Photoswitchable heterotrimetallic chain based on octocyanomolybdate, copper, and nickel : synthesis, characterization, and photomagnetic properties

Jérôme Long (1) , Lise-Marie Chamoreau (1) , Corine Mathonière (2) , Valerie Marvaud (1)

1 CIM2 - Laboratoire de Chimie Inorganique et Matériaux Moléculaires
2 ICMCB - Institut de Chimie de la Matière Condensée de Bordeaux

Taking into account the general interest in photoswitchable nanomagnets, we present an original synthetic route to well-defined photoswitchable heterotrimetallic complexes. Our strategy demonstrates the feasibility of using a “molybdenum−copper” switchable complex with terminal cyanide ligands as relevant synthons for the rational design and synthesis of heterotrimetallic photoswitchable molecular architectures. Starting from a pentanuclear compound based on an octacyanometalated precursor, [Mo^IV(CN)₄(CNCu^II(Me2en)₂)₄]⁴⁺, and a [Ni^II(cyclam)]²⁺ assembling building block, we succeeded in synthesizing a photoswitchable heterotrimetallic chain, denoted as {NiMo₂Cu₇}_n. The compound has been characterized by single-crystal X-ray diffraction, UV−vis and IR spectroscopies, and powder magnetic and photomagnetic susceptibility measurements. Before irradiation, the compound behaves as a paramagnet with eight independent spin carriers (Cu^II d⁹, S = ¹/₂, and Ni^II d⁸, S = 1). After irradiation, a long-lived metastable state persists until relatively high temperature (120 K) and is thermally reversible.

Domaines: Matériaux

Jérôme Long, Lise-Marie Chamoreau, Corine Mathonière, Valerie Marvaud. Photoswitchable heterotrimetallic chain based on octocyanomolybdate, copper, and nickel : synthesis, characterization, and photomagnetic properties. Inorganic Chemistry, 2009, 48 (1), pp.22-24. ⟨10.1021/ic801901j⟩. ⟨hal-00366647⟩