A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Hydrogen and Halogen Bond Mediated Coordination Polymers of Chloro-Substituted Pyrazin-2-Amine Copper(I) Bromide Complexes (2020)


Mailman, Aaron; Puttreddy, Rakesh; Lahtinen, Manu; Svahn, Noora; Rissanen, Kari (2020). Hydrogen and Halogen Bond Mediated Coordination Polymers of Chloro-Substituted Pyrazin-2-Amine Copper(I) Bromide Complexes. Chemistry, 2 (3), 700-713. DOI: 10.3390/chemistry2030045


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Julkaisun tiedot

Julkaisun kaikki tekijät tai toimittajat: Mailman, Aaron; Puttreddy, Rakesh; Lahtinen, Manu; Svahn, Noora; Rissanen, Kari

Lehti tai sarja: Chemistry

eISSN: 2624-8549

Julkaisuvuosi: 2020

Volyymi: 2

Lehden numero: 3

Artikkelin sivunumerot: 700-713

Kustantaja: MDPI AG

Julkaisumaa: Sveitsi

Julkaisun kieli: englanti

DOI: https://doi.org/10.3390/chemistry2030045

Avoin saatavuus: Open access -julkaisukanavassa ilmestynyt julkaisu

Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/71366


Tiivistelmä

A new class of six mono- (1; 3-Cl-, 2; 5-Cl-, 3; 6-Cl-) and di-(4; 3,6-Cl, 5; 5,6-Cl-, 6; 3,5-Cl-) chloro-substituted pyrazin-2-amine ligands (1–6) form complexes with copper (I) bromide, to give 1D and 2D coordination polymers through a combination of halogen and hydrogen bonding that were characterized by X-ray diffraction analysis. These Cu(I) complexes were prepared indirectly from the ligands and CuBr2 via an in situ redox process in moderate to high yields. Four of the pyrazine ligands, 1, 4–6 were found to favor a monodentate mode of coordination to one CuI ion. The absence of a C6-chloro substituent in ligands 1, 2 and 6 supported N1–Cu coordination over the alternative N4–Cu coordination mode evidenced for ligands 4 and 5. These monodentate systems afforded predominantly hydrogen bond (HB) networks containing a catenated (μ3-bromo)-CuI ‘staircase’ motif, with a network of ‘cooperative’ halogen bonds (XB), leading to infinite polymeric structures. Alternatively, ligands 2 and 3 preferred a μ2-N,N’ bridging mode leading to three different polymeric structures. These adopt the (μ3-bromo)-CuI ‘staircase’ motif observed in the monodentate ligands, a unique single (μ2-bromo)-CuI chain, or a discrete Cu2Br2 rhomboid (μ2-bromo)-CuI dimer. Two main HB patterns afforded by self-complimentary dimerization of the amino pyrazines described by the graph set notation R22(8) and non-cyclic intermolecular N–H∙∙∙N’ or N–H∙∙∙Br–Cu leading to infinite polymeric structures are discussed. The cooperative halogen bonding between C–Cl∙∙∙Cl–C and the C–Cl∙∙∙Br–Cu XB contacts are less than the sum of the van der Waals radii of participating atoms, with the latter ranging from 3.4178(14) to 3.582(15) Å. In all cases, the mode of coordination and pyrazine ring substituents affect the pattern of HBs and XBs in these supramolecular structures.


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Viimeisin päivitys 2020-28-10 klo 08:51