Anion-dependent host-guest properties of porous assemblies of coordination complexes (PACs), [Cu(A) sub(2)(py) sub(4)] (A = PF sub(6), BF sub(4), CF sub(3)SO sub(3), and CH sub(3)SO sub(3); py = pyridine), based on Werner-type copper(ii) complexes in the solid state

• Published in: Dalton transactions : an international journal of inorganic chemistry 2013-07, Vol.42 (31), p.11100-11110
• Main Authors: Noro, Shin-ichiro, Fukuhara, Katsuo, Sugimoto, Kunihisa, Hijikata, Yuh, Kubo, Kazuya, Nakamura, Takayoshi
• Format: Article
• Language: English
• Subjects: Acetone; Adsorption; Anions; Assemblies; Atomic structure; Diffraction; Pyridines; Transformations
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c3dt51104a

We report the syntheses and crystal structures of novel porous assemblies of coordination complexes (PACs) with/without guest molecules, alpha -[Cu(A) sub(2)(py) sub(4) ] ( alpha -PAC-2-A (A = PF sub(6), BF sub(4), CF sub(3)SO sub(3), and CH sub(3)SO sub(3)); py = pyridine), gamma -{[Cu(PF sub(6)) sub(2)(p y) sub(4)].2guest} ( gamma -PAC-2-PF sub(6) super( 2guest (guest = acetone and py)), gamma -{[Cu(BF) sub(4) sub(2)(p y) sub(4)].2acetone} ( gamma -PAC-2-BF sub(4) super( 2acetone), and beta -{[Cu(CH) sub(3)O sub(3)) sub(2)(py) sub(4)].2.67H sub(2)O} ( beta -PAC-2-CH sub(3)SO sub(3) super( 2.67H) sub(2)). The single-crystal X-ray diffraction analyses of alpha -PAC-2-A show that alpha -PAC-2-A have dense packing structures, in which anions of the discrete coordination complexes form weak hydrogen-bonding and anion- pi interactions. In contrast, gamma -PAC-2-PF sub(6) super( 2guest, gamma -PAC-2-BF) sub(4) super( 2acetone, and beta -PAC-2-CH) sub(3)O sub(3) super( 2.67H) sub(2) form guest-including structures with coordination environments around the Cu super(II) atoms similar to the alpha -forms. The vapour adsorption measurements for MeCN and acetone in alpha -PAC-2-A suggest that the adsorption associated with structural transformations is induced by weak Lewis-base PF sub(6) super(-) and BF sub(4) super(-) anions covered only with fluorine atoms, which weaken the host-host interactions.