Crystal Structure and Computational Analysis of a Two-Dimensional Coordination Polymer, BiI3(DppeO2)3/2

• Published in: Journal of inorganic and organometallic polymers and materials 2018, Vol.28 (2), p.528-534
• Main Authors: Kelly, Andrew W., Wheaton, Amelia M., Nicholas, Aaron D., Patterson, Howard H., Pike, Robert D.
• Format: Article
• Language: English
• Subjects: Bismuth; Chemistry; Chemistry and Materials Science; Computation; Coordination polymers; Crystal structure; Ethane; Inorganic Chemistry; Organic Chemistry; Polymer Sciences; Polymers; Sandwich structures; Tetrahydrofuran; Two dimensional analysis
• ISSN: 1574-1443; 1574-1451
• DOI: 10.1007/s10904-018-0806-y

Catena-poly[ fac -triiodobismuth(III)-tris-(µ-ethane-1,2-diylbis(diphenylphosphane oxide-κ 2 O,O′))], a 2-D sheet network of BiI 3 was synthesized from BiI 3 and ethane-1,2-diylbis(diphenylphosphane oxide) (DppeO 2 ) in tetrahydrofuran. The crystal structure revealed a trigonal structure with three-fold symmetry at Bi. Bismuth centers show fac -BiI 3 O 3 coordination, with Bi–I = 2.9416(2) Å and Bi–O = 2.4583(17) Å. The I–Bi–I and O–Bi–O angles (95.520(7)° and 79.04(6)°, respectively) indicate trigonal distortion in the Bi octahedron. Bridging DppeO 2 ligands centered on inversion centers give rise to a 2-D sheet polymer. The 8.3 Å thick sheets consist of three layers in a sandwich structure. The outer layers are composed of phenyl rings and BiI 3 groups with the iodide atoms pointing outward. The central layer consists of the O=PCH 2 CH 2 P=O bridging groups. Computational results suggest that semi-conducting behavior arises from Bi(III) centers. A halide to DppeO 2 π* transition is suggested by theoretical results.