Vibrational Spectroscopic Analyses of (en)2-Td-type Clathrates

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G. Indramahalakshmi


The clathrates of Hofmann-(en)2-Td-type, M(en)2M’(CN)4.Aniline (M=Cu,Cd; M’=Cd,Zn) and their hosts were synthesized with the confirmation using FTIR spectra. Hydrogen bonding interaction between π-cloud of phenyl ring of the guest molecule and ethylenediamine(en) of the host lattices was deduced from the upward shift in ν(CH)out of plane bending mode of aniline. A second type of hydrogen bonding between C≡N group of the host lattice and NH2 of aniline guest was also inferred from the downward shift in ν(C≡N) of the clathrates. The relative strength of H-bonding in the clathrates was found to be Hofmann-(en)2-Type > Hofmann-(en)2-Td-Phenol > Hofmann-(en)2-Td-Aniline. The presence of major peaks corresponding to various modes of guest aniline, ligand en and cyanide group in FT Raman spectra also confirms the formation of clathrates. Attempts to synthesize Ni(en)2M’(CN)4.Aniline (M’=Cd,Zn) resulted in the formation of M’(en)2Ni(CN)4.2Aniline (M’=Cd,Zn) due to the exchange of metal ions and greater stability of Ni(CN)4 unit.

Aniline clathrates, Hofmann-(en)2-Td-type, metal ion exchange in clathrates, IR spectra, Raman spectra, guest-host interactions.

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Indramahalakshmi, G. (2020). Vibrational Spectroscopic Analyses of (en)2-Td-type Clathrates. Asian Journal of Physical and Chemical Sciences, 8(1), 37-47.
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Lehn JM. Supramolecular chemistry. Science. 1993;260(5115):1762.
DOI: 10.1126/science/8511582

Iwamoto T. Inclusion compounds. Eds.; J. L. Atwood, J. E. D. Davies, D. D. MacNicol: Academic Press, London. 1984;5:29.

Iwamoto T, Atwood JL, Davies JED, MacNicol DD. Inclusion compounds. Oxford University Press, London. 1991;5: 177.

Saalfrank RW, Decke M, Hempel F, Peters K, Vonchnering HG. Induction of Helicity via Stereogenic Centers: Asymmetric synthesis of (P)‐ and (M)‐coordination polymers. Chem. Ber. Recuil, 1997;130: 1309.

Kantatzidis MG, Wu CG, March HO, Decroot DC, Schindler JL, Kannewarf CR, Benzand M, Le Goff E. Supra molecular architecture, synthetic control in thin films and solids. T. Bein, (Eds)., ACS Symp. Ser. 1992;499:194.

Sopkova A, Singlier M, Bubanec J, Gorenerova T, Kralik P. Czech. Patent. 1983;222(610):9.

Zimmer WJ, Schied WS, Highey AP. Lien: Petrol Engr. 1950;22c:43.

AndyHor TS, Ying-Phoot Leong, Lai-Tee Phang. Environmental monitoring and assessment (Historical Archieve). 1991;19(1-3):143.

Fetterle LC. U.S. Patent 1950;499:820.

Dempster AB, Morehouse RL, Uslu H. Infrared spectra of Hofmann-type furan, thiopene, pyrrole and phenol clathrates: Further evidence for hydrogen bonding interactions between host-lattice and guest molecule. Spectrochimica Acta. 1975;31A: 1775.

Akyuz S, Dempster AB, Morehouse RL. Host-guest interactions and stability of Hofmann-type benzene and aniline clathrates studied by IR spectroscopy, Spectrochimica Acta. 1974;30A:1989.

Bayrak C, Mehemet Civi, Yasemin Kutucu. Infrared spectroscopic study on the Hofmann-Td-type Aniline Clathrates. J. Incl. Phenom. Mac. Chem. 2006;55:303.

Nishikiori S, Takahashi A, Ratcliffe CI, Ripmeester JA. X-ray and 2H NMR studies of structure and dynamics in the Hofmann-Type and Hofmann-en-Type Pyrrole Clathrates. J. Supramol. Chem. 2002;2: 483.

Iwamoto T, Duward F. Shriver: Benzene clathrates with a novel kind of metal complex host lattice: Cd(en)Cd(CN)4.2C6H6 and Cd(en)Hg(CN)4.2C6H6. Inorg. Chem. 1972;11(10):2570.

Kasap E, Kantarci Z. Vibrational spectroscopic studies on the en-Td-Type Benzene clathrates. J. Inclu. Phenom. Mol. Recogn. 1995;23:1.

Thamaraichelvan A. Spectroscopic studies on some transition metal complexes and radicals. Madurai Kamaraj University, Madurai, India: Ph.D. Thesis; 1996.

Juraj Cernak, Ivan Potocnak, Jonef Chomic. Crystal structure of Hofmann-en2-type host, Zn(en)2Ni(CN)4. Acta Cryst. 1990;46:1098.

Sopkova A, Bubanec J. Phenol as a guest molecule in clathrate compounds. J. Mol. Struct. 1981;75:73.

Akyuz S, Dempster AB. Infrared and raman study of the decomposition of the Hofmann aniline clathrates. J. Mol. Struct. 1977;38:43.

Yuge H, Iwamoto T. Different coordinating behavior of en. J. Chem. Soc., Dalton Trans. 1994;1237.

Iwamoto T. A new type of clathrates with an ethylenediamine bridged host lattice of three dimensions. Inorg. Chim. Acta. 1968;2:269.

Evans JC. The vibrational assignments and configuration of aniline, aniline-NHD and aniline-ND2. Spectrochimica Acta. 1960;16(4):428.

Iwamoto T, Kiyoki M, Ohtsu Y, Takeshige KY. The Analogs of Hofmann type Clathrate formed between Diammine-or Diaminemetal(II) Tetracyanometallate(II) host and aromatic guest molecule. Bull. Chem. Soc. Jpn. 1978;51(2):488.

Kantarci Z, Bayrak C, Kasap E. An infrared spectroscopic study on Hofmann- and en-Td-type benzene clathrates. J. Incl. Phenom. Mac. Chem. 2001;39:103.

Akyuz S. Infrared spectra and structure of carbanions. J. Mol. Struct. 1980;68:41.

Yokoseki A, Kuchitsu K. Structure and rotational isomerism of en as studied by gas electron diffraction. Bull. Chem. Soc. Jpn. 1971;44:2926.

Giorgini MG, Pelletti MR, Cataliotti RS. Vibrational spectra and assignments of ethylenediamine and its deuterated derivatives. J. Raman Spectra. 1983;14: 16.

Nishikiori S, Iwamoto T. Crystal structures of ethylenediaminecadmium(II) tetracyanocadmate (II)-benzene(1/2) and ethylenediaminecadmium(II) tetracyanocadmate(II). J. Incl. Phenom. 1985;3:283.

Kasap E, Kantarci Z. Vibrational spectroscopic studies on the Hofmann-Td-type Benzene clathrates. J. Inclu. Phenom. Mol. Recogn. 1995;20:33.

Liljana Andreeva, Biljana Minceva-Sukarova. Vibrational spectra of partially debenzenated analogues in some en-Td-type clathrates. J. Mol. Struct. 1997;408-409:431.

Jones LH. Vibrational spectrum and structure of metal cyanide complexes in the solid state-V: K2Zn(CN)4, K2Cd(CN)4 and K2Hg(CN)4, Spectrochimca Acta. 1961;17:188.

Iwamoto T. The hofmann type related inclusion compounds. J. Mol. Struct. 1981;75:51.