In:
Zeitschrift für anorganische und allgemeine Chemie, Wiley, Vol. 639, No. 8-9 ( 2013-07), p. 1461-1471
Abstract:
The novel coordination compound [Cu I 12 (C 16 H 16 N 4 ) 6 ] · 8DMAc, ( 2 ), (DMAc = N, N ‐dimethylacetamide) was prepared in solvothermal or microwave assisted reaction. It contains four metallamacrocyclic trinuclear copper(I) pyrazolate coordination units, which occupy four (opposite) faces of an imaginary metallosupramolecular octahedron. Six (4,4′‐(1,2‐phenylene)bis(3,5‐dimethylpyrazol‐1‐ide) ligands (L 1 2– ) are placed at the corners of the octahedron. Crystals of the free ligand H 2 L 1 [1,2‐bis(3,5‐dimethyl‐ 1H ‐pyrazol‐4‐yl)benzene, ( 1 )], and [Cu I 12 (C 16 H 16 N 4 ) 6 ] · 8DMAc ( 2 ), were characterized by single‐crystal X‐ray structure analyses. Lingand 1 crystallizes in the monoclinic crystal system, with: a = 9.0118(9), b = 14.0075(11), c = 11.7484(11) Å, β = 104.945(5)°, V = 1432.9(2) Å 3 , space group P 2 1 / c (no. 14). Compound 2 crystallizes in the tetragonal system, with: a = b = 19.506(5), c = 42.888(5) Å, V = 16318(6) Å 3 , space group I 4 1 / amd (no. 141). Compound 2 represents a porous structure, where each metallosupramolecular octahedron encloses a solvent‐filled cavity of 889 Å 3 (accounting for 6 DMAc molecules, 21.8 % of the cell volume). The incomplete crystal packing arrangement of adjacent [Cu I 12 (C 16 H 16 N 4 ) 6 ] moieties in addition leads to solvent‐filled interstitial voids accounting to 8.1 % of the cell volume. Removing solvent molecules in vacuo is accompanied by reversible structural changes, leading to a partial loss of porosity, as revealed by Ar‐BET sorption analysis. Compounds 1 and 2 were further characterized by elemental and thermogravimetric analysis, X‐ray powder diffraction, FTIR‐, UV/Vis‐ and fluorescence spectroscopy. Preliminary results on the activation of molecular oxygen by compound 2 are presented.
Type of Medium:
Online Resource
ISSN:
0044-2313
,
1521-3749
DOI:
10.1002/zaac.v639.8/9
DOI:
10.1002/zaac.201300094
Language:
English
Publisher:
Wiley
Publication Date:
2013
detail.hit.zdb_id:
201094-X
detail.hit.zdb_id:
1481139-X
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