New Metal Phthalocyanines/Metal Simple Hydroxide Multilayers: Experimental Evidence of Dipolar Field-Driven Magnetic Behavior

Abstract

A series of new hybrid multilayers has been synthesized by insertion-grafting of transition metal (Cu(II), Co(II), Ni(II), and Zn(II)) tetrasulfonato phthalocyanines between layers of Cu(II) and Co(II) simple hydroxides. The structural and spectroscopic investigations confirm the formation of new layered hybrid materials in which the phthalocyanines act as pillars between the inorganic layers. The magnetic investigations show that all copper hydroxide-based compounds behave similarly, presenting an overall antiferromagnetic behavior with no ordering down to 1.8 K. On the contrary, the cobalt hydroxide-based compounds present a ferrimagnetic ordering around 6 K, regardless of the nature of the metal phthalocyanine between the inorganic layers. The latter observation points to strictly dipolar interactions between the inorganic layers. The amplitude of the dipolar field has been evaluated from X-band and Q-band EPR spectroscopy investigation (Bdipolar ≈ 30 mT).

Hybrid interfaces in layered hydroxides: magnetic and multifunctional superstructures by design

“…This shift reflects the evolution of the internal dipole field arising from the increase of the magnetic correlation length within the cobalt layers. [101] Thanks to a precise X-band and Q-band EPR study, the value of a purely dipolar internal field developing in between magnetic Layered Simple Hydroxides was determined from the shift of g between 90 and 5 K: B dipolar ≈ 30 mT. A similar similar feature was also observed in the case of CuPcTS 0 inserted into ferromagnetic NiAl-LDH.…”

Electrocatalytic Properties of Metal Phthalocyanine Tetrasulfonate Intercalated in Metal Layered Simple Hydroxides (Metal: Co, Cu, and Zn)

“…All other reagents were of analytical grade, and all solutions were prepared with deionized water. Cu 2 (OH) 3 (DS), 20 Co 2 (OH) 3 (DS 0 ), 22,25 and MPcTS 0 ⊂M′ (M = Cu, Co and M′ = Cu, Co) 18 were prepared as previously described. CoPcTS 0 ⊂Zn was prepared by a similar procedure.…”

“…17 We have recently described the synthesis, structure, and magnetic properties of a family of LSH-based hybrid materials functionalized by transition-metal tetrasulfonato phthalocyanine ( Figure 1). 18 In the present work, we describe the electrochemical behavior of some members of this family, namely CoPcTS 0 ⊂Co, CoPcTS 0 ⊂Cu, CoPcTS 0 ⊂Zn, CuPcTS 0 ⊂Co, and CuPcTS 0 ⊂Cu, where the notation MPcTS 0 ⊂M′ stands for a M′ (Co, Cu, Zn) layered simple hydroxide functionalized by a tetrasulfonato phthalocyanine coordinating a M 2+ cation (Co, Cu). Their electrochemical behaviors are compared to the ones of the starting compounds Co 2 (OH) 3 (DS 0 ) and Cu 2 (OH) 3 (DS) (DS 0 − is dodecylsulfonate, and DS − is dodecylsulfate).…”

Layered Simple Hydroxides Functionalized by Fluorene‐Phosphonic Acids: Synthesis, Interface Theoretical Insights, and Magnetoelectric Effect

“…Many works about multifunctional hybrids concerned layered bimetallic trioxalatometalates, [20,21] hexathiohypodiphosphates, [22] or magnetic layered double hydroxides, [23] because they can be functionalized with various ligands via versatile reactions. [26][27][28][29][30][31] Whereas various organic molecules and coordination complexes bearing carboxylic or sulfonic acid anchoring functions have been successfully inserted into these layered simple hydroxides (LSH), to the best of our knowledge, phosphonic acid anchoring groups have never been used in such systems. [25] Most of the preceding layered functional materials are characterized by weak bonds between subnetworks, which may limit synergy between properties.…”