Synthesis and Crystal Packing of trans‐Bis(2‐aminotroponato)palladium(II) Complexes Bearing Linear Alkyl Chains – Hard Lamellar Structures Self‐Locked by Cross‐Shaped Molecular Units. Issue 1 (15th November 2013)

• Record Type: Journal Article
• Authors: Komiya, Naruyoshi; Hori, Takao; Naito, Masaya; Naota, Takeshi
• Is Part Of: European journal of inorganic chemistry. Issue 1(2014)
• Page Start: 156
• Page End: 163
• Publication Date: 2013-11-15
• Subjects: Palladium -- Aminotroponato complexes -- N, O ligands -- Lamellar structures -- Crystal engineering; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201300914
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The synthesis, structure, and three‐dimensional lamellar array of a series of trans ‐bis(2‐aminotroponato‐κ N, κ O )palladium(II) complexes bearing linear alkyl chains (1a: n = 5;1b: n = 8;1c: n = 14;1d: n = 16;1e: n = 18, where n is the number of carbon atoms in the chain) attached to trans nitrogen donor atoms are described. The trans ‐coordination of the ligands, the cross‐shaped molecular structures, and the crystal packing of1b and1c have been unequivocally established from single‐crystal XRD studies. Highly regulated multilayered lamellar structures are observed for1b and1c, where every lamellar layer in the crystallographic ab plane, formed by π‐stacking interactions of metal cores and van der Waals interactions between alkyl chains, is laminated alternately on the c axis with an orthogonal lamellar array of the identical unit. Powder XRD analysis showed that1b –1e exhibit diffraction peaks attributed to periodic ( n 00) reflections of a typical lamellar structure. A linear correlation between the d ‐spacing and chain lengths in these compounds indicates that they form the same type of three‐dimensional layer‐by‐layer structure of lamellar aggregates. The correlation between the cross‐shaped molecular structures of1b –1e and the dimensionality of molecular constraint in the crystal packing is discussed by comparison with those of rod‐shaped analogues that exhibit high liquid crystallinity. Abstract : Hard lamellar structures of trans ‐bis(2‐aminotroponato)palladium(II) complexes bearing linear alkyl chains attached to the trans nitrogen donor atoms are described in terms of the correlation between their molecular constraint and the specific alternating laminate structure formed by the cross‐shaped molecular units.