Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 24, Issue 61, Pages 16302-16314Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201802933
Keywords
charge transfer; density functional calculations; noncovalent interactions; polycyanide complexes; supramolecular chemistry
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Funding
- National Science Center in Poland, grant OPUS 8 [UMO 2014/15/B/ST5/02098]
- Ministry of Science and Higher Education in Poland
- European Regional Development Fund [POIG.02.01.00-12-023/08]
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The synthesis, crystal structures, spectroscopic characterization, and comprehensive quantum-chemical calculations for a novel series of anion-pi hybrid salts (XPh4)(2)[M(CN)(4)][HAT(CN)(6)]center dot 3MeCN (X=P, M=Ni-II (1), Pd-II (3), Pt-II (5); X=As, M=Ni-II (2), Pd-II (4), Pt-II (6); HAT(CN)(6)=1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile) are presented. The systems comprise 1D {[M(CN)(4)](2-);[HAT(CN)(6)]}(infinity) stacks, in which the electron-rich metal complexes adjust their orientation to match the electron-deficient areas of HAT(CN)(6). Electronic charge-transfer interactions along the stacks result in polarization of electron density within HAT(CN)(6) and in perturbations along the {[M(CN)(4)](2-);[HAT(CN)(6)]}(infinity) contacts. Electronic structure analysis suggests, for example, a relocation of 0.1-0.2 e per molecule from [M(CN)(4)](2-) to HAT(CN)(6) and anion-pi interaction energies of around -65 kcal mol(-1). A reversible structural single-crystal-to-single-crystal transformation, through desolvation/resolvation processes in the solid state, is also reported and a scheme for the formation of anion-pi [M(CN)(4)](2-)/HAT(CN)(6) adducts in MeCN is proposed.
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