New trinuclear metal string complexes containing rigid Hdzp ligands: synthesis, structure, magnetism and DFT calculation (Hdzp = 1,9-diazaphenoxazine)CCDC reference numbers 832185832187. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt11246a

• Main Authors: Cheng, Ming-Chuan, Liu, Isiah Po-Chun, Hsu, Chan-Hsiang, Lee, Gene-Hsiang, Chen, Chun-hsien, Peng, Shie-Ming
• Format: Journal Article
• Language: English
• Published: 24.02.2012
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c2dt11246a

The synthesis, crystal structure, magnetic properties, and single-molecule conductance of two new trinuclear metal string complexes, [Ni 3 (dzp) 4 (NCS) 2 ] ( 2 ) and [Co 3 (dzp) 4 (NCS) 2 ] ( 3 ), containing the rigid Hdzp ligand ( 1 , 1,9-diazaphenoxazine) are reported. X-ray structural analyses show that compounds 2 and 3 exhibit smaller torsion angles and longer metalmetal distances than those exhibited by the corresponding dpa analogues (dpa = dipyridylamido anion) due to the rigidity of Hdzp ligands. The longer metalmetal distance observed for 2 and 3 results in variations in their magnetic properties. The exchange interaction ( J = 160 cm 1 ) between two high spin (HS) Ni( ii ) ions in 2 decreases slightly in comparison with those of trinickel dpa analogues. The doubletquartet gap of 3 is smaller than that of [Co 3 (dpa) 4 (NCS) 2 ] ( 4 ), which causes compound 3 to show spin-crossover behavior even at low temperature. Two new trinuclear metal string complexes containing rigid surrounding ligands are reported. This rigid ligand can avoid the formation of undesired side-products in the synthesis of metal string complexes, which will be a useful basis for developing future longer metal string complexes.