Synthesis, Structure, and Magnetism of a Series of Self-Assembled Polynuclear Mn(II), Co(II), and Cu(II) Cluster Complexes

✍ Scribed by Laurence K. Thompson; Craig J. Matthews; Liang Zhao; Zhiqiang Xu; David O. Miller; Claire Wilson; Michael A. Leech; Judith A.K. Howard; Sarah L. Heath; A.Gavin Whittaker; Richard E.P. Winpenny

• Publisher: Elsevier Science
• Year: 2001
• Tongue: English
• Weight: 521 KB
• Volume: 159
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.2001.9160

✦ Synopsis

The single-crystal structures and magnetic properties of a series of self-assembled cluster complexes of Mn(II), Co(II), Co(II)/Co(III), and Cu(II), with a group of alkoxy-diazine ligands, which have square and rectangular primary architectures, are reported. In one novel case a secondary coordination sphere of metal ions can be built up on a square core, due to the presence of vacant extra-core coordination sites. [Mn 4 (poapz-H) 4 (H 2 O) 4 ](NO 3 ) 4 ' H 2 O (1); monoclinic, C 2/ c, a ‫؍‬ 21.7120(4) A > , b ‫؍‬ 17.421(4) A > , c ‫؍‬ 17.273(4) A > , ‫؍‬ 109.34(3)3. [Co 4 (poap-H) 2 (poap-2H) 2 ](NO 3 ) 4 ' 7H 2 O (3); triclinic, P1 , a ‫؍‬ 9.6855(6) A > , b ‫؍‬ 12.9462(7) A > , c ‫؍‬ 13.7383(8) A > , ‫؍‬ 106.5730(10), ‫؍‬ 99.0400(10) A > , ‫؍‬ 95.737(10)3. [Co 4 (poapz-H) 4 (H 2 O) 4 ](NO 3 ) 4 ' 2H 2 O (4); monoclinic, C 2/ c, a ‫؍‬ 21.160(2) A > , 17.808(2) A > , c ‫؍‬ 17.000(2) A > , ‫؍‬ 106.904(9)3. [Co 4 (pzoapz-H) 4 (H 2 O) 4 ](ClO 4 ) 4 ' 3H 2 O (5); monoclinic, P2 1 / a, a ‫؍‬ 23.24(1) A > , b ‫؍‬ 13.681(3) A > , c ‫؍‬ 23.37(2) A > , ‫؍‬ 118.17(4)3. [Cu 4 (poap-H) 4 ] (ClO 4 ) 4 ' CH 3 CN ' 4.75H 2 O (6); triclinic, P1 , a ‫؍‬ 13.966(1) A > , b ‫؍‬ 14.195(1) A > , c ‫؍‬ 19.452(2) A > , ‫؍‬ 83.435(2)3, ‫؍‬ 80.727(1)3, ‫؍‬ 63.023(1)3. [Cu 5 (3poap-H) 3 (3poap-3H)] (ClO 4 ) 4 ' 7.5H 2 O (7); triclinic, P 1 , a ‫؍‬ 11.8316(12) A > , b ‫؍‬ 14.7017(16) A > , c ‫؍‬ 21.1527(23) A > , ‫؍‬ 92.401(2)3, ‫؍‬ 104.690(2)3, ‫؍‬ 104.586(2)3. Magnetic properties are interpreted in relation to the structures. The Mn(II) complexes (1, 2) and the Co(II) complexes (4, 5) exhibit intramolecular antiferromagnetic coupling associated with large M+O+M angles, the Cu(II) 4 complex 6 exhibits intramolecular ferromagnetic coupling due to magnetic orbital orthogonality, while the Cu(II) 5 complex 7 is best described as a combination of a ferromagnetic trinuclear subunit and an antiferromagnetic dinuclear subunit. 2001 Academic Press