on the basis of microanalytical, spectroscopic and other physico-
2009
chemical properties. Structures of 1 and 2 are solved by single crystal X-ray diffraction measurements.
Accepted 25 September 2009
Available online 30 September 2009
Structural study reveals that in both compounds each cadmium(II) center adopts a distorted pentagonal
bipyramidal geometry with a CdN7 chromophore coordinated by five N atoms of the pentadentate Schiff
base and two nitrile N atoms of single bridged dca in l1,5 fashion. The polynuclear units in 1 are engaged
Keywords:
Cadmium(II)dicyanamides
in weak N–H. . .O and C–H. . .O hydrogen bondings with perchlorate ions embedded among the chains to
N-donor Schiff base give a 2D sheet structure. In the long-range form, the 1D polymeric chains of 2 pack through N–H. . .F and
Synthesis C–H. . .F hydrogen bonds with hexafluorophosphate placed in between chains resulting a 2D continuum.
Superstructure The complexes display intraligand 1(p–p*) fluorescence in DMF solutions at room temperature.
Luminescence Ó 2009 Elsevier B.V. All rights reserved.
0022-2860/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2009.09.043
36 B.N. Sarkar et al. / Journal of Molecular Structure 963 (2010) 35–40
steam-bath, filtration through fine glass-frit, and was preserved in solution was filtered and left in air for slow evaporation. Colourless
a desiccator containing concentrated sulphuric acid (E. Merck, In- shining microcrystals of 2 were obtained in almost quantitative
dia) for subsequent use. All other chemicals and solvents were yield.
AR grade and were used as received. The microanalytical and spectroscopic results of 2 obtained
Caution! Perchlorate compounds of metal ions are potentially from both the methods (A and B) are similar. Anal. Calc. for
explosive [26] especially in presence of organic ligands. Only small C30H27N8F6PCd (2): C, 47.6; H, 3.6; N, 14.9. Found: C, 47.4; H,
amount of the material should be prepared and handled with care. 3.4; N, 14.9%. IR (KBr, cm–1): m(NH) 3315, 3269; m(CH) 2948,
2868; mas + ms(C„N) 2275; mas(C„N) 2220; ms(C„N) 2148;
2.1.2. Physical measurements m(C@N) 1618, 1593; mas(C–N) 1318; ms(C–N) 954; m(PF6) 846,
Elemental analyses (carbon, hydrogen and nitrogen) were per- 542. UV–vis (k, nm): 281.
formed on a Perkin-Elmer 2400 CHNS/O elemental analyzer. IR
spectra (KBr discs, 4000–300 cm–1) were recorded using a Perkin- 2.4. X-ray crystallographic study
Elmer FTIR model RX1 spectrometer. Molar conductances were
measured using a Systronics conductivity meter where the cell Single crystals of 1 and 2 suitable for X-ray analyses were se-
constant was calibrated with 0.01 M KCl solution and dry MeOH lected from those obtained by slow evaporation of methanolic
and DMF were used as solvents. Ground state absorption was mea- solutions of the reaction mixtures at 298 K. Diffraction data were
sured with a Jasco model V-530 UV–vis spectrophotometer. Fluo- collected at 296 K on a Bruker AXS SMART APEX-II CCD area-detec-
rescence measurements were done using Hitachi Fluorescence tor diffractometer using graphite monochromated Mo-Ka radia-
Spectroflurimeter F-4500. Time-resolved fluorescence measure- tion. The unit cell parameters were obtained from SAINT;
ments were carried out using a time-correlated single photon absorption corrections were performed with SADABS [27]. A sum-
counting (TCSPC) spectrometer Edinburgh Instruments, model mary of the crystallographic data and structure determination
199; a hydrogen filled coaxial flash lamp with a pulse width of parameters are given in Table 1. The unique reflections were re-
1.2 ns at FWHM and a Philips XP-2020Q photomultiplier tube were corded using the x scan technique and structures were solved by
used as the excitation source and the fluorescence detector. direct methods using SHELX-97 [28]. All hydrogen atoms were
fixed geometrically and refined using a riding model and the calcu-
2.2. Synthesis of the Schiff base lations were carried out using PLATON [29] and ORTEP-32 [30].
Table 1
Crystallographic data for 1 and 2.
Complex 1 2
Formula C30H27N8O4ClCd C30H27N8F6PCd
Formula weight 711.45 756.97
Crystal system Monoclinic Monoclinic
Space group Cc Cc
a (Å) 10.7523(3) 10.8987(11)
b (Å) 22.9551(7) 23.385(3)
c (Å) 12.2789(3) 12.4357(12)
b (°) 93.4070(10) 91.741(2)
V (Å3) 3025.32(15) 3168.0(6)
k (Å) 0.71073 0.71073
qcalcd (gm cm3) 1.562 1.587
Z 4 4
T (K) 296(2) 296(2)
l (mm1) 0.860 0.810
F (0 0 0) 1440 1520
Crystal size 0.22 0.17 0.13 0.30 0.21 0.12
h ranges (°) 1.77 to 32.90 1.74 and 21.69
h/k/l 16,16/34,31/18,18 11,11/24,24/12,12
Reflections collected 29,693 10,971
Independent reflections 9938 3715
Data/restraints/parameters 9938/2/397 3715/418/415
Goodness-of-fit on F2 1.021 1.050
Final R indices [I > 2r(I)] R = 0.0352 and wR = 0.0746 R = 0.0375 and wR = 0.0765
R indices (all data) R = 0.0489 and wR = 0.0807 R = 0.0435 and wR = 0.0798
Largest peak and hole (eÅ3) 0.608 and 0.458 0.585 and 0.381
P 2 1=2
P P P 2 .h i .h
Weighting scheme: R = |Fo| |Fc||/ |Fo, wR2 = w F o F 2c w F 2o , Calc. w = 1 r2 F 2o þ ð0:0412PÞ2 þ 0:3828P 1 and w = 1 r2 F 2o þ ð0:0260PÞ2 þ5:1125P:
2
.
2, where P = F 2o þ 2F 2c 3.
Fig. 1. An ORTEP diagram of [Cd(L)(dca)]nn+ with atom labeling scheme and 20% probability ellipsoids for all non-hydrogen atoms.
38 B.N. Sarkar et al. / Journal of Molecular Structure 963 (2010) 35–40
Table 2 Table 4
Selected bond distances (Å) and bond angles (°) for 1. Hydrogen bond distances (Å) and angles (°) for 1.
2], C30–N7–C29 [116.1(3)° in 1 and 120.0(6)° in 2] and N8–C30– rings. Excitation at 368 or 273 nm, L does not show any emission
N7 [174.6(3)° in 1 and 175.1(8)° in 2] that reflects non-linearity band. The absorption spectra of the complexes 1 and 2 show band
of the larger pseudohalide rod. maxima at 281 nm. Although dicyanamide, free Schiff base (L) and
In the crystal packing of 1, 1D polymeric chains running along common cadmium(II) salts used as building units are not lumines-
the direction [1 0 1] are engaged in single N–H. . .O and single C– cent, interestingly the cadmium(II) complexes with this pentaden-
H...O hydrogen bondings with the perchlorate ions embedded tate Schiff base containing the pyridine moiety show intense
among the chains leading to a 2D sheet parallel to the bc plane fluorescence band at 570 nm (for 1) and at 566 nm (for 2) upon
(Fig. 2) with interchian Cd...Cd separation 12.674 Å. Similarly, 1D excitation at the corresponding absorption band of the complexes
polymeric chains of 2 running in the direction [1 0 1] pack through in DMF solutions at room temperature. The lifetimes are in the
involvement of single N–H...F and weak multiple C–H. . .F hydrogen range 2.65–2.70 ns. The appearance of the fluorescence [36] upon
bondings with the hexafluorophosphate ions located between the complex formation could be inferred to the change in MO structure
polymeric chains resulting once again in a 2D sheet parallel to in the complexes compared to that in the free L. The HOMO–LUMO
the bc plane (Fig. 3) but with greater (12.900 Å) interchain Cd...Cd n–p* type of forbidden transition of the free L changes to p–p* type
separation as compared to 1. of HOMO–LUMO transition in the metal complexes. Therefore
upon complexation the non-fluorescent free ligand favours fluores-
cence characteristic of the simple coordinated aromatic chromo-
3.3. Absorption and luminescence properties
phore. Spectral results are set in Table 6 and a representative
spectral pattern is shown in Fig. 4.
In DMF solution, the Schiff base L shows absorption bands at
368 and 273 nm assignable to n–p* of transition of the aromatic
4. Conclusion
Table 6 Financial support from the DST, CSIR and UGC, New Delhi, India
Photophysical data. is gratefully acknowledged. The authors also acknowledge the use
of DST-funded National Single Crystal X-ray Diffraction Facility at
Sample Absorption (k/nm) Emission (k/nm) Lifetime (ns)
Fluorescencea
the Department of Inorganic Chemistry, IACS, Kolkata, India for
crystallographic studies. The authors K.B., S.C. and S.D. thank,
1 281 570 2.66
2 281 566 2.68
respectively, to the CSIR and UGC, New Delhi, India for fellowships.
a
In DMF at room temperature (298 K).
Appendix A. Supplementary data
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