Aromatic, conjugated and polymeric species of Sn in the solid state.

Doctoral Dissertation

Abstract

Recent advances in tetrel chemistry (Tt = Si, Ge, Sn, Pb), stimulated the search for other Zintl phases with novel anionic structures. For that reason, we began thorough and systematic studies over the pseudobinary A–AE–Tt systems (A = alkali metal; AE = alkaline-earth). After exploring a great deal of compositions within the pseudo-binary systems with mixed A/AE metals, we have embarked on exploring analogous systems with the help of mixed of alkali and rare-earth metals (RE). The major part of the work presented in this dissertation deals with the synthesis and structural characterization of a variety of novel intermetallic compounds. A few noteworthy examples are: 1) Na8BaSn6 and Na8BaPb6 with aromatic pentagonal rings of Sn56- and Pb56-, respectively, that are isostructural and isoelectronic with the cyclpentadienyl anion, C5H5 -; 2) Li9-xEuSn6+x, Li5Ca7Sn11, L i6Eu5Sn9 with trimers, hexamers and infinite conjugated chains of Sn, in addition to aromatic pentagonal rings; 3) LiMgEu2Sn3 and LiMgSr2Sn3 with infinite conjugated chains of Sn and single atom anions; 4) Na4CaSn6 with channels built of cyclohexane-like units of Sn6 6-; 5)Li2Ln5Sn7 (Ln = Ce, Pr, Sm, Eu) with branched polymeric 1D chains. Another part of this dissertation concentrates on our attempts to synthesize heteroatomic rings isoelectronic with those of group 14 by a combination of elements from groups 13 (Tr) and 15 (Pn), respectively. However all probed reactions produced novel compounds with extended structures based on TrPn4-tetrahedra. All of the above-mentioned compounds nicely illustrate the delicate balance between packing efficiency and electronic requirements, which explains the stabilization of these novel tetrel clusters, which are inaccessible in pure binary systems.

Attributes

Attribute NameValues
URN
  • etd-07132006-110653

Author Iliya Todorov
Advisor Dr. Kenneth Henderson
Contributor Dr. Graham Lappin, Committee Member
Contributor Dr. Kenneth Henderson, Committee Chair
Contributor Dr. Marya Lieberman, Committee Member
Degree Level Doctoral Dissertation
Degree Discipline Chemistry and Biochemistry
Degree Name PhD
Defense Date
  • 2006-06-28

Submission Date 2006-07-13
Country
  • United States of America

Subject
  • X-ray

  • intermatallics

  • Zintl phases

Publisher
  • University of Notre Dame

Language
  • English

Record Visibility and Access Public
Content License
  • All rights reserved

Departments and Units

Files

Please Note: You may encounter a delay before a download begins. Large or infrequently accessed files can take several minutes to retrieve from our archival storage system.