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Published on: April 10, 2015
Multifunctional one-dimensional rhodium(I)-semiquinonato complex: substituent effects on crystal structures and
Minoru Mitsumi1, Shoji Ohtake, Yuki Kakuno
1Department of Material Science and ‡Research Center for New Functional Materials, Graduate School of Material Science, University of Hyogo , 3-2-1 Kouto, Kamigori-cho, Ako-gun, Hyogo 678-1297, Japan.
Two new rhodium(I)-semiquinonato complexes were synthesized to study their magnetic and conductive properties. Compound 4 exhibits a phase transition with a switch from antiferromagnetic to ferromagnetic coupling and semiconductor behavior.
Area of Science:
- Materials Science
- Solid-State Chemistry
- Coordination Chemistry
Background:
- Investigating structure-property relationships in 1D coordination complexes is crucial for developing advanced materials.
- Previous studies on rhodium(I)-semiquinonato complexes revealed unusual phase transitions and magnetic properties.
Purpose of the Study:
- To synthesize and characterize two new 1D rhodium(I)-semiquinonato complexes, [Rh(3,6-DBSQ-4,5-PDO)(CO)2]∞ (4) and [Rh(3,6-DBSQ-4,5-(N,N'-DEN))(CO)2]∞ (5).
- To explore their crystal structures, magnetic behaviors, and electrical conductivity.
- To understand the influence of ligand variations on the properties of these 1D chains.
Main Methods:
- Synthesis of novel rhodium(I)-semiquinonato complexes.
- Single-crystal X-ray diffraction for structural analysis.
- Magnetic susceptibility measurements (DC and AC).
- Electrical conductivity measurements.
Main Results:
- Compounds 4 and 5 form neutral 1D chains with short Rh-Rh distances.
- Compound 4 shows a first-order phase transition at 229.1 K, transitioning from antiferromagnetic to ferromagnetic coupling.
- Compound 4 exhibits semiconductor behavior with a crossover in activation energy and a slow spin relaxation process below 5.2 K.
- Compound 5, with a dimerized structure, is an insulator and lacks strong ferromagnetic interactions.
Conclusions:
- Ligand modification significantly impacts the structural, magnetic, and conductive properties of 1D rhodium(I)-semiquinonato complexes.
- Compound 4 demonstrates complex magnetic and electronic transitions, highlighting its potential for advanced electronic applications.
- Compound 5's insulating and dimerized nature contrasts with the behavior of compound 4, underscoring the sensitivity of these systems to structural details.
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