2004 Fiscal Year Final Research Report Summary
Studies on Magneto-Photo Multifunctional System of Polynuclear Complexes Comprised by Discrete Metal Complexes
| Project/Area Number |
15510092
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Nanostructural science
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| Research Institution | SAGA University |
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Principal Investigator |
KOIKAWA Masayuki Saga University, Faculty of Science and Engineering, Associate Professor, 理工学部, 助教授 (90221952)
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| Co-Investigator(Kenkyū-buntansha) |
TOKII Tadashi Saga University, Faculty of Science and Engineering, Professor, 理工学部, 教授 (40039269)
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| Project Period (FY) |
2003 – 2004
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| Keywords | Trinuclear Complex / Manganese Complex / Copper Complex / Vanadium Complex / Nano-size Complex / X-ray Crystallography / Redox Property / Dye solar cell |
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| Research Abstract |
The new polydentate ligands, H_4L4-X and H_3L5-X(X=H,CH_3,Br), combined two separative coordination sites have been synthesized by reaction of salicylaldehyde homologues and 4,6-diamino-resorcinol. The new trinuclear manganese(III) complexes, [Mn(L5-X)(CH_3OH)]_3 (X=-H;1,-CH_3;2,and -Br;3) have been prepared and characterized by X-ray structure analysis. The trinuclear structure of 1 is shown in Figure 1.Three manganese(III) centers are separated by (L5-H)^<3->, and the Mn...Mn distances lie in the range 8.07(3)-8.18(1) Å. Each manganese ion adopts an elongated octahedral configuration along with O_<solvent>-Mn-N_<oxazoline> axis. The CPK models for 1 are shown in Figure 2.The molecular structure is regarded as a large trigonal pyramid with cavity. Extent of the cavity is estimated as 3 Å in diameter, and the complexes potentially can incorporate small molecules into the cavity. It is expected that the cavity is well adjustable for NH_4^+ because it has hydrophilic oxygens and C_3 symmetry. The reaction of complex 1 and NH_4PF_6 in chloroform gave reddish brown microcrystals. The IR spectrum of the obtained compound showed strong N-H and P-F vibrations at 3212 and 847 cm^<-1>, respectively. Molar conductivity of the products determined in DMF was 96 Scm^2mor^<-1>. The results suggest that the obtained compound formulated as [Mn_3(L5-H)_3(CH_3OH)_3(NH_4)]_3PF_6 (1'). The ammonium ion in 1' was incorporated into the cavity of trinuclear complex unit.
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