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41382-GB10
Synthetic, Structural, and Photocatalytic Studies of Open Framework Oxysulfides
This ACS-PRF grant has had great impact in my research career and in the education of my graduate and undergraduate students, many of them are women and/or minority students. Significant results have been achieved, resulting in several publications. Three M.S. students (all women) and three undergraduate students (two are women) are leading authors or co-authors in multiple publications supported by the ACS-PRF.
(1) New Metal-Organic Open-Framework Sulfites:
While open-framework materials have been made in a variety of chemical compositions, few are known in which three-connected SO32- anions serve as basic building units. We have prepared 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 by hydrothermal method and structurally characterized. In these compounds, low-dimensional 1-D and 2-D inorganic subunits are assembled into higher 2- or 3-D covalent frameworks by organic ligands. In addition to the structure-directing effect of organic ligands, the flexible coordination chemistry of Zn2+ and SO32- also contributes to the observed structural diversity. These results 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
(2) A sodium zinc hydroxide sulfite with a novel Zn3OH geometry
The synthesis and crystal structure of a new sodium zinc hydroxide sulfite, Na[(Zn(OH)]3(SO3)2, with novel structural features and bonding geometry have been achieved. In Na[(Zn(OH)]3(SO3)2, Zn2+ and O2- alternate to form an interesting corrugated hexagonal sheet with rings consisting of (ZnO)3. Another rare occurrence is the bonding geometry of one third of oxygen sites within the sheet. These oxygen sites form a planar Zn3O unit, unlike other known compounds in which Zn3O is pyramidal.
(3) Homochiral coordination polymer with infinite double stranded helices
Hydrothermal reaction of 4,4-trimethylenedipyridine (tmdp) with ZnI2 under 175° yields a novel compound, {[Zn2I4(tmdp)2]n[Zn2I4(tmdp)2]n}, which has a chiral infinite double stranded helical structure consisting of two single stranded helices of the same handedness.
Publications Acknowledging the Support of ACS-PRF (Cumulative)
For the Period between Sep. 1, 2006 and Aug. 31, 2007
Zheng, N.; Zhang, J.; Bu, X.; Feng, P. Cadmium-porphyrin coordination networks: rich coordination modes and three-dimensional 4-connected CdSO4 and (3,5)-connected hms nets. Crystal Growth & Design 2007, xx, xxx-xxx.
Zhang, Q.; Bu, X.; Lin, Z.; Biasini, M.; Beyermann, W.; Feng, P. Metal-Complex Decorated Homochiral Heterobimetallic Telluride Single-Stranded Helix. Inorg. Chem. 2007, 46, 7262-7264.
Austria, C.; Zhang, J.; Valle, H.; Zhang, Q.; Chew, E.; Nguyen, D-T; Gu, J. Y.; Feng, P.; Bu, X. Amine-Controlled Assembly of Metal Sulfite Architecture from 1-D Chains to 3-D Framework. Inorg. Chem. 2007, 46, 6283-6290.
Han, L.; Valle, H.; Bu, X. Homochiral coordination polymer with infinite double stranded helices. Inorg. Chem. 2007, 46, 1511-1513.
Nguyen, D-T; Bu, X. A sodium zinc hydroxide sulfite with a novel Zn3OH geometry. Inorg. Chem. 2006, 45, 10410-10412.
Nguyen, D-T; Chew, E.; Zhang, Q.; Choi, A., Bu, X. Metal-Organic Frameworks from Zinc Sulfite Clusters, Chains, and Sheets: 4-Connected, (3,4)-Connected 3-D Frameworks and 2-D Arrays of Catenane-Like Interlocking Rings. Inorg. Chem. 2006, 45, 10722-10727.
Prior to Aug. 31, 2007
Zheng, N.; Bu, X.; Feng, P. Zero- and Two-Dimensional Organization of Tetrahedral Cadmium Chalcogenide Clusters with Bifunctional Covalent Linkers. Chem. Mater. 2006, 18, 4307-4311.
Zhang, Q.; Bu, X.; Han, L.; Feng, P. Two-Dimensional Indium Sulfide Framework Constructed from Pentasupertetrahedral P1 and Supertetrahedral T2 Clusters. Inorg. Chem. 2006, 45, 6684-6687.
Hai, L.; Bu, X.; Zhang, Q.; Feng, P. Solvothermal in Situ Ligand Synthesis through Disulfide Cleavage: 3D (3,4)-Connected and 2D Square-Grid-Type Coordination Polymers. Inorg. Chem. 2006, 45, 5736-5738.
Chen, L.; Bu, X. (3,4)-Connected Zincophosphites as Structural Analogs of Zinc Hydrogenphosphate. Inorg. Chem. 2006, 45, 4654-4660.
Zheng, N.; Lu, H.; Bu, X.; Feng, P. Metal-Chelate Dye-Controlled Organization of Cd32S14(SPh)404- Nanoclusters into Three-Dimensional Molecular and Covalent Open Architecture. J. Am. Chem. Soc. 2006, 128, 4528-4529.
Chen, L.; Bu, X. Histidine-Controlled Two-Dimensional Assembly of Zinc Phosphite Four-Ring Units. Chem. Mater. 2006, 18, 1857-1860.
Zheng, N.; Bu, X.; Lu, H.; Chen, L.; Feng, P. One-Dimensional Assembly of Chalcogenide Nanoclusters with Bifunctional Covalent Linkers. J. Am. Chem. Soc. 2005, 127, 14990-14991.
Xie, J.; Bu, X.; Zheng, N.; Feng, P. One-dimensional coordination polymers containing penta-supertetrahedral sulfide clusters linked by dipyridyl ligands. Chem. Commun. 2005, 4916-4918.
