The assembly, synthesis and properties of a trinuclear cyano-bridged Cu^II–Mo^IV–Cu^II complex

Irradiation Temperature Dependence of the Photomagnetic Mechanisms in a Cyanido-Bridged CuII2MoIV Trinuclear Molecule

“…2.8 Å) between terminal cyanides and copper(II) centers (Figure 1). Selected structural parameters for 1 are listed in Supporting Information, Table In all the assemblies, the coordination sphere of copper(II) is completed either by four nitrogen atoms of two terminal N-bidentate ligands 40,49,55,68,85,86 or one terminal N-tetradentate ligand. 50,52,58,83,84 Analysis of local geometries of copper(II) centers (Supporting Information, Table S3) reveals that trigonal bipyramid geometry is exceptional among trinuclear systems and can be achieved mainly for tripodal ligands tris(2aminoethyl)amine and tris(2-pyridylmethy)amine 52 and bulky bidentate aromatic 2,2′-bipyridine.…”

“…Incorporation of the unexplored linear N - tetradentate enpnen ligand in the synthesis of Cu­(II)–Mo­(IV) systems resulted in the formation of a trinuclear [Cu II (enpnen)] 2 ­[Mo IV (CN) 8 ]·6.75H 2 O molecule ( 1 ). Trinuclear cyanido-bridged Cu 2 Mo molecules are commonly observed among Cu­(II)–Mo­(IV) systems. ,,,,,,,− Such a structural arrangement is favored due to the charge compensation of two [Cu­(L) n ] 2+ ions by [Mo­(CN) 8 ] 4– anion. In all the assemblies, the coordination sphere of copper­(II) is completed either by four nitrogen atoms of two terminal N - bidentate ligands ,,,,, or one terminal N - tetradentate ligand. ,,,, Analysis of local geometries of copper­(II) centers (Supporting Information, Table S3) reveals that trigonal bipyramid geometry is exceptional among trinuclear systems and can be achieved mainly for tripodal ligands tris­(2-aminoethyl)­amine and tris­(2-pyridylmethy)­amine and bulky bidentate aromatic 2,2′-bipyridine. , In other cases copper­(II) adopts intermediate geometry between square pyramid and vacant octahedron with a slight predominance of the first one.…”

Experimental and theoretical insights into the photomagnetic effects in trinuclear and ionic Cu(ii)–Mo(iv) systems

“…Reagents were purchased from commercial sources (Sigma Aldrich, TCI chemicals) and used without further purification. K 4 [Mo IV (CN) 8 ]•2H 2 O salt 61 and reference compounds [Cu II (tn) 2 ] 2 [Mo IV 62 and [Cu II (tren)] 2 [Mo IV (CN) 8 ]•5.25H 2 O (4) 33 were synthesised according to the literature procedures.…”

“…1). 33,62 As a consequence, the self-assembly of Cu(II) ions in the presence of two types of ligands, tren and tn ligands, as well as octacyanidomolybdate(IV) ions gave two complex salts:…”