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ChemInform Abstract: Inclusion Compounds of Multi-Dimensional Cyanometal Complex Hosts
Abstract
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... If some suitable molecules, as guests, enter the cavities of the Hofmann-type compounds, these new structures are called Hofmann-type clathrates and are given by the formula M(II)LM'(II)(CN) 4 •nG. In this formula, G shows the guest molecule in the Hofmann-type clathrates, whereas n shows the number of the guest molecules [3,4]. ...
... When the transition metal atoms M'(II), such as nickel (Ni), palladium, and platinum (Pt), are used to obtain Hofmann compounds, the compound formed is called a Hofmann-type complex. If the transition metal atoms zinc , cadmium, and mercury are used to obtain the Hofmann compounds, the resulting compounds are called Hofmann-T d -type complexes and clathrates [1][2][3][4]. ...
... Broad and descriptive information about Hofmann-type compounds and clathrates can be found in various studies [1][2][3][4][5][6][7]. ...
... Inclusion compounds are formed by host lattices with voids or tunnels in which guest molecules are enclathrated. Although organic compounds are well known to show inclusion behaviour, only a very few inorganic complexes exhibit such a property, notable examples being the Hofmann-type and related clathrates which originate from the ammine-or amine-metal(II)-tetracyanometallate(II) host structures [1]. Studies on guest-host interactions in inclusion compounds are of current interest due to the importance of these compounds in molecular recognition, separation of isomers and synthesis of asymmetric and polymeric compounds [1][2][3]. ...
... Although organic compounds are well known to show inclusion behaviour, only a very few inorganic complexes exhibit such a property, notable examples being the Hofmann-type and related clathrates which originate from the ammine-or amine-metal(II)-tetracyanometallate(II) host structures [1]. Studies on guest-host interactions in inclusion compounds are of current interest due to the importance of these compounds in molecular recognition, separation of isomers and synthesis of asymmetric and polymeric compounds [1][2][3]. Guest-host interactions in these clathrates provide an explanation for the effects of enclathration on the structural and spectroscopic properties of both the guest and the host molecules. Despite being weak in nature, these interactions produce Author for correspondence. ...
Synthesis and IR spectra of novel Hofmann-T
d
-type aniline clathrates, M(NH3)2Zn(CN)4 2C6H5NH2 (M = Zn or Cd) are reported for the first time. All the vibrational modes of aniline are characterised. The shifts in
a
(NH2) and
s
(NH2) reveal hydrogen bonding between the NH2 group of aniline and the cyanide group of the host lattice to be stronger than in Hofmann-type aniline clathrates. However, the out of plane deformation mode of aniline indicates absence of hydrogen bonding between ammonia and the -cloud of the aniline ring. The related aniline clathrates with bridging Cd(CN)4 M(NH3)2Cd(CN)4 2C6H5NH2 (M=Zn or Cd), exhibit similar behaviour.
Molecular architectures built of inorganic cyanometalate building blocks provide variegated host structures with several organic guest molecules. The strategies to derive novel structures are presented briefly. The formation of a charge-transfer (CT) complex as the guest inside the cavity and the photochemistry of the CT complexes are discussed. The chemical pressure that the guest experiences inside the cavity is also discussed based on the vibrational spectroscopic results.
The rapid growth of interest in inclusion chemistry was highlighted recently by the award of the 1987 Nobel prize for chemistry to Professors D.J. Cram, J-M. Lehn, and C.J. Pedersen. The principal aim of Inclusion Compounds is to provide a comprehensive and up-to-date survey of the field of inclusion chemistry. In-depth coverage of subjects has been achieved by inviting the leading international authorities to write on their particular fields of interest: their contributions include detailed descriptions of the design, synthesis, and structure of organic host molecules, molecular recognition and complexation, and host-guest interactions. Inclusion Compounds, Volume Five is complete in itself as a reference work on inorganic and physical aspects of inclusion phenomena.