Amine-controlled assembly of metal-sulfite architecture from 1D chains to 3D framework.
Whereas open-framework materials have been made in a variety of chemical compositions, few are known in which 3-connected SO3(2)- anions serve as basic building units. Here, we report four new metal-sulfite polymeric structures, (ZnSO3)Py (1, py = pyridine), (ZnSO3)2(2,2'-bipy)H2O (2, 2,2'-bipy = 2,2'-bipyridine), (ZnSO3)2(TMDPy) (3, TMDPy = 4,4'-trimethylenedipyridine), and (MnSO3)2en (4, en = ethylenediamine) that have been synthesized hydrothermally and structurally characterized. In these compounds, low-dimensional 1D and 2D inorganic subunits are assembled into higher 2D or 3D covalent frameworks by organic ligands. In addition to the structure-directing effect of organic ligands, the flexible coordination chemistry of Zn2+ and SO3(2)- also contributes to the observed structural diversity. In compounds 1-3, Zn2+ sites alternate with trigonal pyramidal SO3(2)- anions to form three types of [ZnSO3]n chains, whereas in compound 4, a 2D-corrugated [MnSO3]n layer is present. Compound 1 features a rail-like chain with pendant pyridine rings. The pi-pi interaction between 2,2'-bipy ligands is found between adjacent chains in compound 2, resulting in 2D sheets that are further stacked through interlayer hydrogen bonds. Compound 3 exhibits a very interesting inorganic [(ZnSO3)2]n chain constructed from two chairlike subunits, and such chains are bridged by TMDPy ligands into a 2D sheet. In compound 4, side-by-side helical chains permeate through 2D-corrugated [MnSO3]n layers, which are pillared by neutral ethylenediamine molecules into a 3D framework that can be topologically represented as a (3,6)-connected net. The results presented here illustrate the rich structural chemistry of metal-sulfites and the potential of sulfite anions as a unique structural building block for the construction of novel open-framework materials, in particular, those containing polymeric inorganic subunits that may have interesting physical properties such as low-dimensional magnetism or electronic properties.
Austria
Cristina
C
Department of Chemistry and Biochemistry, California State University Long Beach, Long Beach, CA 90840, USA.
Zhang
Jian
J
Valle
Henry
H
Zhang
Qichun
Q
Chew
Emily
E
Nguyen
Dan-Tam
DT
Gu
J Y
JY
Feng
Pingyun
P
Bu
Xianhui
X
D000588:Amines / Q000737:chemistry*; D000838:Anions; D015392:Chemistry, Inorganic / Q000379:methods*; D019281:Dimerization; D006860:Hydrogen Bonding; D008024:Ligands; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011487:Protein Conformation; D011725:Pyridines / Q000737:chemistry; D013447:Sulfites / Q000737:chemistry*; D013696:Temperature; D014961:X-Ray Diffraction; D015032:Zinc / Q000737:chemistry
D000588:Amines; D000838:Anions; D008024:Ligands; D008670:Metals; D011725:Pyridines; D013447:Sulfites; D015032:Zinc; C023666:pyridine